WO2021241402A1 - 電解質シート、固体電解質被覆繊維及びリチウムイオン電池 - Google Patents

電解質シート、固体電解質被覆繊維及びリチウムイオン電池 Download PDF

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Publication number
WO2021241402A1
WO2021241402A1 PCT/JP2021/019212 JP2021019212W WO2021241402A1 WO 2021241402 A1 WO2021241402 A1 WO 2021241402A1 JP 2021019212 W JP2021019212 W JP 2021019212W WO 2021241402 A1 WO2021241402 A1 WO 2021241402A1
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Prior art keywords
electrolyte
solid electrolyte
fiber
sheet
electrolyte sheet
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PCT/JP2021/019212
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English (en)
French (fr)
Japanese (ja)
Inventor
厚範 松田
和浩 引間
貴宏 小原
康史 高橋
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Toyohashi University of Technology NUC
Nippon Sheet Glass Co Ltd
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Toyohashi University of Technology NUC
Nippon Sheet Glass Co Ltd
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Priority to JP2022526958A priority Critical patent/JPWO2021241402A1/ja
Publication of WO2021241402A1 publication Critical patent/WO2021241402A1/ja
Anticipated expiration legal-status Critical
Priority to JP2025145211A priority patent/JP2025179138A/ja
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to an electrolyte sheet, a solid electrolyte-coated fiber, and a lithium ion battery, which contain a solid electrolyte and are suitable for forming an electrolyte layer or the like constituting a lithium ion battery.
  • a lithium-ion battery is a secondary battery having a structure in which lithium is desorbed as ions from the positive electrode during charging, moves to the negative electrode and is stored, and lithium ions are inserted from the negative electrode to the positive electrode and returned during discharge. Since this lithium-ion battery has features such as high energy density and long life, it has been conventionally used for home appliances such as personal computers and cameras, portable electronic devices or communication devices such as mobile phones, and power tools. It is widely used as a power source for electric tools and the like, and has recently been applied to large batteries mounted on electric vehicles (EV), hybrid electric vehicles (HEV), and the like.
  • EV electric vehicles
  • HEV hybrid electric vehicles
  • the sulfide solid electrolyte is usually in the form of powder.
  • a solid electrolyte sheet in which a solid electrolyte is attached to a fiber such as an electronically insulating inorganic fiber has been proposed (see Patent Document 1).
  • Patent Document 1 includes a solid electrolyte and a support having a plurality of openings, the solid electrolyte is filled in the openings of the support, the support is made of glass (glass fiber woven fabric), and the opening ratio of the support is high.
  • the solid electrolyte is 40 to 90%, the solid electrolyte is made of lithium sulfide and diphosphorus pentasulfide as raw materials, and the molar ratio of lithium sulfide to diphosphorus pentasulfide is 68:32 to 80:20, and the solid electrolyte is dissolved in a solvent.
  • Disclosed is a solid electrolyte sheet for a lithium battery obtained by applying the above to a support and drying it.
  • the internal structure of the lithium-ion battery is diverse, and the electrolyte layer may be flat or curved. In the latter case, it is necessary to bend the solid electrolyte sheet, so that it is necessary to have a structure in which cracks and cracks do not occur on the surface. Further, in the solid electrolyte sheet for a lithium battery shown in Patent Document 1, solid electrolyte particles may be detached during transportation or the like, and stable performance cannot be obtained when a lithium ion battery is mass-produced. There was something.
  • the problem of the present invention is that the desorption (powder falling) of the solid electrolyte is suppressed and it is easy to handle, and the generation of cracks and the powder falling during the bending process are suppressed so that the lithium ion battery can be efficiently manufactured.
  • Another object of the present invention is to provide a product containing the electrolyte sheet and having excellent transportability.
  • the present invention is shown below. 1.
  • An electrolyte sheet containing a plurality of inorganic fibers and a solid electrolyte An electrolyte sheet characterized in that the proportion of the inorganic fibers present is 60% or more in a cross section in the thickness direction cut perpendicular to the surface stretching direction of the electrolyte sheet.
  • 2. Item 2. The electrolyte sheet according to Item 1, wherein the content ratio of the solid electrolyte is 60 to 95% by mass when the total amount of the inorganic fibers and the solid electrolyte is 100% by mass.
  • 3. Item 2.
  • the electrolyte sheet according to Item 1 or 2 wherein the inorganic fiber contains glass fiber. 4. Item 2.
  • the electrolyte sheet of the present invention is easy to handle because it is difficult for the solid electrolyte to come off (powder fall off) and has excellent shape stability. In addition, cracks and powder falling are less likely to occur when bending or the like is performed during the manufacture of a lithium ion battery, so that a lithium ion battery having the desired performance can be efficiently manufactured. According to the electrolyte sheet-containing product of the present invention, the electrolyte sheet can be opened at the manufacturing site of the lithium ion battery, and the electrolyte sheet can be taken out and used for manufacturing the lithium ion battery while maintaining the above-mentioned excellent effects of the electrolyte sheet.
  • the lithium ion battery of the present invention contains an electrolyte sheet having high lithium ion conductivity, it exhibits excellent battery performance. Since the solid electrolyte-coated fiber of the present invention is not a bond between the fiber and the solid electrolyte via an adhesive, it is suitable for forming an electrolyte sheet having high lithium ion conductivity.
