WO2021200621A1 - 固体電解質担持用不織布及び固体電解質シート - Google Patents

固体電解質担持用不織布及び固体電解質シート Download PDF

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Publication number
WO2021200621A1
WO2021200621A1 PCT/JP2021/012789 JP2021012789W WO2021200621A1 WO 2021200621 A1 WO2021200621 A1 WO 2021200621A1 JP 2021012789 W JP2021012789 W JP 2021012789W WO 2021200621 A1 WO2021200621 A1 WO 2021200621A1
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WIPO (PCT)
Prior art keywords
solid electrolyte
woven fabric
supporting
heat
fiber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/012789
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English (en)
French (fr)
Japanese (ja)
Inventor
重松　俊広
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Paper Mills Ltd
Original Assignee
Mitsubishi Paper Mills Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Paper Mills Ltd filed Critical Mitsubishi Paper Mills Ltd
Priority to JP2022512102A priority Critical patent/JPWO2021200621A1/ja
Priority to EP21779732.3A priority patent/EP4130370A4/en
Priority to US17/914,589 priority patent/US12486602B2/en
Priority to CN202180025104.6A priority patent/CN115349194A/zh
Publication of WO2021200621A1 publication Critical patent/WO2021200621A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
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    • D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
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    • D10B2321/021—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins polyethylene
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
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    • D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
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    • D10B2321/022—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins polypropylene
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D10B2321/06—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of unsaturated alcohols, e.g. polyvinyl alcohol, or of their acetals or ketals
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2505/00—Industrial
    • D10B2505/02—Reinforcing materials; Prepregs
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/025—Solid electrolytes
    • H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
    • 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 a solid electrolyte-supporting non-woven fabric and a solid electrolyte sheet having the solid electrolyte-supporting non-woven fabric and a solid electrolyte.
  • the "nonwoven fabric for supporting a solid electrolyte” may be abbreviated as “nonwoven fabric for supporting”.
  • secondary batteries such as large-capacity and high-performance lithium batteries used in mobile information terminals, portable electronic devices, small household power storage devices, motor-powered motorcycles, electric vehicles, hybrid electric vehicles, etc.
  • Demand is increasing.
  • This all-solid-state lithium battery includes a solid electrolyte layer, a positive electrode active material layer, a negative electrode active material layer, and a current collecting member bonded to each active material layer.
  • the solid electrolyte for example, a sulfide-based solid electrolyte having excellent lithium ion conductivity is heavily used.
  • the solid electrolyte used in all-solid-state lithium batteries is usually in the form of powder. Therefore, for convenience of handling, it is required to form a sheet. However, it has been difficult to form a single-layer thin film sheet composed of only powdered solid electrolyte. On the other hand, since the lithium ion conductivity in the solid electrolyte depends on the thickness of the solid electrolyte layer, it is desired to make the solid electrolyte layer thinner.
  • Patent Document 1 describes a method such as screen printing of a coating liquid containing a solid electrolyte on a non-woven fabric having a weight of 8 g or less per square meter and a thickness of 10 ⁇ m or more and 25 ⁇ m or less. A solid electrolyte sheet coated and dried using the above is disclosed.
  • an insulating porous base material is used as a support, the insulating porous base material is composed of a fibrous material, and solid electrolyte particles are contained inside the insulating porous base material. It is characterized in that it contains a binder that binds the solid electrolyte particles to each other, and the thickness of the insulating porous base material is 70% or more of the thickness of the solid electrolyte sheet.
  • the solid electrolyte sheet is disclosed.
  • PET non-woven fabric and Patent Document 2 made by sheeting polyethylene terephthalate (PET) fibers having a basis weight of 3 to 8 g / m 2 by a wet papermaking method, which are disclosed in Examples of Patent Document 1, are carried out.
  • PET non-woven fabric as the insulating porous base material disclosed in the example has no problem in the filling property of the solid electrolyte, but the tensile strength of the non-woven fabric is extremely low, and the process runnability is difficult. Therefore, in the examples of Patent Document 1, the PET film is used as a support base material, and there is a problem that the production cost is high.
  • Patent Document 1 discloses that a non-woven fabric sheeted by a wet papermaking method is preferable, but when the basis weight is very low, the constituent fibers are caught by the papermaking wire or the blanket supporting the wet paper and fall off. However, there is a problem that a hole defect may occur and a solid electrolyte cannot be supported on the hole defect portion.
  • the non-woven fabric for supporting the solid electrolyte contains fibrillated heat-resistant fibers and synthetic resin short fibers.
