Method for conveying sulfide solid electrolyte

Abstract

This method for conveying a sulfide solid electrolyte comprises: a step for obtaining a green compact by compressing a pulverulent sulfide solid electrolyte containing a lithium atom, a sulfur atom and a phosphorus atom; a step for filling a packaging container with the green compact to obtain packaged article; a step for conveying the packaged article; and a step of taking out the green compact from the packaged article and crushing the green compact to obtain a crushed product.

Description

Method for transporting sulfide solid electrolyte

[0001] The present invention relates to a method for transporting a sulfide solid electrolyte.

[0002] With the recent rapid spread of information-related devices and communication devices such as personal computers, video cameras, and mobile phones, the development of batteries to be used as their power sources has become important. Conventionally, batteries used for such applications have used electrolytes containing flammable organic solvents, but by making batteries all-solid-state, flammable organic solvents are not used in the battery, safety devices can be simplified, and manufacturing costs and productivity are excellent. Therefore, development is being carried out on batteries in which the electrolyte is replaced with a solid electrolyte.

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

[0004] JP 2010-105729 A

[0005] When preparing an electrode composite from a sulfide solid electrolyte and an electrode active material, the sulfide solid electrolyte may be first produced, transported to another location, and then mixed with the electrode active material to produce the electrode composite. In this way, after the sulfide solid electrolyte is produced, it may be necessary to transport it to another factory or the like. However, sulfide solid electrolytes are often in the form of powders with particle sizes of approximately 0.1 to several microns, which are bulky and prone to scattering, making them difficult to transport. Furthermore, sulfide solid electrolytes may generate hydrogen sulfide upon contact with air and the moisture contained therein, so it is particularly important to prevent scattering during transportation. The inventors, taking into consideration the properties of sulfide solid electrolytes, have been diligently developing a suitable transportation method for them and have found that this problem can be solved by compacting the sulfide solid electrolyte and then transporting it. That is, an object of the present invention is to provide a method for efficiently transporting a sulfide solid electrolyte while preventing scattering.

[0006] A method for transporting a sulfide solid electrolyte according to the present invention includes the steps of compressing a powdered sulfide solid electrolyte containing lithium atoms, sulfur atoms, and phosphorus atoms to obtain a green compact; filling the green compact into a packaging container to obtain a package; transporting the package; and removing the green compact from the packaging and crushing it to obtain a crushed product.

[0007] According to the present invention, a method for efficiently transporting a sulfide solid electrolyte while preventing scattering can be provided.

[0008] Hereinafter, an embodiment of the present invention (hereinafter, sometimes referred to as "the present embodiment") will be described. In this specification, the upper and lower limit values ​​of a numerical range expressed as "greater than or equal to," "less than or equal to," and "to" can be arbitrarily combined, and the numerical values ​​of the examples can also be used as the upper and lower limit values. Furthermore, preferred specifications can be arbitrarily adopted. In other words, one preferred specification can be adopted in combination with one or more other preferred specifications. It can be said that a combination of preferred items is more preferable.

[0009] (Findings Obtained by the Inventors to Achieve the Present Invention) The present inventors have conducted extensive research to solve the above-mentioned problems, and as a result have found the following, which has led to the completion of the present invention.

[0010]

[0006] Patent Literature 1 relates to a packaging body for protecting a thin-plate solid electrolyte, and discloses a method for protecting a solid electrolyte formed into a thin plate from damage or adhesion of foreign matter, but does not mention a method for transporting a powdered sulfide solid electrolyte. In response to this, the present inventors discovered that by first forming a powdered sulfide solid electrolyte into a compact, filling it into a packaging container to form a package, transporting it, and finally crushing it, it is possible to efficiently transport the sulfide solid electrolyte while preventing it from scattering, and thus completed the present invention.

[0011] (Regarding various aspects of the present embodiment) A method for transporting a sulfide solid electrolyte according to a first aspect of the present embodiment is a method for transporting a sulfide solid electrolyte, comprising: compressing a powdered sulfide solid electrolyte containing lithium atoms, sulfur atoms, and phosphorus atoms to obtain a green compact; filling the green compact into a packaging container to obtain a package; transporting the package; and removing the green compact from the packaging and crushing it to obtain a crushed product.

[0012] In the past, a powdered solid electrolyte was generally transported by directly placing the solid electrolyte in a container such as a bag. However, there was a problem in that the powdered solid electrolyte was prone to scattering during the process of placing the solid electrolyte in the container and during the process after removing the solid electrolyte from the container. In order to solve this problem, the present inventors discovered that the above problem could be solved by a method in which the powdered sulfide solid electrolyte is first compressed into a green compact, which is then transported and crushed at the destination.

[0013] A second aspect of the present embodiment provides a sulfide solid electrolyte transport method according to the first aspect, wherein the density of the powder compact is 0.2 g / cm ３ That's all.

[0014] From the viewpoint of preventing scattering of the sulfide solid electrolyte during transportation and improving the efficiency of transportation, it is preferable that the density of the green compact be within the above range.

[0015] A method for transporting a sulfide solid electrolyte according to a third aspect of the present embodiment is the same as the first or second aspect, except that in the step of obtaining the powder compact, a solvent is added to the powdered sulfide solid electrolyte and then compressed.

