Method for processing sulfur atom-containing material, device for producing sulfur atom-containing material, facility for transporting sulfur atom-containing material, and transport bin

Abstract

The invention provides a method for processing a sulfur atom-containing material, a device for manufacturing a sulfur atom-containing material, a facility for transporting a sulfur atom-containing material, and a transport bin, which can safely and effectively cope with leakage of a sulfur atom-containing material such as a raw material, an intermediate, and a product containing sulfur atoms. The method for treating a sulfur atom-containing material includes: bringing at least one sulfur atom-containing material selected from a raw material containing sulfur atoms, an electrolyte precursor, and a sulfide solid electrolyte into contact with a liquid oil substrate; and contacting the resulting content comprising the sulfur atom-containing material and the liquid oil substrate with an aqueous alkaline solution.

Description

Technical Field

[0001] This invention relates to a method for processing sulfur-containing atomic materials, an apparatus for manufacturing sulfur-containing atomic materials, and equipment and transport warehouses for handling sulfur-containing atomic materials. Background Technology

[0002] In recent years, with the rapid popularization of information-related devices and communication devices such as personal computers, cameras, and mobile phones, the development of batteries used as their power source has also received attention. Previously, batteries used for such applications employed electrolytes containing flammable organic solvents. However, by making the battery entirely solid-state, safety devices are simplified due to the absence of flammable organic solvents within the battery, and manufacturing costs and productivity are significantly improved. Therefore, the development of batteries that replace the electrolyte with a solid electrolyte layer has been undertaken.

[0003] Methods for manufacturing solid electrolytes for use in solid electrolyte layers are broadly classified into solid-phase methods and liquid-phase methods. Liquid-phase methods include homogeneous methods where the solid electrolyte material is completely dissolved in a solvent, and non-homogeneous methods where the solid electrolyte material is not completely dissolved, resulting in a solid-liquid coexistence suspension. For example, as a homogeneous method within the liquid-phase method, a method is known to dissolve the solid electrolyte in a solvent and then precipitate it (see, for example, Patent Document 1). As a non-homogeneous method, methods are known to react solid electrolyte raw materials such as lithium sulfide in a solvent containing a polar aprotic solvent (see, for example, Patent Documents 2 and 3), and methods for manufacturing solid electrolytes using a specific compound with an amino group as a complexing agent (see, for example, Patent Document 4).

[0004] Sulfide solid electrolytes, containing sulfur atoms, react with atmospheric moisture to produce hydrogen sulfide, or exhibit rapid deterioration of ionic conductivity due to deliquescence. In contrast, techniques are known to involve coating sulfide solid electrolytes with insulating oils such as polysiloxanes within the battery container of an all-solid-state battery (see, for example, Patent Document 5), and compositions comprising sulfide solid electrolytes and an impermeable matrix surrounding them (see, for example, Patent Document 6). Furthermore, as a safe and reliable method for detoxification, techniques are known to involve mixing a mixture of crushed asbestos-containing waste and liquid oil, and then detoxifying it by firing it in a rotary kiln or similar furnace (see, for example, Patent Document 7).

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2014-191899

[0008] Patent Document 2: International Publication No. 2014 / 192309

[0009] Patent Document 3: International Publication No. 2018 / 054709

[0010] Patent Document 4: International Publication No. 2020 / 105737

[0011] Patent Document 5: Japanese Patent Application Publication No. 2009-117168

[0012] Patent Document 6: Japanese Patent Application Publication No. 2020-136139

[0013] Patent Document 7: Japanese Patent Application Publication No. 2008-272543 Summary of the Invention

[0014] The technical problem that the invention aims to solve

[0015] The present invention was made in view of the following situation, and its object is to provide a method for handling sulfur-containing materials, such as raw materials, intermediates and products containing sulfur atoms, that can safely and effectively deal with leakage of sulfur-containing materials, as well as an apparatus for manufacturing sulfur-containing materials, and equipment and transport warehouse for handling sulfur-containing materials.

[0016] Solution to the above technical problems

[0017] The method for processing the sulfur-containing atomic material of the present invention is as follows:

[0018] A method for processing a sulfur-containing material includes: contacting at least one sulfur-containing material selected from a sulfur-containing raw material, an electrolyte precursor, and a sulfide solid electrolyte with a liquid oil substrate; and

[0019] The resulting mixture containing the sulfur-containing atomic material and the liquid oil substrate is brought into contact with an alkaline aqueous solution.

[0020] The apparatus for manufacturing the sulfur-containing atomic material of the present invention is as follows:

[0021] An apparatus for manufacturing sulfur-containing atomic materials, comprising: a reaction apparatus for raw materials containing sulfur-containing atomic materials;

[0022] Liquid oil-based material storage container for storing liquid oil-based materials; and

[0023] An alkaline aqueous solution storage container for storing alkaline aqueous solutions.

[0024] The equipment for handling sulfur-containing atomic materials of the present invention is as follows:

[0025] A device for handling sulfur-containing materials includes: a storage container A for storing at least one sulfur-containing material selected from raw materials containing sulfur atoms, electrolyte precursors, and sulfide solid electrolytes; and

[0026] Storage container B stores liquid oil-based materials.

[0027] Furthermore, the transport container for handling sulfur-containing atomic materials of the present invention is,

[0028] A transport container for handling sulfur-containing materials includes at least one storage container selected from storage section A and storage section B, wherein storage section A stores at least one sulfur-containing material selected from raw materials and electrolyte precursors containing sulfur atoms, and sulfide solid electrolytes.

[0029] Storage section B stores liquid oil-based materials.

[0030] Invention Effects

[0031] According to the present invention, a method for handling sulfur-containing materials, an apparatus for manufacturing sulfur-containing materials, and equipment and transport warehouses for handling sulfur-containing materials can be provided to safely and effectively deal with the leakage of sulfur-containing materials such as raw materials, intermediates and products containing sulfur atoms. Attached Figure Description

[0032] Figure 1 This is a schematic diagram of the experimental equipment used in the embodiments.

[0033] Figure 2 This is a graph showing the change in hydrogen sulfide concentration over time in Examples (1-1) and (1-2).

[0034] Figure 3 This is a graph showing the change in hydrogen sulfide concentration over time in Examples (2-1) and (2-2).

[0035] Figure 4 This is a graph showing the change in hydrogen sulfide concentration over time in comparative examples (1-1) and (1-2).

[0036] Figure 5 This is a graph showing the change in hydrogen sulfide concentration over time in comparative examples (2-1) and (2-2).

[0037] Figure 6 This is a graph showing the change in hydrogen sulfide concentration over time in comparative examples (3-1) and (3-2).

[0038] Figure 7 This is a graph showing the change in hydrogen sulfide concentration over time in Comparative Example (4-1).

[0039] Figure 8 This is a graph showing the change in hydrogen sulfide concentration over time in comparative example (4-2). Detailed Implementation

[0040] 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; additionally, the values ​​of the embodiments can also be used as the upper and lower limits. Furthermore, preferred provisions can be adopted arbitrarily. That is, one preferred provision can be combined with one or more other preferred provisions. It can be said that the combination of preferred provisions is more preferred.

[0041] (Discoveries made by the inventors in order to complete this invention)

[0042] 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.

[0043] With the increasing demand for sulfide solid electrolytes, the formal commissioning of facilities, ranging from laboratory-scale to mass-production-ready factory-scale equipment, has commenced, resulting in a significant increase in processing volume. As processing volumes increase, it is necessary to anticipate potential leaks during the manufacturing and transfer of raw materials, intermediates such as slurries containing electrolyte precursors, and finished products, necessitating the prior research into safe and effective countermeasures. This is particularly true in equipment handling materials containing sulfur atoms (hereinafter referred to as "sulfur-containing materials"), such as lithium sulfide, phosphorus pentasulfide, lithium sulfate, sulfur, and other raw materials or intermediates of these solid electrolytes, as well as sulfide solid electrolyte products. This is because these sulfur-containing materials can react with atmospheric moisture to produce hydrogen sulfide.

[0044] Furthermore, the state of these raw materials, intermediates, and products is not limited to powders. For example, in manufacturing apparatuses employing homogenization methods (see, for example, Patent Documents 2-4) that are advantageous for mass production, slurry leakage containing solvent and electrolyte precursors may also occur. Thus, it is necessary to address the various types and states of leaked substances when dealing with leaks of raw materials, intermediates, and products. Moreover, leaks are not limited to factory-scale equipment; they can also occur in laboratory-scale equipment.