  • 6 is a cross-sectional image of the electrolyte sheet obtained in Example 1. It is a Si element map of the part surrounded by the dotted line in FIG. It is a graph which shows the profile of Si in the thickness direction of an electrolyte sheet based on the Si element map of FIG. It is a cross-sectional image of the electrolyte sheet obtained in Comparative Example 1. It is a Si element map of the part surrounded by the dotted line in FIG. It is a graph which shows the profile of Si in the thickness direction of an electrolyte sheet based on the Si element map of FIG. It is a schematic sectional drawing which shows an example of a lithium ion battery. It is a schematic perspective view which shows an example of the solid electrolyte coating fiber of this invention.
  • the electrolyte sheet of the present invention is a sheet containing a plurality of inorganic fibers and a solid electrolyte, and may contain other fibers as needed.
  • the electrolyte sheet of the present invention has a structure in which the proportion of the inorganic fibers present is 60% or more in a cross section in the thickness direction cut perpendicular to the surface stretching direction.
  • a "sheet" includes not only a sheet but also a long one.
  • the inorganic fiber is not particularly limited as long as it contains a portion made of an inorganic compound.
  • a fiber composed of only an inorganic compound, a fiber having a film containing an inorganic material on at least a part of the surface of the resin fiber, or a fiber having a granular portion can be mentioned.
  • the inorganic fiber according to the present invention is preferably a fiber composed of only an inorganic compound.
  • the inorganic compound is not particularly limited, but is preferably an oxide, a nitride, a carbonate, a titanate or the like.
  • Specific inorganic fibers include glass fiber, silica fiber, alumina fiber, silica-alumina fiber, silica-alumina-magnesia fiber, silica-alumina-zirconia fiber, silica-magnesia-calcia fiber, rock wool, slag wool, and titanium.
  • examples thereof include potassium acid whiskers, calcium carbonate whiskers, basalt fibers, sepilite, mineral fibers such as apparaljite and the like.
  • glass fiber is preferable.
  • the glass constituting the glass fiber is not particularly limited, but when the electrolyte sheet of the present invention is used for forming the electrolyte layer of the lithium ion battery, C glass, B glass, E glass and the like are preferable because they are excellent in chemical resistance.
  • the fiber diameter of the inorganic fiber is not particularly limited, but the upper limit is preferably 50 ⁇ m, more preferably 10 ⁇ m, and the lower limit is from the viewpoint of the mechanical strength of the electrolyte sheet of the present invention, flexibility against bending, and the like. It is preferably 0.01 ⁇ m, more preferably 0.1 ⁇ m.
  • the fiber length is not particularly limited, but is preferably in the range of 0.1 to 10 mm, more preferably 0.5 to 6 mm from the viewpoint of productivity of the nonwoven fabric of the electrolyte sheet of the present invention and uniformity of opening. be.
  • the electrolyte sheet of the present invention contains a plurality of inorganic fibers, and in the present invention, the size (diameter or length) of each fiber is uniform or non-uniform among the inorganic fibers containing the same material. But it may be. Further, when the constituent materials include a plurality of types of inorganic fibers different from each other, the diameter or length between the fibers made of one material and the fibers made of another material may be uniform or non-uniform.
  • the electrolyte sheet of the present invention may contain other fibers as described above.
  • the upper limit of the content ratio thereof with respect to the entire fibers is preferably 65% by mass, more preferably 55% by mass.
  • other fibers include organic fibers and natural fibers, and organic fibers are preferable.
  • a resin fiber is preferable.
  • polyester resin polyethylene terephthalate, etc.
  • aliphatic polyamide resin aramid resin
  • polyolefin resin polyolefin resin
  • cyclic olefin resin acrylic resin
  • polyacrylonitrile resin polyvinyl alcohol resin
  • polyacetal resin polyvinyl chloride resin
  • examples thereof include polyvinylidene chloride resin, ethylene / vinyl acetate copolymer, fluororesin, polyether sulfone resin, polyphenylene sulfide resin, cellulose and the like.
  • the resin fiber is a fiber composed of a single phase containing only one type of resin or a plurality of types of resin, or a fiber having a double-phase structure including a low melting point resin portion and a high melting point resin portion (hereinafter referred to as "composite resin fiber"). And so on.
  • composite resin fiber for example, a core-sheath type fiber, a side-by-side type fiber, or the like can be used.
  • the resin combination in the case of the composite resin fiber include PET / low melting point copolymerized polyester, PET / PE, PP (polypropylene) / PE (polyethylene), PP / low melting point copolymerized PP and the like.
  • the low melting point copolymerized polyester a modified resin having PET, PPT (polypropylene terephthalate), PBT (polybutylene terephthalate) or the like as a basic skeleton, that is, these polyesters, isophthalic acid, 5-sodium sulfoisophthalic acid, etc. , Aromatic dicarboxylic acids such as naphthalenedicarboxylic acid, and / or aliphatic dicarboxylic acids such as adipic acid and sebacic acid, and aliphatic polyhydric alcohols such as diethylene glycol, propylene glycol and 1,4-butanediol. Examples include copolymers.
  • polyester fiber is particularly preferable.
  • the fiber diameter and fiber length of the organic fiber are not particularly limited, but can be the same as the fiber diameter and fiber length of the inorganic fiber.
  • the fibers in the electrolyte sheet of the present invention may be either those in which the fibers are simply entangled with each other or those in which the fibers are intertwined with each other and the fibers are joined to each other. In the latter case, it is preferable that the fibers are in a bonded state by an adhesive at the contact point between the fibers.
  • the solid electrolyte is not particularly limited as long as it is conventionally known as a constituent material of the lithium ion battery, and is a sulfide-based solid electrolyte, a garnet-based solid electrolyte, a nitride-based solid electrolyte, and a perovskite-based solid.
  • examples thereof include an electrolyte, a zeolite-based solid electrolyte, a phosphoric acid-based solid electrolyte, and a NASICON-type solid electrolyte.