[0016] It is preferable to obtain a powder compact in a state where a solvent is added to the powdered sulfide solid electrolyte from the viewpoint of preventing scattering of the powder in the step of obtaining the powder compact.

[0017] A fourth aspect of the present embodiment is a method for transporting a sulfide solid electrolyte according to any one of the first to third aspects, wherein in the step of obtaining the crushed product, a solvent is added to the powder compact and then crushed.

[0018] It is preferable to crush the powder compact in a state where a solvent is added, from the viewpoint of preventing the powder from scattering in the step of obtaining the crushed product.

[0019] A fifth aspect of the present embodiment is a method for transporting a sulfide solid electrolyte according to any one of the first to fourth aspects, wherein the packaging container includes one or more bag-shaped bodies, and at least one of the bag-shaped bodies is made of a plastic film provided with a metal thin film layer.

[0020] It is preferable to use a packaging container made of a plastic film with low moisture permeability and provided with a metal thin film layer, from the viewpoint of making it difficult for the sulfide solid electrolyte to come into contact with moisture contained in the outside air.

[0021] A sixth aspect of the present embodiment is a method for transporting a sulfide solid electrolyte according to any one of the first to fifth aspects, wherein the package is further packed in an outer container before being transported.

[0022] When the packaging container is packed in an outer container, the powder compact inside the packaging container can be more easily protected from external impacts during transportation.

[0023] A seventh aspect of the present embodiment is the method for transporting a sulfide solid electrolyte according to the sixth aspect, wherein the outer container is one or more selected from a metal can and a plastic container.

[0024] As the outer container, a metal can or a plastic container is preferred from the viewpoint of protecting the internal packaging container.

[0025] A sulfide solid electrolyte transport system according to an eighth aspect of the present embodiment includes compression molding equipment that compresses a powdered sulfide solid electrolyte containing lithium atoms, sulfur atoms, and phosphorus atoms to obtain a green compact; packaging equipment that fills a packaging container with the green compact to obtain a package; transport means that transports the package; and crushing equipment that removes the green compact from the package and crushes it to obtain a crushed product.

[0026] The above-mentioned transport system realizes the above-mentioned method for transporting a sulfide solid electrolyte according to this embodiment.

[0027] A method for producing an all-solid-state battery material according to a ninth aspect of the present embodiment includes the steps of compressing a powdered sulfide solid electrolyte containing lithium atoms, sulfur atoms, and phosphorus atoms to obtain a green compact; filling the green compact into a packaging container to obtain a package; transporting the package; and removing the green compact from the packaging and crushing it to obtain a crushed product.

[0028] An all-solid-state battery according to a tenth aspect of this embodiment includes an all-solid-state battery material obtained by the manufacturing method according to the ninth aspect in a solid electrolyte layer. An electrode composite according to an eleventh aspect of this embodiment includes an all-solid-state battery material obtained by the manufacturing method according to the ninth aspect and an electrode active material. An all-solid-state battery according to a twelfth aspect of this embodiment includes an electrode composite according to the eleventh aspect in at least one of a positive electrode and a negative electrode.

[0029] The above-described manufacturing method makes it possible to manufacture an all-solid-state battery material and an all-solid-state battery using the same while suppressing scattering of the sulfide solid electrolyte.

[0030] A packaging body according to a thirteenth aspect of the present embodiment is obtained by filling a packaging container with a compact obtained by compressing a powdered sulfide solid electrolyte containing lithium atoms, sulfur atoms, and phosphorus atoms.

[0031] The packaging enables transportation while preventing scattering of the sulfide solid electrolyte.

[0032] A package according to a fourteenth aspect of the present embodiment is the package of the thirteenth aspect, further comprising an outer container. Providing an outer container is preferable from the viewpoint of protecting the powder compact.

[0033] A method for transporting a sulfide solid electrolyte according to a fifteenth aspect of the present embodiment includes a step of compressing a powdered sulfide solid electrolyte containing lithium atoms, sulfur atoms, and phosphorus atoms to obtain a green compact, and the green compact has a density of 0.2 g / cm. ３ That's all.

[0034] When the density of the green compact obtained by compressing the powdered sulfide solid electrolyte is within the above range, the sulfide solid electrolyte can be efficiently transported while being prevented from scattering during transportation.

[0035] A method for producing an all-solid-state battery material according to a sixteenth aspect of the present embodiment includes a step of compressing a powdered sulfide solid electrolyte containing lithium atoms, sulfur atoms, and phosphorus atoms to obtain a green compact, and a density of the green compact is 0.2 g / cm. ３ That's all.

[0036] The green compact obtained by compressing the powdered sulfide solid electrolyte has a density within the above range, which makes it possible to efficiently produce an all-solid-state battery material while suppressing scattering of the sulfide solid electrolyte.

[0037] (Sulfide Solid Electrolyte) The sulfide solid electrolyte to be compacted in the conveying method of this embodiment may be a general sulfide solid electrolyte as described below, and its manufacturing method, etc., are not particularly limited. In this specification, the term "solid electrolyte" refers to an electrolyte that remains solid at 25°C under a nitrogen atmosphere. The sulfide solid electrolyte of this embodiment is a solid electrolyte that contains lithium atoms, sulfur atoms, and phosphorus atoms and has ionic conductivity due to the lithium atoms.

