Transportation method of sulfide solid electrolyte

Abstract

This method for transporting a sulfide solid electrolyte comprises: a step for obtaining a powder compact by compressing a powdery sulfide solid electrolyte containing lithium atoms, sulfur atoms, and phosphorus atoms; a step for filling a packaging container with the powder compact to obtain a package; a step for transporting the packaging body; and a step in which the powder compact is taken out from the package and crushed to obtain a crushed product.

Description

Technical Field

[0001] This invention relates to a method for transporting sulfide solid electrolytes. Background Technology

[0002] With the rapid popularization of information-related and communication devices such as personal computers, cameras, and mobile phones in recent years, the development of batteries used as their power source has received much attention. Previously, batteries used in these applications employed electrolytes containing flammable organic solvents. However, by making batteries entirely solid-state, it is possible to eliminate the use of flammable organic solvents within the battery, simplifying safety devices. Furthermore, this approach offers superior manufacturing costs and productivity. Therefore, the development of batteries that replace the electrolyte with a solid electrolyte is underway.

[0003] As a method for transporting solid electrolytes, Patent Document 1 discloses a bundle for protecting thin-plate solid electrolytes.

[0004] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2010-105729 Summary of the Invention The technical problem that the invention aims to solve In the preparation of electrode composites using sulfide solid electrolytes and electrode active materials, sometimes the sulfide solid electrolyte is temporarily manufactured, then transported to another location, where it is mixed with the electrode active material to manufacture the electrode composite. Thus, there are sometimes needs to transport the manufactured sulfide solid electrolyte to other plants, etc.

[0005] However, sulfide solid electrolytes are mostly powders with particle sizes ranging from 0.1 to several micrometers, resulting in large bulk volumes and easy dispersion, thus posing transportation challenges. Furthermore, given the concern that sulfide solid electrolytes may generate hydrogen sulfide upon contact with air and its moisture, suppressing dispersion during transportation is particularly important.

[0006] Considering the properties of sulfide solid electrolytes, the inventors have conducted in-depth research on suitable transportation methods and found that transporting sulfide solid electrolytes by forming them into powder compacts can solve the above-mentioned problems.

[0007] That is, the purpose of this invention is to provide a method for efficiently transporting sulfide solid electrolytes while preventing scattering.

[0008] Solution to the above technical problems The present invention relates to a method for transporting sulfide solid electrolytes, comprising: The process of compressing a powdered sulfide solid electrolyte containing lithium atoms, sulfur atoms and phosphorus atoms to obtain a powder compact. The process of filling the powder compact into a packaging container to obtain the package; The process of transporting the package; The process of removing the powder compact from the packaging and crushing it to obtain the crushed material.

[0009] Invention Effects According to the present invention, a method for efficiently transporting sulfide solid electrolytes while preventing scattering can be provided. Detailed Implementation

[0010] Hereinafter, embodiments of the present invention (hereinafter sometimes referred to as "this embodiment") will be described. Furthermore, in this specification, the upper and lower limits of the numerical ranges referred to by "above," "below," and "~" are values ​​that can be arbitrarily combined, and the values ​​of the embodiments can also be used as the upper and lower limits. Moreover, preferred provisions can be arbitrarily adopted. That is, one preferred provision can be combined with one or more other preferred provisions. It can also be said that the combination of preferred provisions is more preferred.

[0011] (Insights gained by the inventors in completing this invention) In order to solve the above-mentioned technical problems, the inventors conducted in-depth research and discovered the following matters, thereby completing the present invention.

[0012] Patent document 1 relates to a package for protecting a sheet-like solid electrolyte. Although it discloses a method for protecting a sheet-like solid electrolyte from damage or foreign matter adhesion, it does not mention a method for transporting a powdery sulfide solid electrolyte.

[0013] In response, the inventors discovered that by temporarily shaping the powdered sulfide solid electrolyte into a powder compact, filling it into a packaging container to form a package for transportation, and finally crushing it, efficient transportation can be achieved while preventing the sulfide solid electrolyte from scattering, thus completing the present invention.

[0014] (Various methods of implementing this method) The first embodiment of this invention relates to a method for transporting sulfide solid electrolytes, including: The process of compressing a powdered sulfide solid electrolyte containing lithium atoms, sulfur atoms and phosphorus atoms to obtain a powder compact. The process of filling the powder compact into a packaging container to obtain the package; The process of transporting the package; The process of removing the powder compact from the packaging and crushing it to obtain the crushed material.

[0015] Previously, when transporting powdered solid electrolytes, the common method was to directly pack the solid electrolyte into bags or other containers for transport. However, there is a problem that the powdered solid electrolyte is prone to scattering during the processes before and after packing the solid electrolyte into the container.

[0016] Therefore, in order to solve the above problems, the inventors discovered that by temporarily compressing the powdered sulfide solid electrolyte into a powder compact before transportation and then crushing it at the transportation destination, the above problems can be solved.

[0017] The second embodiment relates to a method for transporting sulfide solid electrolytes, which is the same as the method described in the first embodiment. The density of the powder compact is 0.2 g / cm³. 3 above.

[0018] From the viewpoint of suppressing the scattering of sulfide solid electrolytes during transportation and improving transportation efficiency, it is preferable to set the density of the powder compact within the above-mentioned range.

[0019] The third embodiment relates to a method for transporting sulfide solid electrolytes, which, in the first or second embodiment described above, In the process of obtaining the powder compact, the powdered sulfide solid electrolyte is compressed after adding a solvent.