  • the content of the fibrillated heat-resistant fiber is 2% by mass or more and 40% by mass or less with respect to all the fiber components contained in the non-woven fabric for supporting the solid electrolyte, and a resin having a melting point of 160 ° C. or more is used as a core as a synthetic resin short fiber.
  • a non-woven fabric for supporting a solid electrolyte containing a core-sheath type composite fiber having a polyethylene resin as a sheath is disclosed.
  • the solid electrolyte-supporting non-woven fabric described in Patent Document 2 has a problem that the impregnation time of the solid electrolyte becomes long and the inside of the non-woven fabric is long when the particle size of the solid electrolyte is large or the viscosity of the coating liquid containing the solid electrolyte is high.
  • An object of the present invention is to provide a solid electrolyte supporting non-woven fabric having excellent process runnability, solid electrolyte filling property, thinning suitability of the solid electrolyte sheet, and few hole defects, and a solid electrolyte sheet having excellent independence and flexibility. To do.
  • Non-woven fabric for supporting a solid electrolyte which contains 60% by mass or more and 100% by mass or less of heat-sealing composite fibers having crimps and is heat-sealed.
  • a non-woven fabric for supporting a solid electrolyte which contains 60% by mass or more and 100% by mass or less of heat-sealing composite fibers having crimps and is heat-sealed.
  • a core sheath in which a heat-sealing composite fiber having crimp is composed of a polypropylene-based polymer in the core and a polyolefin-based polymer having a lower melting point than the polypropylene-based polymer used in the core.
  • non-woven fabric for supporting a solid electrolyte according to (5) above, wherein the non-woven fabric B is a non-woven fabric formed by a melt blow method or an electrospinning method.
  • a solid electrolyte sheet comprising the solid electrolyte-supporting non-woven fabric according to any one of (1) to (6) above and the solid electrolyte supported on the solid electrolyte-supporting non-woven fabric.
  • the solid electrolyte-supporting non-woven fabric of the present invention is excellent in process runnability, solid electrolyte filling property, and thinning suitability of the solid electrolyte sheet, and has few hole defects. Further, the solid electrolyte sheet having the lithium ion conductive solid electrolyte and the solid electrolyte supporting non-woven fabric of the present invention can achieve the effects of excellent independence and flexibility.
  • the all-solid-state lithium battery is composed of a positive electrode current collecting member, a positive electrode active material layer, a solid electrolyte layer, a negative electrode active material layer, and a negative electrode current collecting member.
  • the present invention is not limited to the embodiments described below.
  • the positive electrode current collecting member and the negative electrode current collecting member are not particularly limited as long as they are conductors, and are, for example, copper, magnesium, stainless steel, titanium, iron, cobalt, nickel, zinc, aluminum, germanium, indium, lithium, or , A plate-like body or a foil-like body made of these alloys or the like can be used.
  • the positive electrode active material layer contains a solid electrolyte, a positive electrode active material, a positive electrode layer conductive auxiliary agent, and a positive electrode layer binder.
  • Solid electrolyte contains at least lithium sulfide, as the second component preferably comprises silicon sulfide, one or more compounds selected from the group consisting of phosphorus and boron sulfide sulfide, in particular, Li 2 S -P 2 S 5 is preferred.
  • This sulfide-based solid electrolyte is known to have higher lithium ion conductivity than other inorganic compounds.
  • Li 2 SP 2 S 5 may further contain sulfides such as SiS 2 , GeS 2 , B 2 S 3.
  • the solid electrolyte as appropriate, Li 3 O 4, halogen, may be used a solid electrolyte obtained by adding a halogen compound and the like.
  • the sulfide-based solid electrolyte is obtained by heating Li 2 S and P 2 S 5 to a melting temperature or higher, melting and mixing both at a predetermined ratio, holding for a predetermined time, and then quenching (melting). Quenching method).
  • the predetermined time of the heat treatment is preferably 0.1 hour or more.
  • a quenching method a method of putting it in liquid nitrogen and quenching it to obtain a desired vitrified solid electrolyte, a method of vacuum-sealing it in a glass tube, heating and melting it, and then quenching it with ice water or the like, etc. Can be mentioned. It can also be obtained by the Li 2 SP 2 S 5 mechanical milling method.
  • Li 2 S and P 2 S 5 are mixed in molar ratio, preferably 50:50 to 80:20, more preferably 60:40 to 75 :.
  • examples thereof include sulfides obtained by mixing at 25.
  • the solid electrolyte examples include those containing a lithium ion conductor composed of an inorganic compound as an inorganic solid electrolyte in addition to the sulfide-based solid electrolyte.