[0038] The term "sulfide solid electrolyte" includes both amorphous sulfide solid electrolytes and crystalline sulfide solid electrolytes. In this specification, the term "crystalline sulfide solid electrolyte" refers to a sulfide solid electrolyte in which a peak derived from the solid electrolyte is observed in an X-ray diffraction pattern in an X-ray diffraction measurement, regardless of whether or not a peak derived from the raw materials of the sulfide solid electrolyte is present. That is, the crystalline sulfide solid electrolyte includes a crystalline structure derived from the solid electrolyte, and a portion of the crystalline structure may be derived from the solid electrolyte, or the entire crystalline structure may be derived from the solid electrolyte. Furthermore, as long as the crystalline sulfide solid electrolyte has the X-ray diffraction pattern described above, it may also contain an amorphous sulfide solid electrolyte in part. Therefore, the crystalline sulfide solid electrolyte includes so-called glass ceramics obtained by heating an amorphous sulfide solid electrolyte to a temperature equal to or higher than the crystallization temperature.

[0039] In addition, in this specification, the term "amorphous sulfide solid electrolyte" refers to an X-ray diffraction pattern in X-ray diffraction measurement that has a halo pattern in which peaks other than those derived from the raw materials are not substantially observed, regardless of whether or not peaks derived from the raw materials of the sulfide solid electrolyte are present.

[0040] The crystalline structure of the crystalline sulfide solid electrolyte is Li ３ P.S. ４ Crystal structure, Li ４ P ２ S ６ Crystal structure, Li ７ P.S. ６ Crystal structure, Li ７ P ３ S １１ Crystal structure having peaks at 2θ=approximately 20.2° and 23.6° (for example, JP 2013-16423 A), and Li ４－ｘ Ge １－ｘ P ｘ S ４ Thio-LISICON Region II crystal structure (Kanno et al., Journal of the Electrochemical Society, 148(7)A742-746(2001)), Li４－ｘ Ge １－ｘ P ｘ S ４ Examples of the crystal structure include a crystal structure similar to the thio-LISICON Region II type (see Solid State Ionics, 177 (2006), 2721-2725). The crystal structure of the crystalline sulfide solid electrolyte is preferably the thio-LISICON Region II type crystal structure, among the above, in that higher ionic conductivity can be obtained. Here, the "thio-LISICON Region II type crystal structure" refers to a crystal structure in which Li ４－ｘ Ge １－ｘ P ｘ S ４ Thio-LISICON Region II crystal structure, Li ４－ｘ Ge １－ｘ P ｘ S ４ This indicates that the thio-LISICON region II type has a similar crystal structure.

[0041] The crystalline sulfide solid electrolyte may contain the thiolicon region II type crystal structure or may contain it as the main crystal, but from the viewpoint of obtaining higher ionic conductivity, it is preferable that it contains it as the main crystal. In this specification, "containing it as the main crystal" means that the proportion of the target crystal structure in the crystal structure is 80% or more, preferably 90% or more, and more preferably 95% or more. In addition, from the viewpoint of obtaining higher ionic conductivity, the crystalline sulfide solid electrolyte contains crystalline Li ３ P.S. ４ (β-Li ３ P.S. ４ ) is preferably not included.

[0042] In X-ray diffraction measurement using CuKα radiation, Li ３ P.S. ４ Diffraction peaks of the crystal structure appear, for example, at 2θ=17.5°, 18.3°, 26.1°, 27.3°, and 30.0°. ４ P ２ S ６Diffraction peaks of the crystal structure appear, for example, at 2θ=16.9°, 27.1°, and 32.5°. ７ P.S. ６ Diffraction peaks of the crystal structure appear, for example, at 2θ=15.3°, 25.2°, 29.6°, and 31.0°. ７ P ３ S １１ Diffraction peaks of the crystal structure appear, for example, at 2θ=17.8°, 18.5°, 19.7°, 21.8°, 23.7°, 25.9°, 29.6°, and 30.0°, and Li ４－ｘ Ge １－ｘ P ｘ S ４ The diffraction peaks of the thio-LISICON Region II crystal structure appear, for example, at 2θ=20.1°, 23.9°, and 29.5°, and Li ４－ｘ Ge １－ｘ P ｘ S ４ Diffraction peaks of a crystal structure similar to that of thio-LISICON Region II type appear, for example, at 2θ=20.2° and 23.6°. Note that these peak positions may vary within a range of ±0.5°.

[0043] The crystalline sulfide solid electrolyte may be the above-mentioned Li ７ P.S. ６ A preferred example of the crystalline sulfide solid electrolyte is an argyrodite-type crystal structure having a structural skeleton in which part of P is substituted with Si. The composition formula of the argyrodite-type crystal structure is, for example, the composition formula Li ７－ｘ P １－ｙ Si ｙ S ６ and Li ７＋ｘ P １－ｙ Si ｙ S ６(x is −0.6 to 0.6, y is 0.1 to 0.6) The argyrodite-type crystal structure represented by this composition formula is a cubic or orthorhombic crystal, preferably a cubic crystal, and in X-ray diffraction measurement using CuKα radiation, has peaks that appear mainly at 2θ=15.5°, 18.0°, 25.0°, 30.0°, 31.4°, 45.3°, 47.0°, and 52.0°.