[0045] The inventors have focused on deactivating sulfur-containing materials, such as raw materials, intermediates, and products containing sulfur atoms, in the event of a leak. For example, to deactivate a sulfide solid electrolyte, contact with an alkaline aqueous solution containing sodium hydroxide is an example. However, in the event of a leak of such sulfur-containing materials within factory equipment, it is desirable to avoid spraying alkaline aqueous solutions onto the leaking material, considering safety. Furthermore, considering that deactivating such sulfur-containing materials with alkaline aqueous solutions requires a large amount of water and involves a rapid exothermic reaction, this method is not preferred. On the other hand, such sulfur-containing materials sometimes react immediately with moisture in the atmosphere to produce hydrogen sulfide; therefore, considering safety, recovering and handling the leaked material and contacting it with an alkaline aqueous solution is also not a preferred method.

[0046] The inventors further investigated methods for deactivation due to detoxification and found that liquid oil-based materials, such as industrial oil bases (e.g., fuel oil bases, lubricating oil bases, refrigerant oil bases) and commercial oils (e.g., edible oils), are effective. Liquid oil-based materials are safer than the aforementioned alkaline aqueous solutions, are easier to handle, and can be immediately brought into contact with the leaked material. Therefore, the generation of hydrogen sulfide caused by the reaction of sulfur-containing materials with atmospheric moisture can be effectively suppressed. Furthermore, by contacting with an alkaline aqueous solution, not only can the deactivation of sulfur-containing materials due to detoxification be achieved, but the liquid oil-based material can also be treated. Thus, the inventors have established a method for safely and effectively addressing leaks of sulfur-containing materials, such as raw materials, intermediates, and products containing sulfur atoms.

[0047] The technologies described in patent documents 5 and 6 focus on suppressing the generation of hydrogen sulfide when using sulfide solid electrolytes in all-solid-state batteries. However, they do not address the handling of leaks in raw materials, intermediates, and products containing sulfur atoms, and it is not easy to apply the technologies described in these patent documents to the technologies involved in handling leaks of sulfide solid electrolytes, etc.

[0048] Furthermore, Patent Document 7 describes a method for harmless treatment using liquid oil. However, its treatment of asbestos contained in asbestos-containing waste is a method for suppressing the dispersion of asbestos-containing dust, and it completely disregards the treatment of sulfur-containing materials. The suppression of asbestos-containing dust dispersion in Patent Document 7 is aimed at preventing physical damage. In contrast, the treatment method of this embodiment is a method for suppressing chemical reactions such as the reaction between sulfur-containing materials and moisture in the atmosphere. The method described in Patent Document 7 and the treatment method of this embodiment address completely different phenomena. Therefore, similar to Patent Documents 5 and 6 mentioned above, it is not easy to apply the technology described in Patent Document 7 to the technology involved in the treatment method when sulfide solid electrolytes or the like leak.

[0049] Therefore, in existing technologies, there is no method that can safely and effectively address leaks in raw materials, intermediates, and products containing sulfur atoms. With the increasing necessity of addressing leaks as we move towards the mass production of solid electrolytes, the ability to safely and effectively handle leaks in raw materials, intermediates, and products containing sulfur atoms is an urgent technical issue.

[0050] In contrast, the above-described method for processing sulfur-containing materials, apparatus for manufacturing sulfur-containing materials, and equipment and transport container for handling sulfur-containing materials according to the present invention can solve these urgent technical problems.

[0051] (Various solutions regarding this implementation)

[0052] The method for processing sulfur-containing atomic materials in the first aspect of this embodiment is as follows:

[0053] A method for processing a sulfur-containing material includes: contacting at least one sulfur-containing material selected from a sulfur-containing raw material, an electrolyte precursor, and a sulfide solid electrolyte with a liquid oil substrate; and

[0054] The resulting mixture containing the sulfur-containing atomic material and the liquid oil substrate is brought into contact with an alkaline aqueous solution.

[0055] In the processing method for sulfur-containing atomic materials of this embodiment, the solid electrolyte raw material, electrolyte precursor, and sulfide solid electrolyte used as the sulfur-containing atomic material are not limited to powdered substances, but also include, for example, slurry-like substances containing solvents used in the manufacturing process of sulfide solid electrolytes. That is, the processing method of this embodiment is capable of handling various states of the solid electrolyte raw material, electrolyte precursor, and sulfide solid electrolyte.

[0056] Here, "solid electrolyte" refers to a solid electrolyte having ionic conductivity caused by lithium atoms, and "sulfide solid electrolyte" refers to a solid electrolyte containing at least lithium atoms, phosphorus atoms and sulfur atoms.

[0057] "Sulfide solid electrolytes" include both amorphous sulfide solid electrolytes and crystalline sulfide solid electrolytes.

[0058] In this specification, crystalline sulfide solid electrolyte refers to a sulfide solid electrolyte in which peaks originating from a solid electrolyte are observed in the X-ray diffraction pattern during X-ray diffraction measurements, and is a material independent of whether or not it contains peaks originating from a raw material of the sulfide solid electrolyte. That is, a crystalline sulfide solid electrolyte contains a crystal structure originating from a solid electrolyte; it may be a portion of the crystalline structure originating from that solid electrolyte, or it may be entirely composed of the crystal structure originating from that solid electrolyte. Furthermore, a crystalline sulfide solid electrolyte may also contain a portion of an amorphous sulfide solid electrolyte, provided it has the aforementioned X-ray diffraction pattern. Therefore, crystalline sulfide solid electrolytes include so-called glass-ceramics obtained by heating an amorphous sulfide solid electrolyte to above its crystallization temperature.

[0059] Furthermore, in this specification, amorphous sulfide solid electrolyte refers to a halo pattern in which the X-ray diffraction pattern is a halo pattern in which no peaks other than those originating from the material are observed in the X-ray diffraction measurement, regardless of whether there are peaks originating from the raw material of the sulfide solid electrolyte.

[0060] Furthermore, "electrolyte precursor" refers to a precursor of a sulfide solid electrolyte obtained during the manufacturing process of a sulfide solid electrolyte, which is different from both the solid electrolyte raw material (such as lithium sulfide or phosphorus sulfide) and the sulfide solid electrolyte itself. For example, any substance that is different from the solid electrolyte raw material and the sulfide solid electrolyte, generated through some treatment of the solid electrolyte raw material (e.g., mixing or pulverizing the solid electrolyte raw material with or without a solvent), and which can then be processed (e.g., drying or heating) to become a sulfide solid electrolyte, is considered an "electrolyte precursor." As an example, products obtained by reacting a solid electrolyte raw material with a complexing agent such as a solvent containing heteroatoms like nitrogen or oxygen atoms can be cited. The existence of an "electrolyte precursor" can be confirmed, for example, by analyzing the "electrolyte precursor" using FT-IR (diffusion reflectance spectroscopy) and detecting peaks different from both the raw material and the sulfide solid electrolyte, or by detecting the same peaks using powder X-ray diffraction (XRD). Thus, since the "electrolyte precursor" exhibits a specified peak, it is considered to be a complex formed from solid electrolyte raw materials via complexing agents such as solvents containing heteroatoms.

[0061] The processing method of this embodiment is as described above. First, by contacting the sulfur-containing material with the liquid oil substrate, the generation of hydrogen sulfide caused by the reaction between the sulfur-containing material and moisture in the atmosphere can be suppressed to the greatest extent. Then, by contacting with an alkaline aqueous solution, the deactivation caused by the detoxification of the sulfur-containing material can be carried out, and the liquid oil substrate can be processed.

[0062] The processing method of this embodiment can immediately suppress hydrogen sulfide generated by sulfur-containing atomic materials, and then process the liquid oil substrate used for deactivation due to detoxification and suppression of hydrogen sulfide generation. Therefore, it can be a safe and effective method to deal with and handle the leakage of sulfur-containing atomic materials.

[0063] The second embodiment of this method for processing sulfur-containing atomic materials is a processing method, which, in the first embodiment described above, is a different method.

[0064] The liquid oil base material is at least one oil base material selected from fuel oil base oil, lubricating oil base oil and edible oil.

[0065] As the liquid oil base material used in the processing method of this embodiment, by employing at least one oil base material selected from fuel oil base oil, lubricating oil base oil, and edible oil, it is possible to more safely and effectively handle and treat leaked sulfur-containing materials. Here, "liquid" refers to a fluid with fluidity, preferably with a kinematic viscosity of 460 mmHg at ambient temperature. 2 / s or less, more preferably 90mm 2 / s or less, more preferably 35mm 2 Fluids with a viscosity of less than 1 / s. Kinematic viscosity is measured according to the method specified in JIS K2283:2000 (Crude oil and petroleum products - Test method for kinematic viscosity and method for calculation of viscosity index).