  • Li 3 PS 4 since it is excellent in lithium ion conductivity, Li 3 PS 4 , Li 7 P 2 S 8 X, Li 7 P 3 S 11 , Li 2 P 2 S 5 , Li 6 PS 5 X, Li 9.
  • a sulfide-based solid electrolyte such as 6 P 3 S 12 is preferable.
  • X is Cl, Br or I.
  • the solid electrolyte contained in the electrolyte sheet of the present invention may be only one type or two or more types. Further, the crystallinity of the solid electrolyte is not particularly limited, and the solid electrolyte contained in the electrolyte sheet may be either crystalline or amorphous, or may be both.
  • the volume ratio of all fibers and solid electrolytes contained in the electrolyte sheet of the present invention is not particularly limited. From the viewpoint of lithium ion conductivity, mechanical strength and flexibility, the volume ratios of the fiber and the solid electrolyte are preferably 5 to 60% by volume and 40 to 95% by volume, respectively, when the total of the two is 100% by volume. , More preferably 5 to 50% by volume and 50 to 95% by volume.
  • the mass ratio of the inorganic fiber and the solid electrolyte contained in the electrolyte sheet of the present invention is not particularly limited. From the viewpoint of mechanical strength and flexibility, the content ratios of the inorganic fiber and the solid electrolyte are preferably 5 to 50% by mass and 50 to 95% by mass, respectively, more preferably when the total of both is 100% by mass. It is 5 to 40% by mass and 60 to 95% by mass.
  • the electrolyte sheet of the present invention is substantially a medium-solid sheet mainly composed of a fiber containing an inorganic fiber and a solid electrolyte, and as shown in FIG. 1, the fiber 3 from one surface side to the other surface side.
  • the sheet 1 having a structure in which the solid electrolyte (unsigned) is uniformly contained, and the fiber and the solid electrolyte are uniformly contained in the sheet 1, while the surface layer on the one side and the surface layer on the other side are uniformly contained.
  • the thickness of the electrolyte sheet of the present invention is preferably 5 to 100 ⁇ m, more preferably 10 to 75 ⁇ m.
  • the electrolyte sheet of the present invention has a structure in which the proportion of the inorganic fibers present is 60% or more in the cross section in the thickness direction cut perpendicular to the surface stretching direction. This ratio is preferably 70% or more.
  • the method for measuring this ratio is shown in [Example], but is as follows. (1) The electrolyte sheet is photographed with an electron microscope so that the entire cross section in the thickness direction is included in the image (see FIGS. 2 and 5).
  • an element constituting an inorganic fiber contained in an electrolyte sheet by an energy dispersive X-ray analysis method in a region set so as to include the entire cross section in the thickness direction (hereinafter referred to as “measurement region”). Perform mapping analysis on elements not contained in the solid electrolyte.
  • the measurement element the inorganic fiber is a glass fiber containing a Si element, and when the Si element is not contained in the solid electrolyte, it is preferable to select the Si element.
  • the measurement region preferably has a lateral length of at least 40 ⁇ m.
  • the existence range of the Si element is determined by the following method using software.
  • the Si element map After converting the Si element map into an 8-bit grayscale image, this is binarized with a lower limit threshold value of 0 and an upper limit threshold value of 10, and the gray value of each pixel is set to 255 where the Si element is present and non-Si element. Converts the existing location to 0.
  • the range is set so that the upper end to the lower end of the Si element map fits exactly, and the profile of the range from the upper end to the lower end is created and graphed (see FIGS. 4 and 7).
  • the horizontal axis is the vertical distance of the Si element map, and the vertical axis is the average value of the horizontal gray values of the Si element map.
  • the ratio of the region where the pixel determined to be the presence of the Si element is 20% or more, that is, the region where the average value of the horizontal gray values is 51 or more is relative to the measurement region. Calculate whether it is (area ratio).
  • the electrolyte sheet of the present invention is a medium-solid sheet mainly composed of fibers containing inorganic fibers and a solid electrolyte, and has a shape that makes it difficult for the solid electrolyte to come off (powder fall off). Due to its excellent stability, the percentage of voids (presence rate) is low. The percentage of voids is preferably 20% or less, more preferably 10% or less. The void ratio can be calculated in an arbitrary range based on an image of a cross section obtained by cutting the electrolyte sheet in the thickness direction with, for example, an optical microscope, a laser microscope, an electron microscope, or the like. ..
  • the electrolyte sheet of the present invention has excellent lithium ion conductivity, and the conductivity measured at 25 ° C. by the AC impedance method is preferably 10 -4 S / cm or more.
  • Method (1) In a container, an aggregate of fibers containing inorganic fibers, which has a sheet shape (hereinafter referred to as "fiber sheet"), a solid electrolyte forming raw material, and an organic solvent are put into a container to form a solid electrolyte.
  • fiber sheet an aggregate of fibers containing inorganic fibers, which has a sheet shape (hereinafter referred to as "fiber sheet")
  • a solid electrolyte forming raw material and an organic solvent are put into a container to form a solid electrolyte.
  • Method (2) A container contains a plurality of inorganic fibers that are not immobilized on each other, a solid electrolyte forming raw material, and an organic solvent, and then the solid electrolyte forming raw material is reacted to cause a solid electrolyte.
  • Method (3) In a container, the fiber sheet and a solid electrolyte solution in which a solid electrolyte is dissolved in an organic solvent, or a solid electrolyte dispersion in which a solid electrolyte is dispersed in a dispersion medium made of an organic solvent.