  • a lithium ion conductor e.g., Li 3 N, LISICON, LiPON (Li 3 + y PO 4-x N x), Thio-LISICON (Li 3.25 Ge 0.25 P 0.75 S 4), There are Li 2 O-Al 2 O 3- TiO 2- P 2 O 5 (LATP).
  • the solid electrolyte has a structure such as amorphous, glassy, and crystalline (crystallized glass).
  • the solid electrolyte in each of the positive electrode active material layer, the negative electrode active material layer, and the electrolyte layer is composed of, for example, a mixture of an amorphous body and a crystalline body.
  • the amorphous body can be produced by mixing the first component and the second component of the above-mentioned sulfide and treating them by a mechanical milling method. Crystals can be produced by firing an amorphous body or the like.
  • the positive electrode active material is not particularly limited as long as it is a substance capable of reversibly storing and releasing lithium ions, and is, for example, lithium cobalt oxide (LCO), lithium nickel oxide, lithium nickel cobalt oxide, and nickel cobalt aluminum.
  • Lithium oxide hereinafter, may be abbreviated as "NCA”
  • nickel cobalt lithium manganate hereinafter, may be abbreviated as "NCM”
  • lithium manganate lithium iron phosphate, nickel sulfide, copper sulfide
  • Examples include sulfur, iron oxide, vanadium oxide and the like.
  • the positive electrode active material is particularly preferably a lithium salt of a transition metal oxide having a layered rock salt type structure.
  • the "layered” here means a thin sheet-like shape
  • the "rock salt-type structure” is a sodium chloride-type structure which is a kind of crystal structure, and each of a cation and an anion. Refers to a structure in which the face-centered cubic lattice formed by is offset from each other by 1/2 of the ridge of the unit cell.
  • lithium salt of a transition metal oxide having such a layered rock-salt structure for example, Li 1.1-x Ni y Co Z Al 1-y-z O 2 (NCA) or Li 1.1-x Ni y Co z Mn 1-y-z O 2 (NCM) (0 ⁇ x ⁇ 0.6,0 ⁇ y ⁇ 1,0 ⁇ z ⁇ 1 and y + z ⁇ 1) 3-component transition metal oxide represented by Lithium salt can be mentioned.
  • NCA Li 1.1-x Ni y Co Z Al 1-y-z O 2
  • NCM Li 1.1-x Ni y Co z Mn 1-y-z O 2
  • the positive electrode layer conductive auxiliary agent is added to form a conductive network between the positive electrode active materials and reduce the resistance of the positive electrode active material layer.
  • the conductive auxiliary agent may be contained in an appropriate amount in the positive electrode active material layer.
  • Examples of the positive electrode layer conductive auxiliary agent include carbon black such as Ketjen black and acetylene black, graphite, natural graphite, carbon nanotubes, and carbon nanofibers. It is not particularly limited as long as it enhances the conductivity of the positive electrode layer, and may be used alone or in combination of two or more.
  • the positive electrode layer binder examples include styrene-based thermoplastic elastomers such as SBS (styrene butadiene styrene block polymer), SEBS (styrene ethylene butadiene styrene block polymer), and styrene-styrene butadiene-styrene block polymer, and SBR ( Styrene-butadiene rubber), BR (butadiene rubber), NR (natural rubber), IR (isoprene rubber), EPDM (ethylene-propylene-diene ternary copolymer), NBR (nitrile rubber), CR (chloroprene rubber), and These partially hydrides, or completely hydrides, copolymers of polyacrylic acid esters, PVDF (polyvinylidene fluoride), PDF-HFP (vinylidene fluoride-hexafluoropropylene copolymer), and their carboxylic acid modifications.
  • CM chlorinated polyethylene
  • polymethacrylic acid ester polyvinyl alcohol
  • ethylene-vinyl alcohol copolymer polyimide
  • polyamide polyamideimide
  • polystyrene polyolefin, polyolefin-based thermoplastic elastomer, polycycloolefin, silicon resin and the like are exemplified.
  • the ratio of the contents of the solid electrolyte, the positive electrode active material, the positive electrode layer conductive auxiliary agent, and the positive electrode layer binder in the positive electrode active material layer is not particularly limited.
  • the solid electrolyte is 3 to 50% by mass
  • the positive electrode active material is 45 to 95% by mass
  • the positive electrode layer conductive aid is 1 to 10% by mass
  • the positive electrode layer binder is 3 to 50% by mass with respect to the total mass of the positive electrode active material layer. It is preferably 0.5 to 4% by mass.