[0066] The third embodiment of this invention provides a method for processing sulfur-containing atomic materials, which is a processing method that, in the first or second embodiment described above,

[0067] During the process of bringing the sulfur-containing atomic material into contact with the liquid oil substrate, the contact is achieved by spraying or spraying the liquid oil substrate.

[0068] Sulfur-containing materials, such as those used in the manufacture of sulfide solid electrolytes, often leak to the ground. Furthermore, leaks can occur around handling equipment or transport containers, for example, during the handling of sulfur-containing compounds such as lithium sulfide and phosphorus sulfide (used as raw materials for solid electrolytes) or sulfide solid electrolytes (used as finished products), when sulfur-containing materials leak from storage areas.

[0069] Taking these circumstances into account, and considering the urgency of dealing with sulfur-containing materials, spraying or sprinkling liquid oil onto the sulfur-containing materials that have leaked onto the ground is an effective way to safely and efficiently handle and deal with leaked sulfur-containing materials.

[0070] The fourth embodiment of this invention provides a method for processing sulfur-containing atomic materials, which is a processing method that, in the first or second embodiment described above,

[0071] During the process of bringing the sulfur-containing material into contact with the liquid oil substrate, the sulfur-containing material is immersed in the liquid oil substrate to achieve contact.

[0072] In the case of the third solution described above, since the primary consideration is the emergency treatment of sulfur-containing materials leaked onto the ground, it is necessary to recover the contents containing sulfur-containing materials and liquid oil, as well as the contents containing alkaline aqueous solutions in the case of spraying or spreading alkaline aqueous solutions. However, in cases where there is no need for urgency, such as when the sulfur-containing materials are in a slurry state and will not immediately produce hydrogen sulfide due to the reaction between the sulfur-containing materials and moisture in the atmosphere, contact with the liquid oil after recovering the leaked sulfur-containing materials would improve the overall operational efficiency.

[0073] Thus, in the processing method of this embodiment, the contact method between the sulfur-containing atom material and the liquid oil substrate can be selected according to whether there is an urgency.

[0074] The fifth embodiment of this invention provides a method for processing sulfur-containing atomic materials, which is a processing method that, in any of the first to fourth embodiments described above,

[0075] During the process of bringing the sulfur-containing atomic material into contact with the liquid oil substrate, the amount of liquid oil substrate used relative to 0.1L of the sulfur-containing atomic material is more than 0.1L and less than 20L.

[0076] By keeping the amount of liquid oil-based material used within the above range, it is possible to more safely and effectively deal with and handle leaked sulfur-containing atomic materials.

[0077] The sixth embodiment of this invention provides a method for processing sulfur-containing atomic materials, which is a processing method that, in any of the first to fifth embodiments described above,

[0078] The alkaline aqueous solution is an aqueous solution of at least one compound selected from alkali metal hydroxides and carbonates, and alkaline earth metal hydroxides.

[0079] By using the above-mentioned aqueous solution as the alkaline aqueous solution, it is possible to deal with and handle leaked sulfur-containing atomic materials more safely and effectively.

[0080] The method for processing sulfur-containing atomic materials in the seventh embodiment of this invention is a processing method that, in any of the first to sixth embodiments described above,

[0081] During the process of contacting the contained substance with the alkaline aqueous solution, the contained substance is mixed with the alkaline aqueous solution.

[0082] In the contact between the contained material, i.e., the contained material including sulfur-containing material and liquid oil base obtained by contacting sulfur-containing material with liquid oil base, and the alkaline aqueous solution, there are no particular restrictions on the method as long as contact can be achieved. In particular, from a safety point of view, it is preferable to mix the contained material with the alkaline aqueous solution. Furthermore, it is possible to achieve contact between the contained material and the alkaline aqueous solution more effectively.

[0083] The processing method of the eighth solution in this embodiment is a processing method that, in any of the first to seventh solutions described above,

[0084] Discard the contact contents obtained by contacting the contents with an alkaline aqueous solution.

[0085] According to the processing method of this embodiment, by contacting the contained substance with an alkaline aqueous solution, the deactivation of the sulfur-containing atom material due to detoxification can be achieved, and the liquid oil substrate can be treated. Preferably, the contact contained substance obtained by contacting the contained substance with the alkaline aqueous solution is discarded. Since the contact contained substance is deactivated due to detoxification of the sulfur-containing atom material and treated with a liquid oil substrate, leaked sulfur-containing atom material can be safely and effectively disposed of.

[0086] The apparatus for manufacturing sulfur-containing atomic materials in the ninth embodiment of this invention is an apparatus.

[0087] It possesses: a reaction apparatus for raw materials containing sulfur atoms;

[0088] Liquid oil-based material storage container for storing liquid oil-based materials; and

[0089] Containers for storing alkaline aqueous solutions.

[0090] The apparatus for manufacturing sulfur-containing atomic materials in the tenth embodiment is an apparatus that, in the aforementioned ninth embodiment,

[0091] It also includes at least one apparatus selected from an apparatus for spraying or spraying a liquid oil-based substrate and an apparatus for spraying or spraying an alkaline aqueous solution. Furthermore, the apparatus for manufacturing sulfur-containing atomic materials in the eleventh embodiment is an apparatus that, in the aforementioned ninth or tenth embodiment,

[0092] It also has a hydrogen sulfide detection device.

[0093] The apparatus for manufacturing sulfur-containing atomic materials in this embodiment includes, in addition to a reaction apparatus for the raw materials of sulfur-containing atomic materials, a liquid oil-based storage container and an alkaline aqueous solution storage container. The raw materials for sulfur-containing atomic materials are reacted to become sulfur-containing atomic materials. Examples include raw materials used to manufacture sulfide solid electrolytes (also referred to as "solid electrolyte raw materials") and raw materials used to manufacture the raw materials used in the manufacture of the sulfide solid electrolyte (solid electrolyte raw materials).

[0094] By configuring the manufacturing apparatus of this embodiment in such a way, even in the event of leakage of raw materials used in the manufacture of sulfide solid electrolytes such as lithium sulfate and sulfur, or solid electrolyte raw materials such as lithium sulfide and phosphorus pentasulfide, intermediates such as electrolyte precursors, and sulfide solid electrolytes that become finished products, the leakage can be safely and effectively addressed and handled.

[0095] Furthermore, by having at least one device selected from the selection of a device for spraying or distributing liquid oil substrates and a device for spraying or distributing alkaline aqueous solutions, it is possible to deal with and handle leaked sulfur-containing atomic materials more safely and effectively.

[0096] In addition, the presence of a hydrogen sulfide detection device is particularly effective in terms of safety.

[0097] The equipment for handling sulfur-containing atomic materials in the twelfth embodiment of this invention is as follows:

[0098] A device for handling sulfur-containing materials includes: a storage container A for storing at least one sulfur-containing material selected from raw materials containing sulfur atoms, electrolyte precursors, and sulfide solid electrolytes; and

[0099] Storage container B stores liquid oil-based materials.

[0100] The sulfur-containing atom material handling equipment of this embodiment, by having a storage container A for storing sulfur-containing atom materials and a storage container B for storing liquid oil-based materials, can be used as a handling equipment for safely handling sulfur-containing atom materials.

[0101] The transport warehouse for handling sulfur-containing atomic materials in the thirteenth embodiment of this invention is as follows:

[0102] A transport container for handling sulfur-containing materials includes at least one storage container selected from storage section A and storage section B, wherein storage section A stores at least one sulfur-containing material selected from raw materials and electrolyte precursors containing sulfur atoms, and sulfide solid electrolytes.

[0103] Storage section B stores liquid oil-based materials.

[0104] The transport container for transporting sulfur-containing atomic materials according to this embodiment can be used as a transport container for safely transporting sulfur-containing atomic materials by having a storage section A for storing sulfur-containing atomic materials and a storage section B for storing liquid oil-based materials.

[0105] [To bring sulfur-containing atomic materials into contact with liquid oil-based substrates]

[0106] The method for processing sulfur-containing materials according to this embodiment includes contacting at least one sulfur-containing material selected from sulfur-containing raw materials, electrolyte precursors, and sulfide solid electrolytes with a liquid oil substrate. First, the contacting of the sulfur-containing material with the liquid oil substrate will be explained.