  • Method (4) A solid electrolyte solution containing a plurality of inorganic fibers in a container and not immobilized with each other and a solid electrolyte dissolved in an organic solvent, or a dispersion in which the solid electrolyte is composed of an organic solvent. After adding the solid electrolyte dispersion liquid dispersed in the medium, the organic solvent is devolatile and the fiber surface is coated with the solid electrolyte to fill the voids between all the fibers with the solid electrolyte. How to make a medium solid sheet. In all of the above methods, heat treatment, press treatment, or the like may be performed after forming the sheet, if necessary.
  • the fiber sheet used in the above methods (1) and (3) is not particularly limited, and may be a fiber deposit, a non-woven fabric, a woven fabric, a woven fabric, or the like.
  • the fiber sheet may be composed of only fibers, or may be one in which a plurality of fibers are bonded by an adhesive.
  • the fiber sheet preferably contains 35% by mass or more of inorganic fibers with respect to the whole, and the inorganic fibers preferably contain glass fibers. This makes it possible to obtain an electrolyte sheet suitable as an electrolyte layer forming material for a lithium ion battery.
  • the porosity and basis weight of the fiber sheet are not particularly limited.
  • the porosity is preferably 50 to 95%, more preferably 60 to 90%.
  • the basis weight is preferably 1 to 100 g / m 2 , more preferably 1 to 20 g / m 2 .
  • the above fiber sheet is preferably a non-woven fabric.
  • the non-woven fabric may be either one in which the fibers are simply entangled with each other, or one in which the fibers are intertwined with each other and the fibers are joined to each other. In the case of the latter non-woven fabric, it is preferable that the fibers are in a bonded state by an adhesive at the contact point between the fibers.
  • the content ratio of the adhesive to the entire non-woven fabric is preferably 15% by mass or less, more preferably 15% by mass or less, in order to make the obtained electrolyte sheet excellent in conductivity. Is 12% by mass or less.
  • the thickness of the nonwoven fabric is usually 20 ⁇ m or more, but the obtained electrolyte sheet is suitable as an electrolyte layer forming material for giving a lithium ion battery having excellent performance, so it is preferably 5 to 100 ⁇ m, more preferably. It is 10 to 75 ⁇ m.
  • a plurality of fibers are used as a solid electrolyte forming raw material and an organic solvent, an organic solution of a solid electrolyte, or a solid electrolyte is an organic solvent. It means that most of the fibers are scattered before being placed in a container together with the solid electrolyte dispersion liquid dispersed in the dispersion medium consisting of the above to form the solid electrolyte on the fiber surface.
  • the inorganic fiber used in the above methods (2) and (4) is preferably a glass fiber containing C glass, B glass, E glass and the like. The preferred size of the inorganic fiber is as described above. Further, in the methods (2) and (4), the inorganic fiber and the organic fiber or the natural fiber can be used in combination, and in this case, the ratio of the inorganic fiber to the whole fiber is preferably 35% by mass or more. be.
  • the solid electrolyte forming raw material used for forming the solid electrolyte in the presence of the organic solvent is usually composed of a plurality of kinds of compounds. Then, in the organic solvent, a plurality of kinds of compounds are contact-reacted to form a solid electrolyte.
  • the preferred solid electrolyte is a sulfide-based solid electrolyte
  • the raw materials for forming the solid electrolyte are Li 3 PS 4 , Li 7 P 2 S 8 X, Li 7 P 3 S 11 , Li 2 P 2 S. 5 , Li 6 PS 5 X, Li 9.6 P 3 S 12 and the like are preferably contained.
  • X is Cl, Br or I.
  • Examples of the raw material for forming the sulfide-based solid electrolyte include lithium sulfide, phosphorus sulfide, lithium halide and the like.
  • Examples of phosphorus sulfide include diphosphorus pentasulfide (P 2 S 5 ), tetraphosphorus trisulfide (P 4 S 3 ), tetraphosphorus sesquioxide (P 4 S 7 ), and tetraphosphorus pentasulfide (P 4 S 5 ).
  • diphosphorus pentasulfide is preferable.
  • Examples of lithium halide include lithium fluoride, lithium chloride, lithium bromide, lithium iodide and the like.
  • the solid electrolyte forming raw material preferably contains lithium sulfide and diphosphorus pentasulfide, and it is also preferable that it contains lithium sulfide, diphosphorus pentasulfide and lithium halide.
  • the solid electrolyte used in the above methods (3) and (4) is preferably the above sulfide-based solid electrolyte, and is Li 3 PS 4 , Li 7 P 2 S 8 X, Li 7 P 3 S 11 , Li 2 P. 2 S 5 , Li 6 PS 5 X, Li 9.6 P 3 S 12 and the like.
  • Examples of the organic solvent that can be used in the above methods (1), (2), (3) and (4) include alcohols (aliphatic alcohols, alicyclic alcohols, aromatic alcohols, etc.), carboxylic acids, and carboxylic acid esters. Examples thereof include (saturated fatty acid esters and the like), ethers (including cyclic ethers), aldehydes, ketones, carbonate esters (dialkyl carbonates and the like), nitriles, amides, nitros, phosphate esters, halogenated hydrocarbons and the like. Of these, alcohols, carboxylic acid esters and carbonic acid esters are preferable, and carboxylic acid esters and carbonic acid esters are particularly preferable.
  • the organic solvent may be used alone or in combination of two or more.
  • the container used in the above methods (1), (2), (3) and (4) is not particularly limited, and for example, the shape and size are the size of the fiber sheet, the size of the sheet formed of inorganic fibers and the like. Is selected as appropriate.
  • the solid electrolyte formed by the reaction is not suspended alone in the organic solvent, and the fibers constituting the fiber sheet are efficiently coated with the solid electrolyte, and the voids between the fibers are solid.