[0020] From the viewpoint of preventing powder scattering during the process of obtaining powder compacts, it is preferable to obtain the powder compacts in a state where a solvent has been added to the powdered sulfide solid electrolyte.

[0021] The fourth embodiment relates to a method for transporting sulfide solid electrolytes, which is one of the methods described in the first to third embodiments above. In the process of obtaining the crushed material, the powder compact is crushed after adding a solvent.

[0022] From the viewpoint of preventing powder scattering during the process of obtaining the crushed material, it is preferable to crush the powder while the powder compact has been coated with a solvent.

[0023] The fifth embodiment relates to a method for transporting sulfide solid electrolytes, which is, in any of the first to fourth embodiments described above, The packaging container comprises one or more bag-like bodies, and at least one of the bag-like bodies is made of a plastic film having a metal film layer.

[0024] From the viewpoint of making it difficult for sulfide solid electrolytes to come into contact with moisture contained in the outside air, containers made of plastic film with low moisture permeability and having a metal film layer are preferred as packaging containers.

[0025] Furthermore, the sixth method of this embodiment relates to a method for transporting sulfide solid electrolytes, which is in any of the first to fifth methods described above. The packaged items are then further wrapped in an outer packaging container before being transported.

[0026] If the packaging container is wrapped with an outer packaging container, it becomes easier to protect the powder compact inside the packaging container from the impact exerted from the outside during transportation.

[0027] Furthermore, the seventh method of this embodiment relates to a method for transporting sulfide solid electrolytes, which is the same as the sixth method described above. The outer packaging container is selected from one or more types of metal cans and plastic containers.

[0028] From the perspective of protecting the inner packaging container, metal cans or plastic containers are preferred as outer packaging containers.

[0029] The eighth embodiment of this invention relates to a sulfide solid electrolyte transport system, which includes: A compression forming device for compressing a powdered sulfide solid electrolyte containing lithium atoms, sulfur atoms and phosphorus atoms to obtain a powder compact; Packaging equipment that fills the powder compact into a packaging container to obtain the package; The transport mechanism that transports the package; And a crushing device for removing the powder compact from the packaging and crushing it to obtain the crushed material.

[0030] The above-described transportation system is a system for realizing the transportation method of the sulfide solid electrolyte of this embodiment.

[0031] The ninth embodiment of this invention relates to a method for manufacturing all-solid-state battery materials, comprising: The process of compressing a powdered sulfide solid electrolyte containing lithium atoms, sulfur atoms and phosphorus atoms to obtain a powder compact. The process of filling the powder compact into a packaging container to obtain the package; The process of transporting the package; The process of removing the powder compact from the packaging and crushing it to obtain the crushed material.

[0032] The tenth embodiment of this invention relates to an all-solid-state battery in which an all-solid-state battery material obtained by the manufacturing method described in the ninth embodiment is contained in a solid electrolyte layer.

[0033] The electrode composite material according to the eleventh aspect of this embodiment is an electrode composite material comprising an all-solid-state battery material and an electrode active material obtained by the manufacturing method according to the ninth aspect described above.

[0034] The all-solid-state battery according to the twelfth aspect of this embodiment is an all-solid-state battery in which at least one of the positive and negative electrodes contains the electrode composite material according to the eleventh aspect described above.

[0035] The above manufacturing method enables the production of all-solid-state battery materials and all-solid-state batteries using them, while suppressing the dispersion of sulfide solid electrolytes.

[0036] The packaging body involved in the thirteenth aspect of this embodiment is a packaging body formed by filling a packaging container with a powder compact obtained by compressing a powdered sulfide solid electrolyte containing lithium atoms, sulfur atoms and phosphorus atoms.

[0037] The aforementioned packaging is designed to facilitate transportation while suppressing the dispersion of sulfide solid electrolytes.

[0038] The fourteenth embodiment involves a packaging body that, in the thirteenth embodiment described above, Further, it includes outer packaging containers.

[0039] From the perspective of protecting the powder compact, it is preferable to have an outer packaging container.

[0040] The fifteenth embodiment of this invention relates to a method for transporting sulfide solid electrolytes, including: The process of compressing a powdered sulfide solid electrolyte containing lithium, sulfur, and phosphorus atoms to obtain a powder compact. The density of the powder compact is 0.2 g / cm³. 3 above.

[0041] The powder compact obtained by compressing the above-mentioned powdered sulfide solid electrolyte has a density within the above range, thus enabling efficient transportation of the sulfide solid electrolyte during transportation while suppressing scattering.

[0042] The sixteenth embodiment of this invention relates to a method for manufacturing all-solid-state battery materials, including: The process of compressing a powdered sulfide solid electrolyte containing lithium, sulfur, and phosphorus atoms to obtain a powder compact. The density of the powder compact is 0.2 g / cm³. 3 above.

[0043] The powder compact obtained by compressing the above-mentioned powdered sulfide solid electrolyte has a density within the above range, thus enabling the efficient manufacture of all-solid-state battery materials while suppressing the dispersion of the sulfide solid electrolyte.

[0044] (Sulfide solid electrolyte) As for the sulfide solid electrolyte that is prepared into a powder compact in the transportation method of this embodiment, any general sulfide solid electrolyte as described below is acceptable, and there are no particular restrictions on its manufacturing method, etc.