[0107] [Methods for processing sulfur-containing atomic materials]

[0108] The method for processing sulfur-containing atomic materials in this embodiment is as follows:

[0109] A method for processing a sulfur-containing material includes: contacting at least one sulfur-containing material selected from a sulfur-containing raw material, an electrolyte precursor, and a sulfide solid electrolyte with a liquid oil substrate; and

[0110] The resulting mixture containing the sulfur-containing atomic material and the liquid oil substrate is brought into contact with an alkaline aqueous solution.

[0111] The processing method of this embodiment will be described below.

[0112] (Sulfur-containing atomic materials)

[0113] In the processing method of this embodiment, the sulfur-containing material to be processed is a raw material containing sulfur atoms, an electrolyte precursor, and a sulfide solid electrolyte.

[0114] (raw material)

[0115] The raw material is a substance containing sulfur atoms. Examples of such raw materials include substances used as raw materials in the manufacture of sulfide solid electrolytes (solid electrolyte raw materials) and substances used as raw materials for manufacturing such sulfide solid electrolytes (solid electrolyte raw materials). Examples of such raw materials include substances containing at least one atom selected from lithium atoms, sulfur atoms, and phosphorus atoms, and substances containing at least one atom selected from lithium atoms, sulfur atoms, phosphorus atoms, and halogen atoms.

[0116] Substances containing sulfur atoms used in the manufacture of sulfide solid electrolytes, which can serve as raw materials for solid electrolytes, include, more specifically: lithium sulfide; phosphorus sulfides such as phosphorus trisulfide (P2S3) and phosphorus pentasulfide (P2S5); and thiophosphoric fluoride halides such as thiophosphoric fluoride (PSF3), thiophosphoric chloride (PSCl3), thiophosphoric bromide (PSBr3), thiophosphoric iodide (PSI3), dichlorothiophosphoric fluoride (PSCl2F), and dibromothiophosphoric fluoride (PSBr2F). Other examples include: alkali metal sulfides such as sodium sulfide, potassium sulfide, rubidium sulfide, and cesium sulfide; and metal sulfides such as silicon sulfide, germanium sulfide, boron sulfide, gallium sulfide, tin sulfide (SnS, SnS2), aluminum sulfide, and zinc sulfide.

[0117] In addition, substances used as raw materials for manufacturing solid electrolytes include, for example, lithium sulfate, lithium hydrogen sulfide, and sulfur.

[0118] Substances that are not sulfur atoms and can be used as raw materials for sulfide solid electrolytes, other than the raw materials mentioned above, include, for example, substances containing at least one atom selected from the four types of atoms and not containing sulfur atoms. More specifically, examples include: lithium halides such as lithium fluoride, lithium chloride, lithium bromide, and lithium iodide; phosphorus halides such as various phosphorus fluorides (PF3, PF5), various phosphorus chlorides (PCl3, PCl5, P2Cl4), various phosphorus bromides (PBr3, PBr5), and various phosphorus iodides (PI3, P2I4); raw materials composed of at least two atoms selected from the four types of atoms; halogen monomers such as bromine (Br2) and iodine (I2).

[0119] Furthermore, examples can be given of substances containing at least one atom selected from the four types of atoms mentioned above, and also containing atoms other than the four types of atoms mentioned above. More specifically, examples include: lithium compounds such as lithium oxide, lithium hydroxide, and lithium carbonate; phosphoric acid compounds such as sodium phosphate and lithium phosphate; alkali metal halides other than lithium such as sodium iodide, sodium fluoride, sodium chloride, and sodium bromide; metal halide such as aluminum halide, silicon halide, germanium halide, arsenic halide, selenium halide, tin halide, antimony halide, tellurium halide, and bismuth halide; phosphorus halides such as phosphorus trichloride (POCl3) and phosphorus tribromide (POBr3); and so on. The lithium compounds among the substances mentioned above can also be used as raw materials for manufacturing solid electrolytes.

[0120] In the processing method of this embodiment, the cases where the solid electrolyte raw material is one of the above-mentioned substances or a combination of multiple substances are considered, that is, the case where the solid electrolyte raw material leaks alone or the case where multiple solid electrolyte raw materials leak.

[0121] Solid electrolyte raw materials that have leaked in various situations during the manufacture of sulfide solid electrolytes include, for example, combinations of lithium sulfide and phosphorus sulfide, combinations of lithium sulfide, phosphorus sulfide and lithium halide, combinations of lithium sulfide, phosphorus sulfide and halogen monomers, and combinations of lithium sulfide, phosphorus sulfide, lithium halide and halogen monomers.

[0122] (electrolyte precursor)

[0123] As described above, the electrolyte precursor is a precursor of a sulfide solid electrolyte obtained during the manufacturing process of a sulfide solid electrolyte. It exhibits a defined peak and is therefore considered a complex formed from the solid electrolyte raw material via a complexing agent such as a solvent containing heteroatoms. In other words, the electrolyte precursor is the object of a processing method that employs a manufacturing method for a sulfide solid electrolyte that includes reacting the solid electrolyte raw material using a complexing agent.

[0124] The solid electrolyte raw material used to form an electrolyte precursor includes the solid electrolyte raw material required to form a sulfide solid electrolyte. Therefore, the solid electrolyte raw material used to form an electrolyte precursor includes a variety of substances exemplified as the above-mentioned solid electrolyte raw material, namely, combinations of lithium sulfide and phosphorus sulfide, combinations of lithium sulfide, phosphorus sulfide and lithium halide, combinations of lithium sulfide, phosphorus sulfide and halogen monomers, and combinations of lithium sulfide, phosphorus sulfide, lithium halide and halogen monomers, etc.

[0125] Solvents containing heteroatoms are solvents that readily form complexes with solid electrolyte raw materials; they can also be called complexing agents.

[0126] Examples of heteroatoms included in the complexing agent include oxygen atoms, nitrogen atoms, sulfur atoms, chlorine atoms, and phosphorus atoms, with oxygen atoms and nitrogen atoms being preferred. The solvent containing heteroatoms may contain one or more of these heteroatoms.

[0127] Examples of solvents containing heteroatoms include alcohols, ethers, esters, aldehydes, ketones, and other solvents containing oxygen atoms; amines, nitriles, and other solvents containing nitrogen atoms; and amides, and other solvents containing both oxygen and nitrogen atoms. Among these, alcohols and ethers are preferred as solvents containing oxygen atoms, and amines are preferred as solvents containing nitrogen atoms.

[0128] (Sulfide solid electrolyte)

[0129] As described above, the sulfide solid electrolyte is a solid electrolyte containing at least lithium atoms, phosphorus atoms and sulfur atoms, and preferably also includes solid electrolytes containing halogen atoms.

[0130] In the processing method of this embodiment, the sulfide solid electrolyte to be processed can be either an amorphous sulfide solid electrolyte or a crystalline sulfide solid electrolyte.

[0131] As amorphous sulfide solid electrolytes, representative examples include solid electrolytes composed of lithium sulfide, phosphorus sulfide, and further lithium halide, such as Li2S-P2S5, Li2S-P2S5-LiI, Li2S-P2S5-LiCl, Li2S-P2S5-LiBr, and Li2S-P2S5-LiI-LiBr; solid electrolytes containing other atoms such as oxygen atoms and silicon atoms, such as Li2S-P2S5-Li2O-LiI and Li2S-SiS2-P2S5-LiI.

[0132] The types of atoms that make up sulfide solid electrolytes can be identified, for example, by using an ICP-based luminescence spectrophotometer.

[0133] In addition, the crystalline sulfide solid electrolyte may be a so-called glass ceramic obtained by heating an amorphous sulfide solid electrolyte to a crystallization temperature or higher.

[0134] As the crystalline sulfide solid electrolyte, for example, the Li3PS4 crystal structure, the Li4P2S6 crystal structure, the Li7PS6 crystal structure, the Li7P3S 11 crystal structure, the crystal structure having peaks near 2θ = 20.2° and 23.6° (for example, Japanese Patent Application Laid-Open No. 2013-16423), etc.

[0135] A crystalline sulfide solid electrolyte having a thio-lithium superionic conductor region II type crystal structure can be exemplified. As the compositional formula of the thio-lithium superionic conductor region II type crystal structure, Li 4-x Ge 1-x P x S4 type thio-lithium superionic conductor region II (thio-LIS ICON Region II) type crystal structure (see Kanno et al., Journal of The Electrochemical Society, 148(7) A742-746 (2001)), and a crystal structure similar to the Li 4- x Ge 1-x P x S4 type thio-lithium superionic conductor region II (thio-LIS ICON Region II) type crystal structure (see Solid State Ionics, 177(2006), 2721-2725), etc.