[0044] The composition formula of the argyrodite-type crystal structure is Li ７－ｘ－２ｙ P.S. ６－ｘ－ｙ Cl ｘ (0.8≦x≦1.7, 0<y≦−0.25x+0.5) is also included. The argyrodite-type crystal structure represented by this composition formula is preferably a cubic crystal, and in X-ray diffraction measurement using CuKα radiation, has peaks that appear mainly at 2θ=15.5°, 18.0°, 25.0°, 30.0°, 31.4°, 45.3°, 47.0°, and 52.0°. The composition formula of the argyrodite-type crystal structure is preferably the composition formula Li ７－ｘ P.S. ６－ｘ Ha ｘ (Ha is Cl or Br, and x is preferably 0.2 to 1.8). The argyrodite-type crystal structure represented by this composition formula is preferably a cubic crystal, and in X-ray diffraction measurement using CuKα radiation, it has peaks that appear mainly at 2θ = 15.5°, 18.0°, 25.0°, 30.0°, 31.4°, 45.3°, 47.0°, and 52.0°. Note that these peak positions may vary within a range of ±0.5°.

[0045] The composition ratio of atoms contained in the crystalline sulfide solid electrolyte is preferably a composition ratio according to the composition formula corresponding to the above-mentioned various crystal structures. When the composition ratio of each atom is within the range, it is easy to form a thiosilicon region II type crystal structure or an argyrodite type crystal structure, among the above-mentioned crystal structures.

[0046] The crystalline sulfide solid electrolyte may contain one or more complexing agents and solvents used during production. The total content of the complexing agent and solvent contained in the crystalline sulfide solid electrolyte is most 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, even more preferably 3.0% by mass or less, and particularly preferably 1.0% by mass or less.

[0047] The sulfide solid electrolyte contains lithium atoms, sulfur atoms, and phosphorus atoms, and preferably contains lithium atoms, sulfur atoms, phosphorus atoms, and halogen atoms. Representative examples include Li ２ S-P ２ S ５ Solid electrolytes composed of lithium sulfide and phosphorus sulfide such as Li ２ S-P ２ S ５ - LiI, Li ２ S-P ２ S ５ -LiCl, Li ２ S-P ２ S ５ - LiBr, Li ２ S-P ２ S ５ -LiI-LiBr, etc., solid electrolytes composed of lithium sulfide, phosphorus sulfide, and lithium halide; and solid electrolytes further containing other atoms such as oxygen atoms and silicon atoms, for example, Li ２ S-P ２ S ５ -Li ２ O-LiI, Li ２ S-SiS ２ -P ２ S ５ In order to obtain higher ionic conductivity, a solid electrolyte such as Li ２ S-P ２ S ５ - LiI, Li ２ S-P ２ S ５ -LiCl, Li ２ S-P ２ S ５ - LiBr, Li２ S-P ２ S ５ A solid electrolyte composed of lithium sulfide, phosphorus sulfide, and lithium halide, such as LiI-LiBr, is preferred, and Li ２ S-P ２ S ５ A solid electrolyte composed of lithium sulfide, phosphorus sulfide, and two types of lithium halides, such as LiI-LiBr, is more preferred. The types of atoms constituting the sulfide solid electrolyte can be confirmed, for example, by an ICP emission spectrometer.

[0048] In the sulfide solid electrolyte (amorphous sulfide solid electrolyte and crystalline sulfide solid electrolyte), the composition ratio (molar ratio) of lithium atoms, phosphorus atoms, sulfur atoms, and halogen atoms is preferably 1.0 to 1.8: 0.1 to 0.8: 1.0 to 2.0: 0.01 to 0.6, more preferably 1.1 to 1.7: 0.2 to 0.6: 1.2 to 1.8: 0.05 to 0.5, and even more preferably 1.2 to 1.6: 0.25 to 0.5: 1.3 to 1.7: 0.08 to 0.4. Furthermore, when bromine and iodine, or bromine and chlorine are used in combination as halogen atoms, the composition ratio (molar ratio) of lithium atoms, phosphorus atoms, sulfur atoms, bromine, and iodine (or chlorine) is preferably 1.0 to 1.8: 0.1 to 0.8: 1.0 to 2.0: 0.01 to 0.3: 0.01 to 0.3, more preferably 1.1 to 1.7: 0.2 to 0.6: 1.2 to 1.8: 0.02 to 0.25: 0.02 to 0.25, even more preferably 1.2 to 1.6: 0.25 to 0.5: 1.3 to 1.7: 0.03 to 0.2: 0.03 to 0.2, and still more preferably 1.35 to 1.45: 0.3 to 0.45: 1.4 to 1.7: 0.04 to 0.18: 0.04 to 0.18. By setting the composition ratio (molar ratio) of lithium atoms, sulfur atoms, phosphorus atoms, and halogen atoms within the above range, a solid electrolyte having a higher ionic conductivity and a crystal structure described below, particularly a thiolicon region II crystal structure or an argyrodite crystal structure, is likely to be obtained.