[0045] In this specification, "solid electrolyte" refers to an electrolyte that remains solid at 25°C under a nitrogen atmosphere. The sulfide solid electrolyte in this embodiment is a solid electrolyte containing lithium atoms, sulfur atoms, and phosphorus atoms, and having ionic conductivity caused by lithium atoms.

[0046] "Sulfide solid electrolytes" include both amorphous sulfide solid electrolytes and crystalline sulfide solid electrolytes.

[0047] In this specification, "crystalline sulfide solid electrolyte" refers to a sulfide solid electrolyte in which peaks originating from a solid electrolyte are observed in an X-ray diffraction pattern determined by X-ray diffraction, regardless of whether peaks originating from the raw material of the sulfide solid electrolyte are present. That is, a crystalline sulfide solid electrolyte contains a crystal structure originating from a solid electrolyte; this crystal structure may be a part or all of it. Furthermore, as long as a crystalline sulfide solid electrolyte has the X-ray diffraction pattern described above, a portion of it may also contain an amorphous sulfide solid electrolyte. Therefore, crystalline sulfide solid electrolytes include so-called glass-ceramics obtained by heating an amorphous sulfide solid electrolyte to above its crystallization temperature.

[0048] Furthermore, in this specification, "amorphous sulfide solid electrolyte" refers to a halo pattern in which no peaks other than those originating from the raw material are substantially observable in X-ray diffraction measurements, regardless of whether there are peaks originating from the raw material of the sulfide solid electrolyte.

[0049] Examples of crystal structures for the aforementioned crystalline sulfide solid electrolytes include Li3PS4, Li4P2S6, Li7PS6, and Li7P3S6. 11 Crystal structures, crystal structures with peaks near 2θ = 20.2° and 23.6° (e.g., Japanese Patent Application Publication No. 2013-16423), etc., and Li can also be listed as an example. 4-x Ge 1-x P xThe S4 series sulfide crystalline lithium superionic conductor thio-LISICON Region II crystal structure (see Kanno et al., Journal of The Electrochemical Society, 148(7)A742-746(2001)), and Li 4-x Ge 1-x P x The S4 series sulfide crystalline lithium superionic conductor has a similar crystal structure to the thio-LISICON Region II type (see SolidState Ionics, 177 (2006), 2721-2725).

[0050] From the viewpoint of achieving higher ionic conductivity, the crystal structure of the aforementioned crystalline sulfide solid electrolyte is preferably the sulfide crystalline lithium superionic conductor region II crystal structure described above. Here, "sulfide crystalline lithium superionic conductor region II crystal structure" refers to Li... 4-x Ge 1-x P x The S4 series sulfide crystalline lithium superionic conductor has a Region II crystal structure and is similar to Li 4-x Ge 1-x P x Any of the crystal structures similar to the S4-series thio-LISICON Region II type of sulfide crystalline lithium superion conductor.

[0051] The aforementioned crystalline sulfide solid electrolyte may contain the aforementioned sulfide crystalline lithium superionic conductor type II crystal structure, or it may contain the aforementioned sulfide crystalline lithium superionic conductor type II crystal structure as the main crystal. However, from the viewpoint of obtaining higher ionic conductivity, it is preferable to contain it as the main crystal. In this specification, "containing it as the main crystal" means that the proportion of the crystal structure as the target crystal structure in the crystal structure is 80% or more, preferably 90% or more, and more preferably 95% or more. Furthermore, from the viewpoint of obtaining higher ionic conductivity, the aforementioned crystalline sulfide solid electrolyte is preferably free of crystalline Li3PS4 (β-Li3PS4).

[0052] In X-ray diffraction measurements using CuKα rays, the diffraction peaks of the Li3PS4 crystal structure appear, for example, near 2θ = 17.5°, 18.3°, 26.1°, 27.3°, and 30.0°; the diffraction peaks of the Li4P2S6 crystal structure appear, for example, near 2θ = 16.9°, 27.1°, and 32.5°; the diffraction peaks of the Li7PS6 crystal structure appear, for example, near 2θ = 15.3°, 25.2°, 29.6°, and 31.0°; and the diffraction peaks of the Li7P3S... 11 The diffraction peaks of the crystal structure appear, for example, near 2θ = 17.8°, 18.5°, 19.7°, 21.8°, 23.7°, 25.9°, 29.6°, and 30.0°, in Li. 4-x Ge 1-x P x The diffraction peaks of the S4 series sulfide crystalline lithium superionic conductor Region II crystal structure appear, for example, near 2θ = 20.1°, 23.9°, and 29.5°, similar to those of Li. 4-x Ge 1-x P x Diffraction peaks similar to those of the S4-series sulfide crystalline lithium superionic conductor in Region II (thio-LISICON Region II) appear, for example, around 2θ = 20.2° and 23.6°. Furthermore, the positions of these peaks can fluctuate within a range of ±0.5°.

[0053] As the aforementioned crystalline sulfide solid electrolyte, a preferred example is a crystalline sulfide solid electrolyte having a sulfogermanium sulfide crystal structure, which is formed by having the aforementioned Li7PS6 structural framework and replacing a portion of P with Si.

[0054] As a compositional formula for a sulforaphite-germanium type crystal structure, examples can be listed such as those composed of the formula Li. 7-x P 1-y Si y S6 and Li 7+ x P 1-y Si y The crystal structure represented by S6 (x = -0.6 to 0.6, y = 0.1 to 0.6) is cubic or orthorhombic, preferably cubic, and exhibits peaks at 2θ = 15.5°, 18.0°, 25.0°, 30.0°, 31.4°, 45.3°, 47.0°, and 52.0°, as determined by CuKα X-ray diffraction.