[0136] In addition, a crystalline sulfide solid electrolyte having the following crystal structure can be exemplified: a thiogermanate type crystal structure having the above-mentioned structural framework of Li7PS6 and in which a part of P is replaced by Si. As the compositional formula of the thiogermanate type crystal structure, for example, those represented by Li 7-x P 1-y Si y S6 and Li 7+x P 1-y Si y S6 (x is from -0.6 to 0.6, y is from 0.1 to 0.6), the crystal structure represented by Li 7-x-2y PS 6-x-y Cl x (0.8 ≤ x ≤ 1.7, 0 < y ≤ -0.25x + 0.5), the crystal structure represented by Li 7-x PS 6-x Hax (Ha is Cl or Br, and x is preferably 0.2 to 1.8) etc.

[0137] (Liquid oil-based substrate)

[0138] As the liquid oil-based material used in the processing method of this embodiment, any liquid oil, commonly referred to as an oil-based material, can be used without particular limitation. For example, fuel oil base oil, lubricating oil base oil, and edible oil are preferred examples of liquid oil-based materials, considering safer and more effective handling and treatment of leaked sulfur-containing materials and ease of acquisition. These liquid oil-based materials are also preferred from a cost perspective, considering their use in treating sulfur-containing materials after use. A single oil-based material can be used alone, or multiple oil-based materials can be used in combination.

[0139] As described above, the liquid oil substrate needs to be in a liquid state, and preferably has the aforementioned kinematic viscosity. That is, in the processing method of this embodiment, at the temperature (ambient temperature) of the location where the liquid oil substrate is used, it is preferable to have the specified kinematic viscosity, thereby enabling safer and more effective handling and treatment of leaked sulfur-containing materials.

[0140] Examples of base oils for the aforementioned fuel oils include various types of oils such as automotive gasoline, jet fuel, kerosene, light oil, and heavy oil. Examples of base oils for lubricating oils include engine lubricants for vehicles and ships; machine oils such as refrigeration oil, turbine oil, gear oil, and hydraulic fluid; metalworking fluids; and electrical insulating oils.

[0141] In addition, examples of edible oils include vegetable oils such as flaxseed oil, safflower oil, sunflower oil, soybean oil, corn oil, cottonseed oil, sesame oil, olive oil, castor oil, peanut oil, coconut oil, palm kernel oil, rapeseed oil, and rice bran oil; animal oils such as tallow, lard, mutton tallow, whale oil, fish oil, and liver oil; and waste edible oils after the use of these vegetable and animal oils. Waste edible oils can also be refined through processes such as distillation and bleaching.

[0142] The processing method in this embodiment is merely a method aimed at treating and preferably discarding materials containing sulfur atoms. Therefore, considering factors such as cost, the liquid oil substrate described above is preferred. In contrast, the technologies described in, for example, Patent Documents 5 and 6 focus on suppressing hydrogen sulfide and atmospheric degradation when using sulfide solid electrolytes in all-solid-state batteries. That is, it is envisioned to use it together with sulfide solid electrolytes in all-solid-state batteries. Therefore, as a material that does not degrade the performance of all-solid-state batteries, Patent Document 5 uses insulating oils such as polysiloxanes, and Patent Document 6 uses a special material such as a water-impermeable matrix having double or triple bonds and containing additives that do not show reactivity with sulfide solid electrolytes.

[0143] The liquid oil substrate that can be used in the processing method of this embodiment is a liquid oil substrate that is envisioned to be processed and preferably waste. Therefore, the special materials used in the technologies described in Patent Documents 5 and 6 cannot be considered preferred materials in terms of cost and safety. On the contrary, it is difficult to imagine using the liquid oil substrates that can be used in the processing method of this embodiment, especially fuel oil base oil, lubricating oil base oil, and other mineral oil-based substrates containing multiple fractions, as well as waste edible oils, in the technologies described in Patent Documents 5 and 6.

[0144] Thus, the technical concept described in Patent Documents 5 and 6 allows for the direct use of fluids such as oils, which are suitable for the insulation of sulfide solid electrolytes, in all-solid-state batteries. The processing method of this embodiment envisions that the liquid oil substrate is processed after use and preferably discarded. Although both have something in common in that they use fluids to coat powders such as sulfide solid electrolytes, they can be said to belong to completely different technical fields.

[0145] (Contact between sulfur-containing materials and liquid oil-based substrates)

[0146] There are no particular restrictions on the method of contact between sulfur-containing materials and liquid oil substrates, as long as they are brought into contact, any method can be used. From the viewpoint of dealing with and handling leaked sulfur-containing materials more safely and effectively, contact is preferably achieved by either of the following methods (i) and (ii).

[0147] (i) Contact with a liquid oil substrate by spraying or spraying.

[0148] (ii) Contact is achieved by immersing a sulfur-containing material in a liquid oil-based substrate.

[0149] As described above, the contact method (i) can be used when the processing of the sulfur-containing material requires urgency, while the contact method (ii) can be used when there is no need for urgency. In the processing method of this embodiment, the contact method between the sulfur-containing material and the liquid oil substrate can be selected according to whether there is urgency.

[0150] In the case of the contact method described above (i), an apparatus that sprays or spreads liquid oil substrate can be used. As an apparatus, any apparatus capable of spraying or spreading liquid oil substrate can be used without particular restrictions, such as a pressurized sprayer, an oil spreading device, or a hose (which may also be equipped with a nozzle).

[0151] In the case of the contact method described in (ii) above, sulfur-containing materials can be added to a storage tank containing the liquid oil substrate for contact. To promote contact between the liquid oil substrate and the sulfur-containing materials, stirring blades can be attached to the storage tank. That is, a mixing tank with stirring blades can also be used as the storage tank. If it is considered that the contents described later should be contacted with an alkaline aqueous solution, a mixing tank is preferred.

[0152] Alternatively, sulfur-containing atomic materials can be added to a storage tank or mixing tank before supplying a liquid oil-based substrate.

[0153] (Amount of liquid oil-based base material used)

[0154] There are no particular limitations on the amount of liquid oil-based material used, as long as sufficient contact between the sulfur-containing material and the liquid oil-based material is achieved. From the viewpoint of more safely and effectively handling and dealing with leaked sulfur-containing material, the amount of liquid oil-based material used relative to 0.1L of sulfur-containing material is preferably 0.1L or more, more preferably 0.2L or more, and even more preferably 0.3L or more. The upper limit is preferably 20L or less, more preferably 15L or less, and even more preferably 10L or less. Representative examples of numerical ranges include 0.1L or more and 20L or less, 0.1L or more and 15L or less, 0.1L or more and 10L or less, 0.2L or more and 20L or less, 0.2L or more and 15L or less, 0.2L or more and 10L or less, 0.3L or more and 20L or less, 0.3L or more and 15L or less, and 0.3L or more and 10L or less. Furthermore, using the above-mentioned amounts allows for contact between the sulfur-containing material and the liquid oil-based material in a shorter time.

[0155] [Bring the substance into contact with an alkaline aqueous solution]

[0156] The processing method of this embodiment includes contacting an alkaline aqueous solution with a substance containing sulfur-containing material and a liquid oil substrate obtained by contacting the aforementioned sulfur-containing material with a liquid oil substrate.

[0157] (Alkaline aqueous solution)

[0158] As for the alkaline aqueous solution used in the processing method of this embodiment, any alkaline aqueous solution can be used without particular limitation. As an alkaline aqueous solution, considering safer and more effective handling and treatment of leaked sulfur-containing materials, as well as ease of acquisition, aqueous solutions of compounds such as alkali metal hydroxides and carbonates, and alkaline earth metal hydroxides are preferably examples. These compounds can be used alone or in combination.

[0159] Sodium and potassium are preferred as alkali metals, with sodium being more preferred. Calcium and magnesium are preferred as alkaline earth metals. Furthermore, hydroxides are preferred.

[0160] More specifically, aqueous solutions of the following substances are preferably provided: hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; carbonates of alkali metals such as sodium carbonate and potassium carbonate; hydroxides of alkaline earth metals such as calcium hydroxide and magnesium hydroxide; more preferably aqueous solutions of sodium hydroxide and sodium carbonate; and even more preferably aqueous solutions of sodium hydroxide.