[0049] The average particle size (D ５０) is, for example, preferably 0.01 μm or more, more preferably 0.03 μm or more, even more preferably 0.05 μm or more, and particularly preferably 0.1 μm or more, and is 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.

[0050] [Method for transporting sulfide solid electrolyte] A method for transporting a sulfide solid electrolyte according to the present embodiment includes the steps of compressing a powdered sulfide solid electrolyte containing lithium atoms, sulfur atoms, and phosphorus atoms to obtain a green compact, filling the green compact into a packaging container to obtain a package, transporting the package, and removing the green compact from the packaging and crushing it to obtain a crushed product. Another method for transporting a sulfide solid electrolyte according to the present embodiment includes the steps of compressing a powdered sulfide solid electrolyte containing lithium atoms, sulfur atoms, and phosphorus atoms to obtain a green compact, and crushing the green compact to obtain a crushed product. ３ That's all.

[0051] The above-described method for transporting a sulfide solid electrolyte according to another embodiment of the present invention includes a step of obtaining a powder compact. As long as the density of the obtained powder compact is within the above-described range, the subsequent steps are not particularly limited. However, from the viewpoint of further exerting the effects of this embodiment, it is preferable to include a step of obtaining a package, a step of transporting, and a step of obtaining a crushed product, which will be described later.

[0052] [Step of Obtaining a Powder Compact] The conveying method of the present embodiment includes a step of compressing a powdered sulfide solid electrolyte containing lithium atoms, sulfur atoms, and phosphorus atoms to obtain a powder compact. The step of obtaining a powder compact is performed in compression molding equipment.

[0053] Methods for compressing the powdered sulfide solid electrolyte include placing the sulfide solid electrolyte in a mold having a predetermined shaped depression and pressing it to form pellets, or using a roller compactor to place the sulfide solid electrolyte between two rotating rolls, pressing it, and optionally further pulverizing it into flakes. The temperature when pressing with a roller compactor is typically 20 to 60°C, and the pressure is typically 0.1 to 1 ton per cm of roll width.

[0054] The step of obtaining a powder compact can also involve adding a solvent to the powdered sulfide solid electrolyte and then compressing it. The solvent can be a wide variety of solvents that have traditionally been used in the production of solid electrolytes, including hydrocarbon solvents such as aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, and aromatic hydrocarbon solvents, as well as compounds containing heteroatoms such as nitrogen, oxygen, and halogen atoms such as chlorine, and sulfur atoms. The amount of the solvent added is preferably 1.0 to 20 mass%, more preferably 3.0 to 15 mass%, and even more preferably 5.0 to 12 mass%, based on the total amount of the sulfide solid electrolyte. An amount of solvent added relative to the sulfide solid electrolyte of 1.0 mass% or more is preferred from the viewpoint of preventing powder scattering during the step of obtaining a powder compact, while an amount of solvent of 20 mass% or less is preferred because the solvent is less likely to leach out of the sulfide solid electrolyte during the step of obtaining a powder compact.

[0055] 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. The shape of the powder compact is not particularly limited, but may be a cylindrical, elliptical, triangular prism, cylinder, rectangular parallelepiped, cube, ellipse, sphere, lens, or flake shape. The density of the powder compact is not particularly limited, but is preferably 0.2 g / cm. ３ or more, more preferably 0.4 to 1.6 g / cm ３ and more preferably 0.8 to 1.5 g / cm ３ The density of the green compact is 0.2 g / cm ３When the density of the powder compact is 1.6 g / cm or more, scattering of the sulfide solid electrolyte can be effectively suppressed, and the efficiency of transportation can be improved. ３ If the temperature is below this, the powder compact will be easily crushed.

[0056] [Step of Obtaining a Package] The conveying method of this embodiment includes a step of filling the powder compact into a packaging container to obtain a package. The step of obtaining a package is performed in packaging equipment.

[0057] Any packaging container may be used, and examples thereof include bags, cans, bottles, etc. The material of the packaging container is preferably one with low moisture permeability from the viewpoint of preventing the sulfide solid electrolyte from coming into contact with moisture contained in the outside air, and specifically, is preferably selected from metal, glass, and plastic. When the packaging container is a bag made of a plastic film, it is preferably made of a plastic film provided with a metal thin film layer. Furthermore, two or more types of packaging containers may be combined.

[0058] More specifically, the packaging container preferably comprises one or more bag-shaped bodies from the viewpoint of ease of handling when removing the powder compact in the process of obtaining the crushed material described below, and at least one of the bag-shaped bodies is preferably made of a plastic film provided with a metal thin film layer.

[0059] From the viewpoint of protecting the contents during transportation, it is preferable that the package be further packed in an outer container before transportation. The outer container may be one, or a combination of multiple containers. Specifically, the outer container is preferably selected from a metal can and a plastic container. Furthermore, the inside of the outer container can be filled with air or an inert gas and kept pressurized to prevent moisture from entering from the outside. Examples of the inert gas include nitrogen gas.