  • a container in which the contact angle of the organic solvent on the inner surface of the container is 5 degrees or more higher than the contact angle of the organic solvent in at least one kind of fiber (preferably inorganic fiber) constituting the fiber sheet. Is preferable.
  • the contact angle with respect to the fibers made of at least one kind of material is 5 degrees or more lower than the contact angle with respect to the inner surface of the container. good.
  • the contact angle of the organic solvent on the inner surface of the container is at least at least in order to efficiently fill the voids between the fibers with the solid electrolyte while efficiently covering the fiber surface with the solid electrolyte. It is preferable to use a container having a contact angle of 5 degrees or more higher than the contact angle of the organic solvent in one type of fiber (preferably inorganic fiber).
  • the contact angle with respect to the fiber made of at least one kind material may be 5 degrees or more lower than the contact angle with respect to the inner surface of the container. ..
  • a plurality of non-immobilized fiber sheets or inorganic fibers are contained on the inner surface of the container before the electrolyte sheet is formed. Since at least the organic solvent of the fiber, the solid electrolyte forming raw material, the solid electrolyte and the organic solvent comes into contact with the fiber, a fluororesin; a silicone resin or the like is preferable as the material constituting the inner surface thereof.
  • fluororesins are preferable, and for example, polytetrafluoroethylene (hereinafter, may be referred to as “PTFE”), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), and tetrafluoroethylene / hexafluoropropylene are used together.
  • PTFE polytetrafluoroethylene
  • FEP tetrafluoroethylene / hexafluoropropylene copolymer
  • tetrafluoroethylene / hexafluoropropylene are used together.
  • the container may be made of these materials, or a film or sheet made of these materials may be processed into a container shape and arranged on the inner surface of a container made of another material. May be good. Further, the inner surface of the container made of other materials may have a film made of these materials.
  • the volume ratio of the fiber sheet and the solid electrolyte forming raw material or the solid electrolyte to be put in the container is preferably 5:95 to 60:40, more preferably 5:95 to 50:50.
  • the total amount of the plurality of fibers and the volume ratio of the solid electrolyte forming raw material or the solid electrolyte to be put in the container are preferably 5:95 to 60:40, more preferably 5. : 95 to 50:50.
  • the mass ratio of the solid electrolyte forming raw material or the solid electrolyte and the organic solvent is preferably 1:10 to 1:22, more preferably 1. : 14 to 1:18.
  • the reaction conditions for reacting the solid electrolyte forming raw materials to form the solid electrolyte are not particularly limited.
  • the reaction temperature is appropriately selected depending on the type of solid electrolyte to be formed, but is preferably 20 ° C to 200 ° C, more preferably 120 ° C to 180 ° C.
  • the solid electrolyte may be formed in an organic solvent, and depending on the type of the organic solvent, the reaction temperature may be the same as or close to the boiling point of the organic solvent. When the organic solvent is volatilized at the reaction temperature of No. 1, a solid electrolyte can be formed by this volatilization.
  • the atmosphere in the container can be an argon atmosphere, a dew point: ⁇ 30 ° C. or lower, or the like.
  • a method of reacting a solid electrolyte forming raw material in two steps can be applied.
  • the rest of the solid electrolyte forming raw material is organically prepared.
  • the organic solvent when the organic solvent adheres to the obtained electrolyte sheet, the organic solvent is applied by natural drying, heat drying, vacuum drying or the like. It is preferable to evaporate.
  • the electrolyte sheet can be heat-treated in order to obtain a solid electrolyte having the desired chemical properties or physical properties. This heat treatment may be performed in the above-mentioned heat drying or vacuum drying. By this heat treatment, for example, the solid electrolyte can be crystallized or non-crystallized.
  • the electrolyte sheet after devolatile or heat treatment may be pressed.
  • the above heat treatment may be performed after the press treatment.
  • the electrolyte sheet of the present invention is suitable for forming an electrolyte layer of a lithium ion battery, and can also be used for forming an electrode layer.
  • the electrolyte sheet of the present invention When the electrolyte sheet of the present invention is used for forming an electrolyte layer or an electrode layer of a lithium ion battery, it is a precision component regardless of its size, so that it is transported from the electrolyte sheet manufacturing site to the lithium ion battery manufacturing site. It is preferable that the air is shut off from the outside air. In such a case, since it is possible to suppress deterioration, deterioration, etc. of the electrolyte sheet, the electrolyte sheet-containing product of the present invention (electrolyte sheet packaging product) in which the electrolyte sheet is housed in the package. Is useful.
  • the package it is preferable to seal the package with the electrolyte sheet and an inert gas such as argon contained therein.
  • an inert gas such as argon contained therein.
  • two films can be used, and the electrolyte sheet can be accommodated in the space of the package forming a space between them.
  • a resin film or a metal-deposited resin film (aluminum-deposited resin film, etc.) is used, and the peripheral portion thereof is sealed so that one electrolyte sheet is held between the two films.
  • a resin film or a metal-deposited resin film aluminum-deposited resin film, etc.
  • the electrolyte sheet may be housed in the recess of the package having a container portion having a recess and a flange portion and a lid portion for at least sealing the recess. can. In this case, it can be obtained by using the resin container portion and the resin film lid portion.
  • the lithium ion battery of the present invention includes the above-mentioned electrolyte sheet of the present invention, and the structure thereof is not particularly limited, but can have, for example, the laminated structure shown in FIG.
  • the lithium ion battery 10 of FIG. 8 includes a positive electrode layer 11, a negative electrode layer 13, and an electrolyte layer 15 arranged between the positive electrode layer 11 and the negative electrode layer 13, and the electrolyte layer 15 is the electrolyte sheet of the present invention. Can consist of.