[0161] The content of the aforementioned compounds in the alkaline aqueous solution is not particularly limited as long as it is sufficient to allow for treatment with a liquid oil-based substrate through contact with the contained material. This liquid oil-based substrate is used to deactivate sulfur-containing materials contained in the contained material due to detoxification and to inhibit the generation of hydrogen sulfide. For safer and more effective handling and treatment of leaked sulfur-containing materials, the content of the aforementioned compounds in the alkaline aqueous solution is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 3% by mass or more, and preferably 10% by mass or less as an upper limit, more preferably 8% by mass or less, and further preferably 6% by mass or less.

[0162] (Contact between the substance and alkaline aqueous solution)

[0163] Regarding the contact method between the contents containing sulfur-containing materials and liquid oil-based materials and the alkaline aqueous solution, there are no particular limitations as long as they can be brought into contact, and any method can be used. From the viewpoint of dealing with and handling leaked sulfur-containing materials more safely and effectively, contact is preferably carried out by either of the following methods (iii) and (iv).

[0164] (iii) Mix the contents with the alkaline aqueous solution.

[0165] (iv) Contact by spraying or sprinkling an alkaline aqueous solution.

[0166] The contact method described in (iii) above is a better method in terms of safety than that described in (iv) above, and it can more effectively achieve contact between the substance and the alkaline aqueous solution.

[0167] Regarding the contact method described in (iii) above, when combined with the contact method described in (ii) above, it is easier, safer, and more effective to handle and deal with leaked sulfur-containing materials. This is because, using the contact method described in (ii) above, for example, after immersing the sulfur-containing material in the liquid oil substrate to make contact, an alkaline aqueous solution is then supplied to the storage tank or mixing tank.

[0168] Similarly, if the contact method described in (i) is used, the leaked sulfur-containing material can be dealt with more easily, safely, and effectively. In this case, by using the contact method described in (i), the contents containing sulfur-containing material and liquid oil base material are recovered, and the contents are put into a mixing tank and mixed with an alkaline aqueous solution.

[0169] Furthermore, in cases where the detoxification of sulfur-containing materials is urgently needed, the contact method described in (iv) above is effective. Spraying or spraying alkaline aqueous solutions can be performed using equipment capable of spraying or spraying alkaline aqueous solutions. As equipment for spraying or spraying alkaline aqueous solutions, devices such as those exemplified as those capable of spraying or spraying the aforementioned liquid oil-based materials can be used.

[0170] Contact inclusions obtained by contacting a mixture containing sulfur-containing materials and a liquid oil-based substrate with an alkaline aqueous solution are preferably disposed of. The sulfur-containing materials in the contact inclusions have been detoxicated, and the liquid oil-based substrate has been treated. Therefore, leaked sulfur-containing materials can be safely and effectively disposed of as contact inclusions.

[0171] [Apparatus for manufacturing sulfur-containing atomic materials]

[0172] The apparatus for manufacturing sulfur-containing atomic materials according to this embodiment is an apparatus comprising a reaction apparatus for raw materials containing sulfur-containing atomic materials, a liquid oil base material storage container for storing liquid oil base material, and an alkaline aqueous solution storage container for storing alkaline aqueous solution.

[0173] As long as there are at least a reaction device, a liquid oil-based storage container, and an alkaline aqueous solution storage container, it is possible to safely and effectively deal with the leakage of substances used as raw materials in the manufacture of sulfide solid electrolytes, or sulfur-containing materials such as solid electrolyte raw materials, electrolyte precursors, and products (sulfide solid electrolytes) that may exist during the manufacturing stage of sulfide solid electrolytes.

[0174] The sulfur-containing material manufactured in the manufacturing apparatus, as described above, is at least one selected from sulfur-containing raw materials and electrolyte precursors, and sulfide solid electrolytes, preferably sulfur-containing raw materials and sulfide solid electrolytes. Examples of sulfur-containing raw materials include sulfur-containing solid electrolyte raw materials, such as lithium sulfide and phosphorus pentasulfide.

[0175] (Reaction apparatus for raw materials containing sulfur atoms)

[0176] Examples of sulfur-containing materials used as raw materials for reactions in a reaction apparatus include substances containing sulfur atoms, such as substances used as raw materials in the manufacture of sulfide solid electrolytes (solid electrolyte raw materials) and substances used as raw materials for the manufacture of such sulfide solid electrolytes (solid electrolyte raw materials).

[0177] The reaction apparatus used as a raw material for sulfur-containing atomic materials can be used without particular restriction, as long as it is an apparatus capable of reacting the aforementioned raw material for sulfur-containing atomic materials to produce raw materials (solid electrolyte raw materials) or sulfide solid electrolytes used in the manufacture of sulfide solid electrolytes. For example, the reaction of the solid electrolyte raw material in the manufacture of sulfide solid electrolytes can be carried out by known methods such as mechanical grinding, melt cooling, slurry method (including solution method), etc., as long as the apparatus corresponds to these methods.

[0178] For example, when using mechanical grinding, at least the following equipment is required: a ball mill, a bead mill, or other pulverizer; and various heating equipment such as hot plates, vacuum heating devices, argon atmosphere furnaces, firing furnaces, and vacuum firing furnaces, as needed for heating for crystallization, etc.

[0179] When using the melt quenching method, at least the following equipment is required: various heating equipment such as argon atmosphere furnace, firing furnace, vacuum firing furnace, etc., for the reaction of solid electrolyte raw materials; and a quenching tank for quenching the fired products produced by these heating equipment.

[0180] When using a slurry method (including a solution method), for example, when reacting a solid electrolyte raw material while mixing in a solvent (complexing agent) containing heteroatoms, the following equipment is sufficient: a mixing tank with stirring blades for generating a mixture (slurry-like) containing an electrolyte precursor and a residual complexing agent through the reaction of the solid electrolyte raw material and the complexing agent; various dryers such as horizontal dryers and horizontal vibrating flow dryers for removing residual complexing agents from the mixture (slurry-like); heating equipment for removing complexing agents from the electrolyte precursor; and heating equipment for crystallization, etc.

[0181] Heating equipment used for removing complexing agents from electrolyte precursors, and for crystallization, varies depending on the scale of the process, but examples include hot plates, vacuum heating devices, argon atmosphere furnaces, calcining furnaces, and vacuum calcining furnaces. Furthermore, these heating devices can also be used interchangeably.

[0182] In addition, the reaction apparatus may also include pulverizers, classifiers, etc., for particle size adjustment such as micronization.

[0183] The reaction of a substance used as a raw material for manufacturing solid electrolytes can be carried out, as needed, in the presence of a solvent, for example, in a reaction vessel equipped with stirring blades, while the substance is being mixed. When using a solvent, various dryers described above can be used to remove the solvent.

[0184] (Storage container)

[0185] The manufacturing apparatus of this embodiment includes the following storage containers: a liquid oil base material storage container for storing liquid oil base material and an alkaline aqueous solution storage container for storing alkaline aqueous solution.

[0186] As a form of storage container, there are no particular restrictions as long as it can store liquid oil-based materials or alkaline aqueous solutions.

[0187] The preferred location for the storage container is close to areas where sulfur-containing materials such as solid electrolyte raw materials, electrolyte precursors, and products (sulfide solid electrolytes) flow and are prone to leakage. More preferably, it is located within the site of a manufacturing apparatus for sulfide solid electrolytes. More specifically, the location is preferably within a radius of 100m from the reaction apparatus containing the solid electrolyte raw materials, and more preferably within a radius of 50m.

[0188] Furthermore, there can be one liquid oil-based material storage container and one alkaline aqueous solution storage container, or multiple containers. When multiple liquid oil-based material storage containers and alkaline aqueous solution storage containers are provided, they can be located near, for example, the flow points of the solid electrolyte raw materials, the electrolyte precursors, and the various flow points of the finished product.

[0189] (Spraying or spraying equipment)

[0190] The manufacturing apparatus of this embodiment preferably includes at least one device selected from a device for spraying or spreading a liquid oil substrate and a device for spraying or spreading an alkaline aqueous solution. Specifically, for the contact method described above (i) involving spraying or spreading a liquid oil substrate in urgent situations requiring the treatment of sulfur-containing atomic materials, it is preferable to include at least a device for spraying or spreading the liquid oil substrate.

[0191] The apparatus that can be used as a sprayer or sprayer of liquid oil substrate and an apparatus that can be used as a sprayer or sprayer of alkaline aqueous solution is consistent with the apparatus described as an apparatus that can be used in the contact method described above (i).

[0192] (Hydrogen sulfide detection device)

[0193] The manufacturing apparatus of this embodiment preferably includes a hydrogen sulfide detection device. In the event of a leak of sulfur-containing material, by measuring the concentration of hydrogen sulfide in the surrounding environment using the hydrogen sulfide detection device, it is possible to handle the situation quickly while ensuring safety.