[0055] As a compositional formula for the silver-germanium sulfide crystal structure, other examples of compositional formulas include Li. 7-x-2y PS6-x-y Cl x (0.8≤x≤1.7, 0<y≤-0.25x+0.5). The crystal structure of the silver-germanium sulfide type represented by this formula is preferably cubic, and in X-ray diffraction using CuKα rays, it has peaks mainly appearing at positions of 2θ=15.5°, 18.0°, 25.0°, 30.0°, 31.4°, 45.3°, 47.0° and 52.0°.

[0056] Furthermore, as a compositional formula for the silver-germanium sulfide type crystal structure, the compositional formula Li can also be listed. 7-x PS 6-x Ha x (Ha is Cl or Br, and x is preferably 0.2 to 1.8). The crystal structure of the silver-germanium sulfide type represented by this formula is preferably cubic, and in X-ray diffraction using CuKα rays, it has peaks mainly appearing at positions of 2θ = 15.5°, 18.0°, 25.0°, 30.0°, 31.4°, 45.3°, 47.0°, and 52.0°.

[0057] Furthermore, the positions of these peaks can fluctuate within a range of ±0.5°.

[0058] Furthermore, the atomic composition ratio contained in the crystalline sulfide solid electrolyte is preferably a composition ratio corresponding to the composition formulas of the various crystal structures described above. If it is within the range of the atomic composition ratio, then in the above crystal structures, it becomes easier to form a sulfide crystalline lithium superion conductor Region II crystal structure or a sulfide-germanium type crystal structure.

[0059] The aforementioned crystalline sulfide solid electrolyte may contain one or more complexing agents and solvents selected during manufacturing.

[0060] The total content of complexing agent and solvent contained in the crystalline sulfide solid electrolyte is preferably 0% by mass, but from the viewpoint of efficiently obtaining a sulfide solid electrolyte with high ionic conductivity, it is usually 10% by mass or less, preferably 8% by mass or less, more preferably 5% by mass or less, further preferably 3.0% by mass or less, and particularly preferably 1.0% by mass or less.

[0061] The aforementioned sulfide solid electrolytes contain lithium atoms, sulfur atoms, and phosphorus atoms, preferably lithium atoms, sulfur atoms, phosphorus atoms, and halogen atoms. As representative examples, solid electrolytes composed of lithium sulfide and phosphorus sulfide, such as Li2S-P2S5, are preferably listed; solid electrolytes composed of lithium sulfide, phosphorus sulfide, and lithium halide, such as Li2S-P2S5-LiI, Li2S-P2S5-LiCl, Li2S-P2S5-LiBr, and Li2S-P2S5-LiI-LiBr; and solid electrolytes containing other atoms such as oxygen atoms and silicon atoms, such as Li2S-P2S5-Li2O-LiI and Li2S-SiS2-P2S5-LiI. From the viewpoint of obtaining higher ionic conductivity, solid electrolytes composed of lithium sulfide, phosphorus sulfide and lithium halide, such as Li2S-P2S5-LiI, Li2S-P2S5-LiCl, Li2S-P2S5-LiBr, and Li2S-P2S5-LiI-LiBr, are preferred, and solid electrolytes composed of lithium sulfide, phosphorus sulfide and two kinds of lithium halide, such as Li2S-P2S5-LiI-LiBr, are even more preferred.

[0062] The types of atoms that make up sulfide solid electrolytes can be identified, for example, by using an ICP-based luminescence spectrophotometer.

[0063] In the sulfide solid electrolyte (amorphous sulfide solid electrolyte and crystalline sulfide solid electrolyte), the molar ratio of lithium atoms, phosphorus atoms, sulfur atoms and halogen atoms is preferably 1.0-1.8:0.1-0.8:1.0-2.0:0.01-0.6, more preferably 1.1-1.7:0.2-0.6:1.2-1.8:0.05-0.5, and even more preferably 1.2-1.6:0.25-0.5:1.3-1.7:0.08-0.4. Furthermore, as halogen atoms, when bromine and iodine, or bromine and chlorine are used together, the composition ratio (molar ratio) of lithium atoms, phosphorus atoms, sulfur atoms, bromine and iodine (or chlorine) is preferably 1.0-1.8:0.1-0.8:1.0-2.0:0.01-0.3:0.01-0.3, more preferably 1.1-1.7:0.2-0.6:1.2-1.8:0.02-0.25:0.02-0.25, even more preferably 1.2-1.6:0.25-0.5:1.3-1.7:0.03-0.2:0.03-0.2, and even more preferably 1.35-1.45:0.3-0.45:1.4-1.7:0.04-0.18:0.04-0.18.

[0064] By setting the composition ratio (molar ratio) of lithium atoms, sulfur atoms, phosphorus atoms and halogen atoms within the above range, it is easy to create a solid electrolyte with higher ionic conductivity, which has the crystal structure described later, especially the sulfide crystalline lithium superionic conductor Region II crystal structure or the sulfide silver germanite type crystal structure.

[0065] The average particle size (D) of powdered sulfide solid electrolytes 50 For example, it is preferred to be 0.01 μm or more, more preferably 0.03 μm or more, even more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, and further preferably 200.0 μm or less, more preferably 100.0 μm or less, even more preferably 10.0 μm or less, particularly preferably 5.0 μm or less, and most preferably 1.0 μm or less.