[0060] More specifically, the package preferably has the following configurations (1) to (3): (1) A package in which a powder compact is packaged in a packaging container having one or more bag-shaped bodies, which is then packaged in an outer container selected from one or more metal cans and plastic containers. (2) A package in which a powder compact is packaged in a packaging container having a plurality of bag-shaped bodies, at least one of which is made of a plastic film with a metal thin film layer, which is then packaged in an outer container selected from one or more metal cans and plastic containers. (3) A package in which a powder compact is packaged in a packaging container having a plurality of bag-shaped bodies, at least one of which is made of a plastic film with a metal thin film layer, which is then packaged in a plastic container, which is then packaged in a metal can.

[0061] [Transporting Step] The transporting method of this embodiment includes a step of transporting the package. The step of transporting the package is performed by a transporting device.

[0062] The conveying means is a means for conveying the packaged body from the packaging equipment to a crushing equipment described later. The conveying means is not particularly limited, and examples thereof include one or more means selected from human power, vehicles, ships, and aircraft, and a combination of multiple means is also possible. Specific examples of vehicles include automobiles such as trucks, as well as railway vehicles.

[0063] [Step of Obtaining Crushed Material] The conveying method of this embodiment includes a step of removing the powder compact from the package and crushing it to obtain a crushed material. The step of obtaining the crushed material is performed by crushing equipment.

[0064] The crushing equipment is not particularly limited as long as it can crush the powder compact and return it to a powder state, and for example, a grinder can be used. Specific examples of grinders include dry grinders and wet grinders, and dry or wet media grinders using grinding media are preferably used. When crushing the powder compact in a state where a solvent has been added, it is preferable to use a wet grinder that can handle wet grinding. The solvent used here can be the same as that used in the step of obtaining the powder compact described above.

[0065] Examples of the dry grinding machine include dry media grinding machines such as dry bead mills, dry ball mills, and dry vibration mills, and dry non-media grinding machines such as jet mills. Representative examples of the wet grinding machine include wet bead mills, wet ball mills, and wet vibration mills, with wet bead mills that use beads as grinding media being preferred because they allow for free adjustment of grinding operation conditions and are easily adaptable to smaller particle sizes. Examples of the grinding machine include machines that can grind objects using ultrasound, such as ultrasonic grinders, ultrasonic homogenizers, and probe ultrasonic grinders.

[0066] The step of obtaining the crushed product may be performed alone, or may be performed while mixing the sulfide solid electrolyte with other materials, such as an electrode active material, a conductive material, a binder, etc.

[0067] As the electrode active material, a positive electrode active material or a negative electrode active material is adopted depending on whether the electrode mixture is used for the positive electrode or the negative electrode.

[0068] The positive electrode active material can be any material that can promote a battery chemical reaction involving the movement of lithium ions due to atoms that are used to exhibit ionic conductivity, preferably lithium atoms, in relation to the negative electrode active material. Examples of such positive electrode active materials that can insert and extract lithium ions include oxide-based positive electrode active materials and sulfide-based positive electrode active materials.

[0069] Oxide-based positive electrode active materials include LMO (lithium manganese oxide), LCO (lithium cobalt oxide), NMC (lithium nickel manganese cobalt oxide), NCA (lithium nickel cobalt aluminate), LNCO (lithium nickel cobalt oxide), and olivine-type compounds (LiMeNPO ４ , Me=Fe, Co, Ni, Mn) and other lithium-containing transition metal composite oxides are preferred. Examples of sulfide-based positive electrode active materials include titanium sulfide (TiS ２ ), molybdenum sulfide (MoS ２ ), iron sulfide (FeS, FeS ２ ), copper sulfide (CuS), nickel sulfide (Ni ３ S２ In addition to the above positive electrode active materials, niobium selenide (NbSe) ３ The positive electrode active material may be used alone or in combination of two or more.

[0070] The negative electrode active material can be any atom that exhibits ionic conductivity, preferably a metal capable of forming an alloy with lithium atoms, its oxide, or an alloy of the metal with lithium atoms, as long as it can promote a battery chemical reaction involving the migration of lithium ions due to lithium atoms. As such a negative electrode active material capable of inserting and extracting lithium ions, any material known in the battery field as a negative electrode active material can be used without limitation. Examples of such a negative electrode active material include metallic lithium, metals that can form alloys with metallic lithium, such as metallic indium, metallic aluminum, metallic silicon, and metallic tin, oxides of these metals, and alloys of these metals with metallic lithium.

[0071] The electrode active material used in this embodiment may have a coating layer on its surface. Examples of materials for forming the coating layer include ion conductors such as nitrides, oxides, or composites of atoms that exhibit ionic conductivity in the sulfide solid electrolyte, preferably lithium atoms. Specifically, lithium nitride (Li ３ N), Li ４ GeO ４ The main structure is, for example, Li ４－２ｘ Zn ｘ GeO ４ Conductors having a lysicone-type crystal structure such as Li ３ P.O. ４ For example, Li ４－ｘ Ge １－ｘ P ｘ S ４ Conductors having a thiolicon-type crystal structure such as La ２／３－ｘ Li ３ｘ TiO ３ Conductors having a perovskite crystal structure such as LiTi ２ (P.O. ４ )３ Conductors having a NASICON type crystal structure such as Li ｙ Ti ３－ｙ O ４ (0<y<3), Li ４ Ti ５ O １２ Lithium titanate (LTO), LiNbO ３ , LiTaO ３ Lithium metal oxides of metals belonging to Group 5 of the periodic table, such as Li ２ Alumni ２ O ３ -P ２ O ５ system, Li ２ Alumni ２ O ３ -ZnO-based, Li ２ O-Al ２ O ３ -SiO ２ -P ２ O ５ -TiO ２ Examples of suitable conductors include oxide-based conductors such as those based on ZnO.