[0194] As a hydrogen sulfide detection device, any device can be used without particular restrictions as long as it can detect hydrogen sulfide, such as a commercially available hydrogen sulfide detector.

[0195] Equipment for handling sulfur-containing atomic materials

[0196] The equipment for handling sulfur-containing materials according to this embodiment includes: a storage container A for storing at least one sulfur-containing material selected from raw materials containing sulfur atoms, electrolyte precursors, and sulfide solid electrolytes; and a storage container B for storing liquid oil-based materials.

[0197] In the case of sulfur-containing materials, it is conceivable to transport, for example, solid electrolyte raw materials such as lithium sulfide and phosphorus sulfide containing sulfur atoms, lithium sulfate and sulfur containing sulfur atoms as raw materials for solid electrolytes, and sulfide solid electrolytes as products obtained using solid electrolyte raw materials. The sulfur-containing material handling equipment of this embodiment is extremely useful in handling these sulfur-containing materials.

[0198] The handling equipment in this embodiment is used, for example, on a loading platform mounted on a truck, a train, or a ship.

[0199] In the event of leakage of sulfur-containing materials during handling, it is extremely important from a safety perspective to first bring the leaked sulfur-containing materials into contact with the liquid oil-based material through methods such as spraying or sprinkling, especially for the loading platform of trucks or the loading area of ​​ships. Therefore, the sulfur-containing material handling equipment of this embodiment includes not only a storage container A for storing the sulfur-containing materials but also a storage container B for storing the liquid oil-based material. Thus, the sulfur-containing material handling equipment of this embodiment can be considered as a device designed for preliminary handling of sulfur-containing material leaks.

[0200] As for the form of the handling equipment, there are no particular restrictions as long as it has a storage container A for storing sulfur-containing atomic materials and a storage container B for storing liquid oil-based materials. For example, the following forms are preferred: a form in which a partition plate is provided in a container to divide it into a storage container A for storing sulfur-containing atomic materials and a storage container B for storing liquid oil-based materials; and a form consisting of independent storage containers A and B.

[0201] As a method of using the handling equipment in this embodiment, for example, in the case of having a storage container A for storing sulfur-containing atomic materials and a storage container B for storing liquid oil substrate, when the sulfur-containing atomic materials leak from the storage container A, the leaked sulfur-containing atomic materials can be recovered and put into the storage container B, or the leaked sulfur-containing atomic materials can be sprayed or sprinkled onto the liquid oil substrate stored in the storage container B.

[0202] Furthermore, the handling equipment of this embodiment may further include at least one storage container selected from a storage container C containing a substance comprising sulfur-containing atomic material and a liquid oil base material and a storage container D containing an alkaline aqueous solution.

[0203] For example, in the case of spraying or spraying the leaked sulfur-containing material into the liquid oil-based material stored in storage container B, storage container C is useful when recovering and storing the contents containing the sulfur-containing material and the liquid oil-based material. Furthermore, storage container D is useful when spraying or spraying the liquid oil-based material to create a mixture containing the sulfur-containing material and the liquid oil-based material, and when performing deactivation due to detoxification, while simultaneously processing the liquid oil-based material.

[0204] The handling equipment of this embodiment may also include a storage container E for storing substances obtained by contacting a substance containing sulfur-containing materials and a liquid oil-based material with an alkaline aqueous solution. For example, the storage container E can perform the following: by adding the substance obtained by spraying or sprinkling the liquid oil-based material onto the sulfur-containing material and supplying the alkaline aqueous solution stored in the storage container D to the storage container E, deactivation due to non-toxicity and treatment of the liquid oil-based material can be carried out during handling.

[0205] [Transport warehouse for handling sulfur-containing atomic materials]

[0206] The transport container for handling sulfur-containing materials in this embodiment includes at least one storage container selected from storage section A and storage section B. Storage section A stores at least one sulfur-containing material selected from raw materials and electrolyte precursors containing sulfur atoms, as well as sulfide solid electrolytes; storage section B stores liquid oil-based materials.

[0207] The transport container for handling in this embodiment, like the aforementioned transport equipment, can be considered as a preliminary treatment for situations where sulfur-containing atomic materials are leaked.

[0208] Regarding the appearance of the transport container, considering versatility, it is preferable to have a form similar to that used in loading platforms of trucks, trains, ships, etc. Furthermore, the form of storage units A and B is not particularly limited as long as they can be installed inside the transport container.

[0209] For example, the following forms are preferred: a form in which a partition is provided in a container to divide it into a storage section A for storing sulfur-containing atomic materials and a storage section B for storing liquid oil substrate; and a form consisting of separate containers constituting storage section A and containers constituting storage section B.

[0210] The transport container of this embodiment, like the transport equipment described above, may further include at least one storage section selected from a storage section C for storing a substance containing sulfur-containing materials and a liquid oil-based material, and a storage section D for storing an alkaline aqueous solution. Furthermore, similar to the transport equipment described above, it may also include a storage section E for storing a substance obtained by contacting the substance containing sulfur-containing materials and a liquid oil-based material with an alkaline aqueous solution.

[0211] The usage of these storage sections C to E is the same as the usage of the storage containers C to E of the aforementioned handling equipment.

[0212] Example

[0213] The invention will now be described in detail by way of examples, but the invention is not limited to these examples.

[0214] (Experimental equipment)

[0215] use Figure 1 The experimental setup shown is used to measure the amount (concentration) of hydrogen sulfide produced. Figure 1 The experimental setup shown includes a humidification tank filled with water, a holding tank containing sulfur-containing materials, a hydrogen sulfide concentration measuring device, a hydrogen sulfide collection tank, and a flow meter. Air humidified in the humidification tank comes into contact with the sulfur-containing materials in the holding tank, thereby generating hydrogen sulfide through the interaction of moisture in the air and the sulfur-containing materials. For the air containing hydrogen sulfide, the concentration of hydrogen sulfide is measured in the hydrogen sulfide concentration measuring device, and then the hydrogen sulfide is collected in the hydrogen sulfide collection tank containing an aqueous sodium hydroxide solution before being released into the atmosphere.

[0216] While humidifying the air, liquid oil and alkaline aqueous solution are injected into the holding tank from the liquid oil-based injection device and the alkaline aqueous solution injection device, respectively, so that they come into contact with the sulfur-containing material. The amount of hydrogen sulfide produced (the concentration of hydrogen sulfide) is measured, thereby confirming the behavior of hydrogen sulfide.

[0217] (Example 1-1)

[0218] Add 0.2 g of a sulfide solid electrolyte with a sulfide-germanium sulfide crystal structure to a holding tank (Schrank bottle). Immediately immerse the solid electrolyte in 50 mL of edible oil, stir for 30 seconds, and let stand. Next, begin supplying air at a flow rate of 300 cc / min (relative humidity: 0.3%), while maintaining a humidification tank with 90% humidity, and allow it to contact the contents of the holding tank containing the sulfide solid electrolyte and edible oil. Sixty minutes after the start of air supply, further add 50 mL of sodium hydroxide aqueous solution (4% by mass) and stir. The concentration of hydrogen sulfide in the air, measured using a measuring instrument, is shown below. Figure 2 .

[0219] (Examples 1-2)

[0220] In Example 1-1 above, the sulfide solid electrolyte was replaced with lithium sulfide, and the experiments were otherwise performed in the same manner as in Example 1-1. The results of measuring the concentration of hydrogen sulfide in the air using a measuring instrument are shown below. Figure 2 .

[0221] (Example 2-1)

[0222] Add 0.2 g of a sulfide solid electrolyte with a sulfide-germanium sulfide crystal structure to a holding tank (Schrank bottle). Initiate air supply at a flow rate of 300 cc / min while maintaining 90% humidity in a humidifying tank, ensuring contact between the air and the sulfide solid electrolyte in the holding tank. Ten minutes after the start of air supply, add 50 mL of edible oil, gently shake to mix, and allow to stand. Forty minutes after the start of air supply, add a further 50 mL of sodium hydroxide aqueous solution (4% by mass). The concentration of hydrogen sulfide in the air, measured using a measuring instrument, is shown below. Figure 3 .

[0223] (Example 2-2)

[0224] In Example 2-1 above, the sulfide solid electrolyte was replaced with lithium sulfide. Edible oil was injected 6 minutes after the start of air supply, followed by an aqueous sodium hydroxide solution 60 minutes later. Otherwise, the experiment was conducted in the same manner as in Example 2-1. The results of measuring the concentration of hydrogen sulfide in the air using a measuring instrument are shown below. Figure 3 .in addition, Figure 3The concentration of hydrogen sulfide after 60 minutes is not plotted, but since the concentration of hydrogen sulfide is already below 1.0 ppm by mass, it is omitted.