[0066] [Transportation methods for sulfide solid electrolytes] The method for transporting the sulfide solid electrolyte of this embodiment includes: The process of compressing a powdered sulfide solid electrolyte containing lithium atoms, sulfur atoms and phosphorus atoms to obtain a powder compact. The process of filling the powder compact into a packaging container to obtain the package; The process of transporting the package; The process of removing the powder compact from the packaging and crushing it to obtain the crushed material.

[0067] In addition, another embodiment of the method for transporting sulfide solid electrolytes includes: The process of compressing a powdered sulfide solid electrolyte containing lithium, sulfur, and phosphorus atoms to obtain a powder compact. The density of the powder compact is 0.2 g / cm³. 3 above.

[0068] The method for transporting the sulfide solid electrolyte according to another embodiment described above includes a process of obtaining a powder compact. As long as the density of the obtained powder compact is within the above range, there are no particular restrictions on subsequent processes. However, from the viewpoint of better utilizing the effect of this embodiment, it is preferable to include the process of obtaining a package, the process of transporting, and the process of obtaining broken pieces, which will be described later.

[0069] [The process of obtaining powder compacts] The transportation method of this embodiment includes a process of compressing a powdered sulfide solid electrolyte containing lithium atoms, sulfur atoms and phosphorus atoms to obtain a powder compact.

[0070] The process of obtaining the powder compact is carried out in a compression molding machine.

[0071] Methods for compressing powdered sulfide solid electrolytes include: placing the sulfide solid electrolyte into a mold with a recess of a specified shape and pressing it to granulate it into a particle shape; or using a roller compactor to place the sulfide solid electrolyte between two rotating rollers for pressing, and further crushing it into flakes as needed.

[0072] The temperature for compaction using a roller compactor is typically 20–60°C, and the pressure is typically 0.1–1 ton per 1 cm of roller width.

[0073] In the process of obtaining the powder compact, it is also possible to compress the powdered sulfide solid electrolyte after adding a solvent.

[0074] As solvents, solvents that have been used in the manufacture of solid electrolytes can be widely used, such as aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, aromatic hydrocarbon solvents, and compounds containing halogen atoms such as nitrogen atoms, oxygen atoms, and chlorine atoms, and heteroatoms such as sulfur atoms.

[0075] The amount of solvent added is based on the total amount of sulfide solid electrolyte, preferably 1.0 to 20% by mass, more preferably 3.0 to 15% by mass, and even more preferably 5.0 to 12% by mass. If the amount of solvent added relative to the sulfide solid electrolyte is 1.0% by mass or more, it is preferred from the viewpoint of preventing powder scattering during the process of obtaining the powder compact; if it is 20% by mass or less, the solvent is unlikely to seep out from the sulfide solid electrolyte during the process of obtaining the powder compact, and therefore it is preferred.

[0076] The size of the powder compact is not particularly limited, but the maximum diameter or length is preferably 0.1 to 100 mm, more preferably 0.5 to 50 mm. In addition, the shape of the powder compact is not particularly limited, and it can be cylindrical, elliptical, triangular prism, cylindrical, cuboid, cubic, elliptical, spherical, lens-shaped, sheet-like, etc.

[0077] Furthermore, the density of the powder compact is not particularly limited, but is preferably 0.2 g / cm³. 3 More preferably, it is 0.4–1.6 g / cm³. 3 More preferably, it is 0.8–1.5 g / cm³. 3 If the density of the powder compact is 0.2 g / cm³ 3 The above methods can effectively suppress the dispersion of sulfide solid electrolytes and improve transportation efficiency. On the other hand, if the density of the powder compact is 1.6 g / cm³... 3 In the following cases, the powder compact becomes easier to break.

[0078] [The process of obtaining the package] The transportation method of this embodiment includes the process of filling the powder compact into a packaging container to obtain a package.

[0079] The process of obtaining the packaged product is carried out in packaging equipment.

[0080] Any container can be used as the packaging container, such as bags, cans, bottles, etc.

[0081] Furthermore, from the viewpoint of making it difficult for the sulfide solid electrolyte to come into contact with moisture contained in the outside air, the material of the packaging container is preferably a material with low moisture permeability. Specifically, it is preferably a material selected from metal, glass, and plastic. In addition, when the packaging container is a bag made of plastic film, it is preferably made of plastic film having a metal film layer.

[0082] In addition, two or more of the above-mentioned packaging containers can be combined.

[0083] As the packaging container, more specifically, from the viewpoint of operability when taking out the powder compact from the process of obtaining the broken material described later, it is preferable to have one or more bag-shaped bodies, and at least one of the bag-shaped bodies is preferably made of a plastic film having a metal film layer.

[0084] From the viewpoint of protecting the contents during transportation, it is preferable to further wrap the package with an outer packaging container before transportation.

[0085] The outer packaging container can be a single unit or a combination of multiple units.

[0086] Furthermore, as the outer packaging container, metal cans and plastic containers are preferably selected.

[0087] Furthermore, by filling the interior of the outer packaging container with air or an inert gas and pressurizing it, the intrusion of moisture from the outside can be suppressed. Nitrogen is an example of such an inert gas.

[0088] More specifically, the packaging body is preferably a packaging body having the following (1) to (3) configurations.

[0089] (1) A package in which a powder compact is bundled with a packaging container having one or more bag-like bodies and further bundled with an outer packaging container selected from one or more metal cans and plastic containers.