[0072] An electrode active material having a coating layer can be obtained, for example, by applying a solution containing various atoms constituting the material forming the coating layer to the surface of the electrode active material and then baking the electrode active material after application, preferably at 200°C to 400°C. Here, the solution containing various atoms may be, for example, a solution containing alkoxides of various metals such as lithium ethoxide, titanium isopropoxide, niobium isopropoxide, or tantalum isopropoxide. In this case, the solvent may be an alcoholic solvent such as ethanol or butanol; an aliphatic hydrocarbon solvent such as hexane, heptane, or octane; or an aromatic hydrocarbon solvent such as benzene, toluene, or xylene. The application may be performed by immersion, spray coating, or the like.

[0073] From the viewpoint of improving production efficiency and battery performance, the firing temperature is preferably 200°C or higher and 400°C or lower, more preferably 250°C or higher and 390°C or lower, and the firing time is usually about 1 minute to 10 hours, preferably 10 minutes to 4 hours.

[0074] The coverage of the coating layer is preferably 90% or more, more preferably 95% or more, and even more preferably 100% based on the surface area of ​​the electrode active material, i.e., the entire surface is preferably covered. The thickness of the coating layer is preferably 1 nm or more, more preferably 2 nm or more, and the upper limit is preferably 30 nm or less, more preferably 25 nm or less. The thickness of the coating layer can be measured by cross-sectional observation using a transmission electron microscope (TEM), and the coverage can be calculated from the thickness of the coating layer, elemental analysis value, and BET specific surface area.

[0075] Examples of the conductive material, from the viewpoint of improving battery performance by improving electronic conductivity, include carbon-based materials such as artificial graphite, graphite carbon fiber, resin-baked carbon, pyrolytic vapor-grown carbon, coke, mesocarbon microbeads, furfuryl alcohol resin-baked carbon, polyacene, pitch-based carbon fiber, vapor-grown carbon fiber, natural graphite, and non-graphitizable carbon.

[0076] The use of the binder improves the strength of the produced positive and negative electrodes. The binder is not particularly limited as long as it can impart functions such as binding property and flexibility, and examples thereof include fluorine-based polymers such as polytetrafluoroethylene and polyvinylidene fluoride, thermoplastic elastomers such as butylene rubber and styrene-butadiene rubber, and various resins such as acrylic resins, acrylic polyol resins, polyvinyl acetal resins, polyvinyl butyral resins, and silicone resins.

[0077] The compounding ratio (mass ratio) of the electrode active material to the sulfide solid electrolyte in the electrode mixture 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, in order to improve battery performance and in consideration of production efficiency.

[0078] When a conductive material is contained, the content of the conductive material in the electrode mixture is not particularly limited, but in consideration of improving battery performance and manufacturing efficiency, it is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 1.5% by mass or more, with the upper limit being preferably 10% by mass or less, preferably 8% by mass or less, and even more preferably 5% by mass or less. Furthermore, when a binder is contained, the content of the binder in the electrode mixture is not particularly limited, but in consideration of improving battery performance and manufacturing efficiency, it is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, with the upper limit being preferably 20% by mass or less, preferably 15% by mass or less, and even more preferably 10% by mass or less.

[0079] [Transport System for Sulfide Solid Electrolyte] The transport system for the sulfide solid electrolyte of this embodiment includes compression molding equipment that compresses a powdered sulfide solid electrolyte containing lithium atoms, sulfur atoms, and phosphorus atoms to obtain a green compact; packaging equipment that fills a packaging container with the green compact to obtain a package; transport means that transports the package; and crushing equipment that removes the green compact from the package and crushes it to obtain a crushed product.

[0080] Details of the compression molding equipment, packaging equipment, conveying means, and crushing equipment are the same as those described in relation to the method for conveying a sulfide solid electrolyte of this embodiment.

[0081] [Method for producing all-solid-state battery material] A method for producing an all-solid-state battery material according to this embodiment includes the steps of compressing a powdered sulfide solid electrolyte containing lithium atoms, sulfur atoms, and phosphorus atoms to obtain a green compact, filling the green compact into a packaging container to obtain a package, transporting the package, and removing the green compact from the packaging and crushing it to obtain a crushed product. Another method for producing an all-solid-state battery material according to this embodiment includes the steps of compressing a powdered sulfide solid electrolyte containing lithium atoms, sulfur atoms, and phosphorus atoms to obtain a green compact, and crushing the green compact to obtain a crushed product. ３ That's all.

[0082] The above-described method for producing an all-solid-state battery material according to another embodiment of the present invention includes a step of obtaining a powder compact. As long as the density of the obtained powder compact is within the above-described range, the subsequent steps are not particularly limited. However, from the viewpoint of further exerting the effects of the embodiment of the present invention, it is preferable that the method include a step of obtaining a package, a step of conveying, and a step of obtaining a crushed product.