[0225] (Comparative Example 1-1)

[0226] In Example 1-1, air supply was initiated without the injection of edible oil, followed by the injection of sodium hydroxide aqueous solution after 30 minutes. Otherwise, the experiment was conducted in the same manner as in Example 1-1. The results of measuring the concentration of hydrogen sulfide in the air using a measuring instrument are shown below. Figure 4 .

[0227] (Comparative Examples 1-2)

[0228] In Examples 1-2, air supply was initiated without the injection of edible oil, followed by the injection of sodium hydroxide aqueous solution after 8 minutes. Otherwise, the experiment was conducted in the same manner as in Examples 1-2. The results of measuring the concentration of hydrogen sulfide in the air using a measuring instrument are shown below. Figure 4 .

[0229] (Comparative Example 2-1)

[0230] In Example 1-1, 4 cc of quicklime was injected instead of cooking oil. The mixture was gently shaken and mixed after 41 minutes and 48 minutes from the start of air supply. After 50 minutes, an aqueous sodium hydroxide solution was injected. Otherwise, the experiment was conducted in the same manner as in Example 1-1. The results of measuring the concentration of hydrogen sulfide in the air using a measuring instrument are shown below. Figure 5 .

[0231] (Comparative Example 2-2)

[0232] In Examples 1-2, 4 cc of quicklime was injected instead of cooking oil, and an aqueous sodium hydroxide solution was injected 15 minutes after the start of air supply. Otherwise, the experiment was conducted in the same manner as in Examples 1-2. The results of measuring the concentration of hydrogen sulfide in the air using a measuring instrument are shown below. Figure 5 .

[0233] (Comparative Example 3-1)

[0234] In Example 1-1, 4 cc of potassium bicarbonate was injected instead of cooking oil. Sodium hydroxide aqueous solution was injected and stirred 20 minutes after the start of air supply. Otherwise, the experiment was conducted in the same manner as in Example 1-1. The results of measuring the concentration of hydrogen sulfide in the air using a measuring instrument are shown below. Figure 6 .

[0235] (Comparative Example 3-2)

[0236] In Examples 1-2, 4 cc of potassium bicarbonate was injected instead of cooking oil, and an aqueous solution of sodium hydroxide was injected 10 minutes after the air supply began. Otherwise, the experiments were conducted in the same manner as in Examples 1-2. The results of measuring the concentration of hydrogen sulfide in the air using a measuring instrument are shown below. Figure 6 .

[0237] (Comparative Example 4-1)

[0238] In Example 1-1, edible oil and sodium hydroxide aqueous solution were not used; otherwise, the experiment was conducted in the same manner as in Example 1-1. The results of measuring the concentration of hydrogen sulfide in the air using a measuring instrument are shown below. Figure 7 .

[0239] (Comparative Example 4-2)

[0240] In Examples 1-2, edible oil and sodium hydroxide aqueous solution were not used; dry air (relative humidity: 0.3%) was used (the dry air was not used through a humidification tank), and the experiments were otherwise conducted in the same manner as in Examples 1-2. The results of measuring the concentration of hydrogen sulfide in the air using a measuring instrument are shown below. Figure 8 .

[0241] The results of the embodiments confirm that, according to the processing method of this embodiment, by contacting the sulfur-containing material with the liquid oil substrate, the amount of hydrogen sulfide generated immediately decreases, and then by contacting with the alkaline aqueous solution, the amount of hydrogen sulfide generated is further reduced, resulting in complete detoxification and inactivation. Furthermore, after contact with the liquid oil substrate, the amount of hydrogen sulfide generated does not increase. Additionally, in Examples (1-2), a slight tendency for the amount of hydrogen sulfide generated was observed, because, experimentally, lithium sulfide remained in an adhered state in the holding tank (Schrank flask).

[0242] On the other hand, the results of the comparative examples confirmed that the amount of hydrogen sulfide generated increased if it did not come into contact with a liquid oil-based substrate. The quicklime used in Comparative Example 2 is known to be an alkaline compound, and while it had a slight effect in suppressing the generation of hydrogen sulfide, it did not reach a sufficient level of suppression. In Comparative Example 3, which used potassium bicarbonate, a common fire extinguishing agent, the generation of hydrogen sulfide was not further suppressed compared to Comparative Example 2, which used quicklime. Furthermore, it was confirmed that in Comparative Example 4, without the use of a liquid oil-based substrate and an alkaline aqueous solution, a large amount of hydrogen sulfide was generated, posing a safety concern.

[0243] Industrial applicability

[0244] The method for handling sulfur-containing materials according to this embodiment can safely and effectively address leaks of sulfur-containing materials such as raw materials, intermediates, and products containing sulfur atoms. Therefore, it is suitable for use in places where sulfur-containing materials are handled, such as laboratory equipment and factory equipment equipped with manufacturing apparatuses for sulfur-containing materials such as sulfide solid electrolytes and solid electrolyte raw materials containing sulfur atoms. Furthermore, the equipment and transport container for handling sulfur-containing materials according to this embodiment can be suitable for handling sulfur-containing materials using trucks, trains, and ships.

Claims

1. A method for processing sulfur-containing atomic materials, characterized in that, include: Contact at least one sulfur-containing material selected from sulfur-containing raw materials and electrolyte precursors, as well as sulfide solid electrolytes, with a liquid oil substrate. and The resulting mixture containing the sulfur-containing atomic material and the liquid oil substrate is brought into contact with an alkaline aqueous solution.

2. The method for processing sulfur-containing atomic materials as described in claim 1, characterized in that, The liquid oil base material is at least one oil base material selected from fuel oil base oil, lubricating oil base oil and edible oil.

3. The method for processing sulfur-containing atomic materials as described in claim 1 or 2, characterized in that, During the process of bringing the sulfur-containing atomic material into contact with the liquid oil substrate, the contact is achieved by spraying or spraying the liquid oil substrate.

4. The method for processing sulfur-containing atomic materials as described in claim 1 or 2, characterized in that, During the process of bringing the sulfur-containing material into contact with the liquid oil substrate, the sulfur-containing material is immersed in the liquid oil substrate to achieve contact.

5. The method for processing sulfur-containing atomic materials as described in any one of claims 1 to 4, characterized in that, During the process of bringing the sulfur-containing atomic material into contact with the liquid oil substrate, the amount of liquid oil substrate used relative to 0.1L of the sulfur-containing atomic material is more than 0.1L and less than 20L.

6. The method for processing sulfur-containing atomic materials as described in any one of claims 1 to 5, characterized in that, The alkaline aqueous solution is an aqueous solution of at least one compound selected from alkali metal hydroxides and carbonates, and alkaline earth metal hydroxides.

7. The method for processing sulfur-containing atomic materials according to any one of claims 1 to 6, characterized in that, During the process of contacting the contained substance with the alkaline aqueous solution, the contained substance is mixed with the alkaline aqueous solution.

8. The method for processing sulfur-containing atomic materials as described in any one of claims 1 to 7, characterized in that, Discard the contact contents obtained by contacting the contents with an alkaline aqueous solution.

9. An apparatus for manufacturing sulfur-containing atomic materials, characterized in that, It possesses: a reaction apparatus for raw materials containing sulfur atoms; Liquid oil-based material storage container for storing liquid oil-based materials; and An alkaline aqueous solution storage container for storing alkaline aqueous solutions.

10. The apparatus for manufacturing sulfur-containing atomic materials as described in claim 9, characterized in that, It also includes at least one device selected from a spraying or spraying device for a liquid oil substrate and a spraying or spraying device for an alkaline aqueous solution.

11. The apparatus for manufacturing sulfur-containing atomic materials as described in claim 9 or 10, characterized in that, It also has a hydrogen sulfide detection device.

12. A device for handling sulfur-containing atomic materials, characterized in that, It comprises: a storage container A for storing at least one sulfur-containing material selected from raw materials and electrolyte precursors containing sulfur atoms, and sulfide solid electrolytes; and Storage container B stores liquid oil-based materials.

13. A transport container for handling sulfur-containing atomic materials, characterized in that, It has at least one storage container selected from storage section A and storage section B, wherein storage section A stores at least one sulfur-containing material selected from raw materials and electrolyte precursors containing sulfur atoms and sulfide solid electrolytes; Storage section B stores liquid oil-based materials.

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