[0090] (2) A package containing a powder compact wrapped in a packaging container having multiple bag-like bodies, at least one of which is made of a plastic film having a metal film layer, and further wrapped in an outer packaging container selected from one or more metal cans and plastic containers.

[0091] (3) The powder compact is bundled in a packaging container with multiple bag-shaped bodies, at least one of which is made of a plastic film with a metal film layer, and further bundled in a plastic container, and then further bundled in a metal can.

[0092] [Transportation process] The transportation method of this embodiment includes the process of transporting the package.

[0093] The process of transporting the aforementioned packages is carried out by a transportation agency.

[0094] The transport mechanism is the mechanism that transports the packaged goods from the packaging equipment to the crushing equipment described later. The transport mechanism is not particularly limited; for example, one or more types can be selected from manpower, vehicles, ships, and aircraft, or a combination of multiple types can be used. Specific examples of vehicles include not only automobiles such as trucks, but also railway vehicles.

[0095] [The process of obtaining crushed material] The transportation method of this embodiment includes the process of removing the powder compact from the package and crushing it to obtain the crushed material.

[0096] The process of obtaining the crushed material is carried out by crushing equipment.

[0097] As a crushing device, there are no particular restrictions as long as the device can crush the powder compact and restore it to powder form; for example, a pulverizer can be used.

[0098] Specific examples of pulverizers include dry pulverizers and wet pulverizers. Furthermore, dry or wet media pulverizers that utilize pulverizing media are preferred. When pulverizing powder in a state where solvent has been added to the powder compact, a wet pulverizer capable of handling wet pulverization is preferred.

[0099] The solvent used here can be the same solvent used in the process of obtaining the powder compact described above.

[0100] Examples of dry pulverizers include dry bead mills, dry ball mills, dry vibratory mills, and other dry media pulverizers, as well as air jet mills and other dry media-free pulverizers.

[0101] Examples of wet pulverizers include wet bead mills, wet ball mills, and wet vibratory mills. From the viewpoint that the pulverizing conditions can be freely adjusted and that it is easy to handle smaller particle sizes, a wet bead mill that uses beads as the pulverizing medium is preferred.

[0102] In addition, as mentioned above, there are machines that can use ultrasound to crush objects, such as those called ultrasonic pulverizers, ultrasonic homogenizers, probe-type ultrasonic pulverizers, etc.

[0103] The process of obtaining the crushed material described above can be carried out as a standalone crushing process, or it can be carried out simultaneously with the mixing of sulfide solid electrolyte and other materials.

[0104] Other materials include, for example, electrode active materials, conductive materials, and binders.

[0105] As electrode active materials, positive electrode active materials and negative electrode active materials are used respectively, depending on whether the electrode composite material is used for the positive electrode or the negative electrode.

[0106] As a positive electrode active material, any material that can promote the battery chemical reaction accompanying the movement of lithium ions in relation to the negative electrode active material can be used without particular restrictions. The lithium ions are derived from atoms that exhibit ionic conductivity, preferably lithium atoms. Examples of positive electrode active materials capable of lithium ion insertion and extraction include oxide-based positive electrode active materials and sulfide-based positive electrode active materials.

[0107] As oxide-based positive electrode active materials, preferred examples include lithium-containing transition metal composite oxides such as LMO (lithium manganese oxide), LCO (lithium cobalt oxide), NMC (lithium nickel manganese cobalt oxide), NCA (lithium nickel cobalt aluminum oxide), LNCO (lithium nickel cobalt oxide), and olivine-type compounds (LiMeNPO4, Me=Fe, Co, Ni, Mn).

[0108] Examples of sulfide-based positive electrode active materials include titanium sulfide (TiS2), molybdenum sulfide (MoS2), iron sulfide (FeS, FeS2), copper sulfide (CuS), and nickel sulfide (Ni3S2).

[0109] In addition to the aforementioned positive electrode active materials, niobium selenide (NbSe3) and other materials can also be used.

[0110] A single positive electrode active material can be used alone, or multiple materials can be used in combination.

[0111] As a negative electrode active material, any material capable of promoting the battery chemical reaction accompanying the movement of lithium ions can be used without particular restriction. The lithium ions originate from atoms that exhibit ionic conductivity, preferably lithium atoms from metals capable of forming alloys with lithium atoms, their oxides, or alloys of such metals and lithium atoms. As such a negative electrode active material capable of lithium ion insertion and extraction, materials known in the battery field as negative electrode active materials can be used without restriction.

[0112] Examples of such negative electrode active materials include lithium metal, or metals such as indium metal, aluminum metal, silicon metal, and tin metal that can form alloys with lithium metal, oxides of these metals, and alloys of these metals with lithium metal.

[0113] The electrode active material used in this embodiment can also be a material with a coating layer on its surface.

[0114] Materials forming the coating layer include nitrides, oxides, or complexes thereof that exhibit ionic conductivity in sulfide solid electrolytes, preferably lithium atoms. Specifically, lithium nitride (Li3N) and materials with a Li4GeO4-based structure, such as Li... 4-2x Zn x Conductors with a crystalline lithium superionic conductor-type crystal structure, such as GeO4; conductors with a Li3PO4-type framework structure, such as Li 4-x Ge 1-x P x S4 and other conductors with a sulfide-crystalline lithium superionic conductor-type crystal structure; La 2 / 3-x Li 3x Conductors such as TiO3 with perovskite-type crystal structure; conductors such as LiTi2(PO4)3 with sodium fast ion conductor (NASICON)-type crystal structure, etc.