  • the electrolyte layer 15 is a layer capable of moving lithium ions by an electric field applied from the outside.
  • the thickness of the electrolyte layer 15 is preferably 5 to 100 ⁇ m, more preferably 10 to 75 ⁇ m.
  • the positive electrode layer 11 is an electrode layer containing a positive electrode active material that emits lithium ions during charging and occludes lithium ions during discharging.
  • the positive electrode active material is an oxide containing at least one metal element selected from manganese (Mn), cobalt (Co), nickel (Ni), iron (Fe), molybdenum (Mo) and vanadium (V). Examples include sulfides and phosphor oxides.
  • the negative electrode layer 13 is an electrode layer containing a negative electrode active material that occludes lithium ions during charging and releases lithium ions during discharging.
  • a carbon material lithium (Li), indium (In), aluminum (Al), silicon (Si) or the like of a metal or an alloy containing these; Sn x O y, MoO x , WO x, Li x Oxides such as CoO y (LiCoO 2 etc.), Li x Mn y Ni z Co w O (LiNi 1/3 Co 1/3 Mn 1/3 O 2 etc.), Li x CuP x O y ( LiCuPO 4 etc.) And so on.
  • the negative electrode layer 13 may be a composite negative electrode layer further containing a solid electrolyte, a conductive auxiliary agent and the like.
  • a material made of a carbon material, a metal powder, a metal compound, or the like can be used, and among these, the carbon material is preferably used.
  • carbon materials plate-like conductive substances such as graphene; linear conductive substances such as carbon nanotubes and carbon fibers; carbon black such as Ketjen black, acetylene black, thermal black and channel black, and granular conductivity such as graphite. Substances and the like can be mentioned.
  • the lithium ion battery of the present invention may further include a positive electrode collector that collects electricity from the positive electrode layer 11 and a negative electrode collector that collects electricity from the negative electrode layer 15.
  • the positive electrode current collector or the negative electrode current collector may be made of, for example, stainless steel, gold, platinum, copper, zinc, nickel, tin, aluminum or an alloy thereof, and may be a plate-like body or a foil-like body. , A mesh-like body and the like can be provided.
  • the solid electrolyte-coated fiber of the present invention is a composite fiber including a fiber portion made of a fiber and a solid electrolyte-coated layer containing a solid electrolyte and covering at least a part of the surface of the fiber portion.
  • the structure of the solid electrolyte-coated fiber of the present invention is not particularly limited, but may be, for example, the structure shown in FIG. FIG. 9 is a solid electrolyte-coated fiber 20 having a fiber portion 21 and a solid electrolyte-coated portion 23 that covers the surface of the fiber portion 21. Further, although not shown, the solid electrolyte-coated portion 23 may be a solid electrolyte-coated fiber formed on all the side surfaces of the fiber portion 21.
  • the mass ratio of the solid electrolyte in the solid electrolyte-coated fiber of the present invention depends on the constituent material of the fiber portion, but is preferably 50 to 95% by mass.
  • the fiber portion 21 constituting the solid electrolyte-coated fiber of the present invention may be derived from any of inorganic fiber, organic fiber and natural fiber. These fibers can be fibers made of the materials exemplified above.
  • the solid electrolyte contained in the solid electrolyte coating portion 23 is not particularly limited, but is preferably a sulfide-based solid electrolyte, and particularly preferably Li 3 PS 4 , Li 7 P 2 S 8 X, Li 7 P 3. S 11 , Li 2 P 2 S 5 , Li 6 PS 5 X, Li 9.6 P 3 S 12 and the like. In addition, X is Cl, Br or I.
  • the solid electrolyte contained in the solid electrolyte coating portion 23 may be only one type or two or more types.
  • the method for producing the solid electrolyte-coated fiber of the present invention is not particularly limited.
  • a preferred production method is, for example, to put the fiber, the solid electrolyte forming raw material, and the organic solvent in a container, and react the solid electrolyte forming raw material in the organic solvent to form a solid electrolyte on the surface of the fiber. It is a method of covering.
  • fibers can be used in place of the fiber sheet used in the above-mentioned method for manufacturing an electrolyte sheet.
  • heat treatment after the reaction for forming the solid electrolyte the same method as in the above-mentioned method for producing an electrolyte sheet can be used, and the description thereof will be omitted.
  • a nonwoven fabric containing a solid electrolyte-coated fiber By subjecting the solid electrolyte-coated fiber of the present invention to a conventionally known nonwoven fabric manufacturing process or the like, a nonwoven fabric containing a solid electrolyte-coated fiber can be produced.
  • the obtained solid electrolyte-coated fiber-containing nonwoven fabric can be further subjected to a heat treatment step, a pressing step, or the like.
  • non-woven fabric electrolyte sheets glass fibers (fiber diameter: 0.3 ⁇ m, fiber length: about 0.1 to 1 mm) produced by subjecting B glass to the flame method as inorganic fibers, and polyester resin as organic fibers.
  • a non-woven fabric (hereinafter referred to as "nonwoven fabric (N1)") obtained by wet-making using fibers (fiber diameter: 2 ⁇ m, fiber length: 3 mm) and then dip-coated with styrene / butadiene rubber as a binder is used. Using.
  • This non-woven fabric (N1) contains inorganic fibers, organic fibers and a binder in proportions of 52% by mass, 37% by mass and 11% by mass, respectively, when the total of these is 100% by mass, and the void ratio is It is 73% by volume, has a thickness of 22 ⁇ m, and has a basis weight of 10 g / m 2 .