[0083] Details of the steps of obtaining a compact, obtaining a package, transporting, and obtaining a crushed material are the same as those described for the method for transporting a sulfide solid electrolyte of this embodiment. The all-solid-state battery material obtained by the manufacturing method of this embodiment is the crushed material obtained in the crushing step, that is, the sulfide solid electrolyte itself. Therefore, details of the all-solid-state battery material are the same as those described for the sulfide solid electrolyte.

[0084] [Electrode Mixture] The electrode mixture of the present embodiment contains the all-solid-state battery material obtained by the method for producing an all-solid-state battery material and an electrode active material.

[0085] The details of the electrode active material are the same as those described in relation to the method for transporting a sulfide solid electrolyte of this embodiment.

[0086] [All-Solid-State Battery] The all-solid-state battery of this embodiment includes the all-solid-state battery material obtained by the method for producing an all-solid-state battery material in a solid electrolyte layer, or includes the electrode mixture in at least one of a positive electrode and a negative electrode.

[0087] [Package] The package of the present embodiment is formed by filling a packaging container with a green compact obtained by compressing a powdered sulfide solid electrolyte containing lithium atoms, sulfur atoms, and phosphorus atoms. From the viewpoint of protecting the green compact, the package of the present embodiment preferably further includes an outer container.

[0088] The details of the sulfide solid electrolyte, the compact, the packaging container, and the outer container are the same as those described in relation to the method for transporting a sulfide solid electrolyte of this embodiment.

[0089] According to the conveying method of the present embodiment, a sulfide solid electrolyte that is suitably used in information-related devices and communication devices such as personal computers, video cameras, and mobile phones, as well as batteries used in automotive applications, can be efficiently conveyed while preventing scattering.

Claims

1. A method for transporting a sulfide solid electrolyte, comprising the steps of compressing a powdered sulfide solid electrolyte containing lithium atoms, sulfur atoms, and phosphorus atoms to obtain a green compact, filling the green compact into a packaging container to obtain a package, transporting the package, and removing the green compact from the packaging and crushing it to obtain a crushed product.

2. The density of the powder compact is 0.2 g / cm ３ The method for transporting a sulfide solid electrolyte according to claim 1 .

3. The method for transporting a sulfide solid electrolyte according to claim 1 or 2, wherein in the step of obtaining the green compact, a solvent is added to the powdered sulfide solid electrolyte before compression.

4. The method for transporting a sulfide solid electrolyte according to any one of claims 1 to 3, wherein in the step of obtaining the crushed product, a solvent is added to the compact before crushing.

5. A method for transporting a sulfide solid electrolyte according to any one of claims 1 to 4, wherein the packaging container comprises one or more bag-shaped bodies, and at least one of the bag-shaped bodies is made of a plastic film provided with a metal thin film layer.

6. The method for transporting a sulfide solid electrolyte according to any one of claims 1 to 5, wherein the package is further packed in an outer container before being transported.

7. The method for transporting a sulfide solid electrolyte according to claim 6, wherein the outer container is at least one selected from the group consisting of a metal can and a plastic container.

8. A sulfide solid electrolyte transport system comprising: compression molding equipment for compressing a powdered sulfide solid electrolyte containing lithium atoms, sulfur atoms, and phosphorus atoms to obtain a green compact; packaging equipment for filling a packaging container with the green compact to obtain a package; transport means for transporting the package; and crushing equipment for removing the green compact from the package and crushing it to obtain a crushed product.

9. A method for producing an all-solid-state battery material, comprising: compressing a powdered sulfide solid electrolyte containing lithium atoms, sulfur atoms, and phosphorus atoms to obtain a green compact; filling the green compact into a packaging container to obtain a package; transporting the package; and removing the green compact from the packaging and crushing it to obtain a crushed product.

10. An all-solid-state battery comprising in a solid electrolyte layer the all-solid-state battery material obtained by the method for producing an all-solid-state battery material according to claim 9.

11. An electrode mixture comprising an all-solid-state battery material obtained by the method for producing an all-solid-state battery material according to claim 9 and an electrode active material.

12. An all-solid-state battery comprising the electrode mixture according to claim 11 in at least one of the positive electrode and the negative electrode.

13. A packaged body obtained by compressing a powdered sulfide solid electrolyte containing lithium atoms, sulfur atoms, and phosphorus atoms and filling the compressed powder into a packaging container.

14. The package of claim 13, further comprising an outer container.

15. A method for producing a lithium-ion-containing solid electrolyte comprising compressing a powder of a sulfide solid electrolyte containing lithium atoms, sulfur atoms, and phosphorus atoms to obtain a green compact, the green compact having a density of 0.2 g / cm ３ The above is the method for transporting a sulfide solid electrolyte.

16. A method for producing a lithium-ion-containing solid electrolyte comprising compressing a powder of a sulfide solid electrolyte containing lithium atoms, sulfur atoms, and phosphorus atoms to obtain a green compact, the green compact having a density of 0.2 g / cm ３ This is the method for producing an all-solid-state battery material.