[0115] In addition, Li can be listed y Ti 3-y O4 (0 < y < 3), Li4Ti5O 12 Lithium titanate (LTO), lithium metal oxides such as LiNbO3 and LiTaO3 belonging to Group 5 of the periodic table, and oxide conductors such as Li2O-B2O3-P2O5, Li2O-B2O3-ZnO, and Li2O-Al2O3-SiO2-P2O5-TiO2 systems.

[0116] Electrode active materials with a coating can be obtained, for example, by attaching a solution containing various atoms constituting the coating forming material to the surface of the electrode active material, and preferably by firing the attached electrode active material at a temperature of 200°C to 400°C.

[0117] Here, as a solution containing various atoms, a solution containing alkoxides of various metals such as lithium ethoxide, titanium isopropoxide, niobium isopropoxide, and tantalum isopropoxide can be used. In this case, as a solvent, alcohol solvents such as ethanol and butanol, aliphatic hydrocarbon solvents such as hexane, heptane, and octane, and aromatic hydrocarbon solvents such as benzene, toluene, and xylene can be used.

[0118] In addition, the above-mentioned adhesion can be achieved through dipping, spraying, etc.

[0119] From the viewpoint of improving manufacturing efficiency and battery performance, the firing temperature is preferably 200°C to 400°C, more preferably 250°C to 390°C. The firing time is usually about 1 minute to 10 hours, preferably 10 minutes to 4 hours.

[0120] The coating coverage rate, based on the surface area of ​​the electrode active material, is preferably 90% or more, more preferably 95% or more, and even more preferably 100%, meaning the entire surface is preferably covered. Furthermore, the thickness of the coating layer is preferably 1 nm or more, more preferably 2 nm or more, and preferably 30 nm or less, more preferably 25 nm or less, as an upper limit.

[0121] The thickness of the coating layer can be measured by cross-sectional observation using a transmission electron microscope (TEM), and the coating efficiency can be calculated based on the coating layer thickness, elemental analysis values, and BET specific surface area.

[0122] From the perspective of improving battery performance by enhancing electronic conductivity, carbon-based materials such as artificial graphite, graphite carbon fiber, resin-calcined carbon, thermally decomposed vapor-grown carbon, coke, mesophase carbon microspheres, furfuryl alcohol resin-calcined carbon, polyphenylene oxide, pitch-based carbon fiber, vapor-grown carbon fiber, natural graphite, and difficult-to-graphitize carbon can be listed.

[0123] By using the binder, the strength during the fabrication of the positive and negative electrodes can be improved.

[0124] As an adhesive, there are no particular limitations as long as it can impart functions such as adhesion and flexibility. For example, fluorinated polymers such as polytetrafluoroethylene and polyvinylidene fluoride, thermoplastic elastomers such as butene rubber and styrene-butadiene rubber, and various resins such as acrylic resin, acrylic polyol resin, polyvinyl alcohol acetal resin, polyvinyl alcohol butyral resin, and silicone resin can be listed.

[0125] In the electrode composite material, the mixing ratio (mass ratio) of the electrode active material and the sulfide solid electrolyte is preferably 99.5:0.5 to 40:60, more preferably 99:1 to 50:50, and even more preferably 98:2 to 60:40, taking into account the improvement of battery performance and manufacturing efficiency.

[0126] When conductive materials are present, there is no particular limitation on the content of conductive materials in the electrode composite material. However, considering the improvement of battery performance and manufacturing efficiency, it is preferable to have 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 1.5% by mass or more, and preferably 10% by mass or less as an upper limit, more preferably 8% by mass or less, and even more preferably 5% by mass or less.

[0127] Furthermore, when a binder is present, there is no particular limitation on the binder content in the electrode composite material. However, considering the improvement of battery performance and manufacturing efficiency, it is preferable to have 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, and preferably 20% by mass or less as an upper limit, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

[0128] [Transportation system for sulfide solid electrolytes] The sulfide solid electrolyte transport system of this embodiment includes: A compression forming device for compressing a powdered sulfide solid electrolyte containing lithium atoms, sulfur atoms and phosphorus atoms to obtain a powder compact; Packaging equipment that fills the powder compact into a packaging container to obtain the package; The transport mechanism that transports the package; And a crushing device for removing the powder compact from the packaging and crushing it to obtain the crushed material.

[0129] The details of the compression molding equipment, packaging equipment, transportation mechanism, and crushing equipment are the same as those described in the description of the transportation method of the sulfide solid electrolyte of this embodiment.

[0130] [Manufacturing Methods for All-Solid-State Battery Materials] The method for manufacturing the all-solid-state battery material according to this embodiment includes: The process of compressing a powdered sulfide solid electrolyte containing lithium atoms, sulfur atoms and phosphorus atoms to obtain a powder compact. The process of filling the powder compact into a packaging container to obtain the package; The process of transporting the package; The process of removing the powder compact from the packaging and crushing it to obtain the crushed material.

[0131] In addition, another embodiment of the method for manufacturing an all-solid-state battery material includes: The process of compressing a powdered sulfide solid electrolyte containing lithium, sulfur, and phosphorus atoms to obtain a powder compact. The density of the powder compact is 0.2 g / cm³. 3 above.

[0132] The manufacturing method of the all-solid-state battery material in another embodiment described above includes a process of obtaining a powder compact. As long as the density of the obtained powder compact is within the above range, there are no particular restrictions on subsequent processes. However, from the viewpoint of better realizing the effect of this embodiment, it is preferable to include a process of obtaining a packaging body, a transportation process, and a process of obtaining crushed material.