  • Electrolyte sheets of Examples and Comparative Examples were produced using the above-mentioned non-woven fabric (N1) or the above-mentioned glass fibers, and various evaluations were performed.
  • Example 1 Under an argon atmosphere, charged with Li 2 S powder of ethanol 5 ml, and stirred to obtain a Li 2 S solution. Then, the polytetrafluoroethylene in the Petri dish, put and the Li 2 S solution and a circular nonwoven diameter 30 mm (N1), allowed to stand for 30 minutes at 25 ° C., vacuum dried (0.99 ° C., 1 hour) Was done. Thus, the surface of the fibers of the nonwoven fabric (N1) Li 2 S was obtained impregnated nuclear adhered nonwoven fabric.
  • Li 2 S powder and P 2 S 5 powder and LiI powders 1: 1: 1 (molar ratio)
  • Li 2 This P 2 S 5 powder was impregnated in the above nucleus adhesion nonwoven
  • Each was weighed and mixed so as to have a molar ratio of 1/3 with respect to the total Li 2 S composed of S and the above Li 2 S powder.
  • the ethyl propionate of the mixed powder and 10 ml stirred while irradiating ultrasonic waves, Li 2 S powder was dissolved P 2 S 5 powder and LiI powders.
  • the obtained solution was put into a petri dish made of polytetrafluoroethylene, and then the above-mentioned non-woven fabric with nuclei was put in, and the mixture was allowed to stand at room temperature for 6 hours. Then, vacuum drying (170 ° C., 2 hours) was performed.
  • a sheet (A1) with an electrolyte is obtained in which the voids of the nonwoven fabric (N1) are filled with the solid electrolyte Li 7 P 2 S 8 I (crystalline) and both sides are coated with Li 7 P 2 S 8 I. rice field.
  • the volume ratio of the non-woven fabric (N1) to the solid electrolyte in the sheet with electrolyte (A1) was 11:89.
  • the mass ratio of the glass fiber and the solid electrolyte was 8:92.
  • a test piece obtained by punching the obtained sheet with electrolyte (A1) to ⁇ 10 mm with a punch is filled inside a tubular body (inner diameter 10 mm) made of polyetheretherketone (PEEK), and then a flat surface having a diameter of 10 mm.
  • the test piece was inserted from both sides of the tubular body and pressed at 250 MPa with a hydraulic press to obtain an electrolyte sheet with a thickness of 52 ⁇ m. Then, in order to observe the cross section of this electrolyte sheet, the surface of the sheet was used under the conditions of a temperature of -70 ° C. and an acceleration voltage of 4 kW using a cross-section sample preparation device "IB-19520CCP" (model name) manufactured by JEOL Ltd.
  • FIG. 2 It was cut perpendicular to the stretching direction, and the image of FIG. 2 was obtained with a scanning electron microscope "JSM-7800F" (model name) manufactured by JEOL Ltd. Then, by the energy dispersive X-ray analysis method, mapping analysis on the Si element contained in the glass fiber constituting the nonwoven fabric (N1) was performed.
  • the analysis target is the portion surrounded by the dotted line in FIG. 2 (horizontal: about 54 ⁇ m, vertical: about 52 ⁇ m).
  • the image surrounded by the dotted line was cut out and shown in FIG. 3 as a mapping image of Si element (Si element map).
  • the black portion is a portion having a Si element.
  • the existence range of the Si element was determined by the following procedure using the software "ImageJ".
  • the Si element map of FIG. 3 was converted into an 8-bit grayscale image, which was binarized with a lower limit threshold value of 0 and an upper limit threshold value of 10.
  • the range was set so that the upper end to the lower end of the cross section of FIG. 3 fit exactly, and the profile of the selected range was created by using the "Plot profile" function of the above software, and the graph of FIG. 4 was obtained.
  • the horizontal axis is the vertical distance of the image of FIG. 3, and the vertical axis is the average value of the horizontal gray values of the image of FIG.
  • the ratio of the region where the average value of the gray values in the horizontal direction is 51 or more (that is, the number of pixels determined to be the presence of the Si element is 20% or more) to the cross-sectional thickness is calculated to be 73.
  • Was% see Table 1).
  • Powder drop test The electrolyte sheet was finely moved on the black sheet, and at this time, whether or not the solid electrolyte powder fell was visually observed and the weight change was confirmed to determine the powder drop property.
  • the weight change due to the weight loss was investigated by the following method. That is, the solid electrolyte sheet was punched into a circular shape ( ⁇ 10 mm) by punching, and this was designated as “test piece A”. Then, the weight (mg) of the test piece A is measured, placed in a cylindrical screw tube bottle (Maruem Co., Ltd., No.
  • Example 2 Under an argon atmosphere, the Li 2 S powder, the P 2 S 5 powder, and the Li I powder were weighed to a ratio of 3: 1: 1 (molar ratio) to obtain a total of 1.37 g of mixed powder. Next, this mixed powder, 10 ml of ethyl propionate, and 30 g of zirconia balls (diameter 4 mm) were placed in a resin conical tube (capacity 50 ml), and the shaker "ASCM-1" (model name) manufactured by AS ONE Co., Ltd. was placed. ) Was shaken at 25 ° C.
  • ASCM-1 model name
  • a slurry (suspension) containing a precursor of the solid electrolyte Li 7 P 2 S 8 I. Then, in this slurry, 0.15 g of glass fiber (fiber diameter: 0.3 ⁇ m, fiber length: about 0.1 to 1 mm) produced by subjecting B glass to the flame method was well dispersed in ethyl propionate. The dispersion was added and mixed well. Then, this mixed solution was put into a petri dish made of polytetrafluoroethylene, allowed to stand at room temperature for 1 hour, and then vacuum dried (170 ° C., 2 hours).