[0133] The details of the processes for obtaining the powder compact, obtaining the package, transporting the powder, and obtaining the crushed material are the same as those described in the method for transporting the sulfide solid electrolyte of this embodiment.

[0134] The all-solid-state battery material obtained by the manufacturing method of this embodiment refers to the crushed material obtained in the crushing process, namely, the sulfide solid electrolyte itself. Therefore, the details of the all-solid-state battery material are the same as those described regarding the sulfide solid electrolyte.

[0135] [Electrode Composite Material] The electrode composite material of this embodiment, It includes an all-solid-state battery material and an electrode active material obtained by the manufacturing method of the all-solid-state battery material.

[0136] The details of the electrode active material are the same as those described regarding the transportation method of the sulfide solid electrolyte of this embodiment.

[0137] [All-solid-state battery] The all-solid-state battery of this embodiment, A battery in which the solid electrolyte layer contains an all-solid-state battery material obtained by the manufacturing method of the all-solid-state battery material, or It is a battery in which the electrode composite material is included in at least one of the positive and negative electrodes.

[0138] [Packaging] The packaging body of this embodiment, It is made by filling a packaging container with a powder compact obtained by compressing a powdered sulfide solid electrolyte containing lithium atoms, sulfur atoms and phosphorus atoms.

[0139] From the viewpoint of protecting the powder compact, the packaging body of this embodiment preferably further includes an outer packaging container.

[0140] The details of the sulfide solid electrolyte, powder compact, packaging container, and outer packaging container are the same as those described in the description of the transportation method of the sulfide solid electrolyte of this embodiment.

[0141] Industrial applicability According to the transportation method of this embodiment, sulfide solid electrolytes can be transported efficiently while preventing scattering. These sulfide solid electrolytes are suitable for batteries used in information-related devices or communication devices such as personal computers, cameras, and mobile phones, as well as for vehicle applications.

Claims

1. A method for transporting a sulfide solid electrolyte, characterized in that, include: The process of compressing a powdered sulfide solid electrolyte containing lithium atoms, sulfur atoms and phosphorus atoms to obtain a powder compact. The process of filling the powder compact into a packaging container to obtain the package; The process of transporting the package; The process of removing the powder compact from the packaging and crushing it to obtain the crushed material.

2. The method for transporting sulfide solid electrolytes as described in claim 1, characterized in that, The density of the powder compact is 0.2 g / cm³. 3 above.

3. The method for transporting sulfide solid electrolytes as described in claim 1 or 2, characterized in that, In the process of obtaining the powder compact, the powdered sulfide solid electrolyte is compressed after adding a solvent.

4. The method for transporting the sulfide solid electrolyte according to any one of claims 1 to 3, characterized in that, In the process of obtaining the crushed material, the powder compact is crushed after adding a solvent.

5. The method for transporting the sulfide solid electrolyte according to any one of claims 1 to 4, characterized in that, The packaging container has one or more bag-like bodies, and at least one of the bag-like bodies is made of a plastic film having a metal film layer.

6. The method for transporting the sulfide solid electrolyte according to any one of claims 1 to 5, characterized in that, The packaged items are then further wrapped in an outer packaging container before being transported.

7. The method for transporting sulfide solid electrolytes as described in claim 6, characterized in that, The outer packaging container is selected from one or more types of metal cans and plastic containers.

8. A transport system for a sulfide solid electrolyte, characterized in that, include: A compression forming device for compressing a powdered sulfide solid electrolyte containing lithium atoms, sulfur atoms and phosphorus atoms to obtain a powder compact; Packaging equipment that fills the powder compact into a packaging container to obtain the package; The transport mechanism that transports the package; And a crushing device for removing the powder compact from the packaging and crushing it to obtain the crushed material.

9. A method for manufacturing an all-solid-state battery material, characterized in that, include: The process of compressing a powdered sulfide solid electrolyte containing lithium atoms, sulfur atoms and phosphorus atoms to obtain a powder compact. The process of filling the powder compact into a packaging container to obtain the package; The process of transporting the package; The process of removing the powder compact from the packaging and crushing it to obtain the crushed material.

10. An all-solid-state battery, characterized in that, The solid electrolyte layer contains an all-solid-state battery material obtained by the manufacturing method of the all-solid-state battery material as described in claim 9.

11. An electrode composite material, characterized in that, It includes an all-solid-state battery material and an electrode active material obtained by the manufacturing method of the all-solid-state battery material according to claim 9.

12. An all-solid-state battery, characterized in that, The electrode composite material of claim 11 is included in at least one of the positive and negative electrodes.

13. A packaging body, characterized in that, It is made by filling a packaging container with a powder compact obtained by compressing a powdered sulfide solid electrolyte containing lithium atoms, sulfur atoms and phosphorus atoms.

14. The packaging body as described in claim 13, characterized in that, Further, it includes outer packaging containers.

15. A method for transporting a sulfide solid electrolyte, characterized in that, include: The process of compressing a powdered sulfide solid electrolyte containing lithium, sulfur, and phosphorus atoms to obtain a powder compact. The density of the powder compact is 0.2 g / cm³. 3 above.

16. A method for manufacturing an all-solid-state battery material, characterized in that, include: The process of compressing a powdered sulfide solid electrolyte containing lithium, sulfur, and phosphorus atoms to obtain a powder compact. The density of the powder compact is 0.2 g / cm³. 3 above.