  • a sheet (A2) with an electrolyte was obtained in which glass fibers were contained as a dispersed phase in the matrix phase composed of the solid electrolyte Li 7 P 2 S 8 I and the glass fibers did not protrude on both sides of the sheet.
  • the mass ratio of the glass fiber and the solid electrolyte in the sheet with electrolyte (A2) was 10:90.
  • Example 2 the sheet with an electrolyte (A2) was press-processed in the same manner as in Example 1 to obtain an electrolyte sheet having a thickness of 20 ⁇ m. Then, in the same manner as in Example 1, a graph (not shown) showing the Si profile in the thickness direction of the electrolyte sheet is created, and the average value of the gray values in the horizontal direction is 51 or more (that is, the location where the Si element is present). When the ratio of the area where the pixel determined to be (20% or more) to the cross-sectional thickness was determined, it was 100% (see Table 1). Further, in the same manner as in Example 1, a powder drop test, a bending test and a conductivity measurement were performed, and the results are also shown in Table 1.
  • the lithium ion conductivity of this solid electrolyte was 1.5 ⁇ 10 -4 S / cm (room temperature).
  • the solid electrolyte powder was ground with a pestle and a pestle until the average particle size was 10 ⁇ m or less.
  • the obtained solid electrolyte particles were dispersed in dehydrated heptane under an argon atmosphere to obtain a solid electrolyte-containing slurry.
  • the mass ratio of the solid electrolyte particles and the dehydrated heptane in this solid electrolyte-containing slurry is 1: 1.
  • the solid electrolyte-containing slurry was applied to the nonwoven fabric (N1) having a size of 30 mm ⁇ 90 mm by the following operation.
  • the nonwoven fabric (N1) was placed on a fluororesin plate, and the gap between the nonwoven fabric (N1) and the applicator roll was set to 200 ⁇ m, and the solid electrolyte-containing slurry was applied to the one-sided surface of the nonwoven fabric (N1). After air-drying, the solid electrolyte-containing slurry was applied to the other surface of the nonwoven fabric (N1) under the same conditions and air-dried.
  • the obtained solid electrolyte-coated sheet was placed on a hot plate at 100 ° C. and desolubilized to obtain a sheet with an electrolyte (B1).
  • the volume ratio of the non-woven fabric (N1) to the solid electrolyte in the sheet with electrolyte (B1) was 12:88.
  • the mass ratio of the glass fiber and the solid electrolyte was 9:91.
  • the sheet with an electrolyte (B1) was press-processed in the same manner as in Example 1 to obtain an electrolyte sheet having a thickness of 88 ⁇ m.
  • the image of FIG. 5 was obtained with a scanning electron microscope in the same manner as in the electrolyte sheet of Example 1.
  • mapping analysis on the Si element contained in the glass fiber constituting the nonwoven fabric (N1) was performed.
  • the analysis target is the portion surrounded by the dotted line in FIG. 5 (horizontal: about 142 ⁇ m, vertical: about 88 ⁇ m). The image surrounded by the dotted line was cut out and shown in FIG.
  • the black portion is a portion having a Si element.
  • the region where the average value of the gray values in the horizontal direction is 51 or more that is, the number of pixels determined to be the presence of the Si element is 20% or more
  • the ratio to the thickness was calculated, it was 50% (see Table 1).
  • a powder drop test, a bending test and a conductivity measurement were performed, and the results are also shown in Table 1.
  • Examples 1 and 2 are examples of the electrolyte sheet of the present invention, and there was no desorption (powder drop) of the solid electrolyte, and no cracks or cracks were confirmed in the bending test.
  • the present invention is not limited to Examples 1 and 2 described above, and the electrolyte sheet may be obtained by improving individual steps.
  • Li 2 S powder after obtaining a slurry containing P 2 S 5 powder and LiI powders, although mixed with a dispersion of glass fibers, glass fibers, during the preparation of the slurry may be produced the mixture was added, from the beginning, a glass fiber, Li 2 S powder, used with P 2 S 5 powder and LiI powders, the mixture may be produced.
  • the electrolyte sheet of the present invention includes personal computers, home appliances such as cameras, power storage devices, portable electronic devices or communication devices such as mobile phones, electric tools such as power tools, electric bicycles, passenger cars such as electric vehicles, and wind power generation. It is suitable for forming an electrolyte layer for a lithium ion battery, which constitutes a stationary storage battery of a solar cell device, a watch, glasses, a wearable terminal, a drone, a flying object, a robot structure, etc., which make the best use of safety.
  • Electrolyte sheet 3 Fiber (inorganic fiber) 10: Lithium ion battery 11: Positive electrode layer 13: Negative electrode layer 15: Electrolyte layer 20: Solid electrolyte coated fiber 21: Fiber 23: Solid electrolyte

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WO2025046660A1 (ja) * 2023-08-25 2025-03-06 日産自動車株式会社 全固体電池
WO2025225694A1 (ja) * 2024-04-26 2025-10-30 東レ株式会社 固体電解質シート、固体電解質シートの製造方法および二次電池

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JP6041162B2 (ja) * 2012-08-01 2016-12-07 国立大学法人九州大学 炭化水素の改質用のペーパー状触媒及びペーパー状触媒配列体並びにペーパー状触媒又はペーパー状触媒配列体を備えた固体酸化物形燃料電池
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JP2020009548A (ja) * 2018-07-03 2020-01-16 川上 総一郎 蓄電デバイス

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WO2025225694A1 (ja) * 2024-04-26 2025-10-30 東レ株式会社 固体電解質シート、固体電解質シートの製造方法および二次電池

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