  • the solid electrolyte layer is made of the solid electrolyte sheet of the present invention, and is produced as a self-supporting solid electrolyte sheet by supporting the supporting non-woven fabric and the supporting non-woven fabric described later.
  • the solid electrolyte may be supported with the electrolyte binder. Since the solid electrolyte, particularly the sulfide-based solid electrolyte, has high reactivity, the electrolyte binder is preferably a non-polar resin having no polar functional group.
  • the electrolyte binder of the solid electrolyte layer preferably contains the above-mentioned positive electrode layer binder.
  • the ratio of the contents of the solid electrolyte and the electrolyte binder in the solid electrolyte layer is not particularly limited.
  • the solid electrolyte is preferably 95 to 99.5% by mass and the electrolyte binder is preferably 0.5 to 5% by mass with respect to the total mass of the solid electrolyte and the electrolyte binder.
  • the method for producing the solid electrolyte sheet of the present invention will be described.
  • the solid electrolyte sheet of the present invention can be produced by applying a solid electrolyte slurry (coating liquid containing a solid electrolyte) in which a solid electrolyte is dissolved or dispersed in a medium to a supporting non-woven fabric and drying it.
  • the medium used for the solid electrolyte slurry is not particularly limited as long as it does not adversely affect the performance of the solid electrolyte. Examples of the medium include non-aqueous media.
  • non-aqueous medium examples include a medium used for an electrolytic solution such as dried heptane, toluene, hexane, tetrahydrofuran (THF), N-methylpyrrolidone, acetonitrile, dimethoxyethane, and dimethyl carbonate.
  • the water content of the medium is preferably 100 ppm or less, more preferably 50 ppm or less.
  • Various coating devices can be used as the device for coating the solid electrolyte slurry on both sides or one side of the supporting non-woven fabric.
  • various coaters such as a gravure coater, a die coater, a lip coater, a blade coater, a curtain coater, an air knife coater, a rod coater, a roll coater, a kiss touch coater, and a dip coater can be used.
  • the solid electrolyte slurry After applying the solid electrolyte slurry, it is dried to form a solid electrolyte layer.
  • a drying device using hot air, a heater, a high frequency, or the like can be used. Drying may be performed from both sides of the solid electrolyte sheet, or may be performed from one side. At this time, it is necessary to adjust the drying conditions so that the removal of the medium in the solid electrolyte slurry is not insufficient. For example, in the case of hot air drying, it is necessary to optimally adjust the temperature and air volume.
  • the dried solid electrolyte sheet can be used as it is, but the strength can be further increased by a pressure treatment such as pressurization (press) or heat pressurization (heat press).
  • a sheet press, a roll press, or the like can be used for the pressurizing treatment. If the pressure during the pressure treatment is low, the thickness of the solid electrolyte layer may be non-uniform, and if the pressure is high, the solid electrolyte layer and the non-woven fabric for carrying may be damaged.
  • the negative electrode active material layer contains a negative electrode active material, a negative electrode layer binder, and a solid electrolyte.
  • the negative electrode active material layer binder the same binder as the above-mentioned positive electrode layer binder can be used.
  • the negative electrode active material examples include graphite-based active material graphite, for example, artificial graphite, natural graphite, a mixture of artificial graphite and natural graphite, natural graphite coated with artificial graphite, metallic lithium, silicon alloy, tin alloy and the like. At least a part of the graphite powder may be coated with an inorganic compound, a metal, or the like.
  • the ratio of the contents of the negative electrode active material, the solid electrolyte, and the negative electrode layer binder is not particularly limited.
  • the sulfide-based solid electrolyte is 0 to 40% by mass
  • the negative electrode active material is 60 to 99.5% by mass
  • the negative electrode layer binder is 0.5 to 5% by mass with respect to the total mass of the negative electrode active material layer. It is preferable to include it.
  • the non-woven fabric for supporting the solid electrolyte of the present invention is a non-woven fabric that supports a solid electrolyte.
  • the non-woven fabric for supporting a solid electrolyte of the present invention is a non-woven fabric A containing and heat-sealing heat-sealing composite fibers having crimps, and the content of the heat-sealing composite fibers having crimps is 60. It is characterized in that it is 100% by mass or more and 100% by mass or less.
  • heat-fused composite fiber having crimp may be abbreviated as “crimp heat-fused composite fiber”.
  • the non-woven fabric A becomes bulky, the air permeability tends to be high, and the solid electrolyte can be easily filled. Further, the crimp heat-sealing composite fiber is easily entangled with other fibers, and the tensile strength of the supporting non-woven fabric can be increased.
  • Examples of the type of crimp heat-sealing composite fiber include core sheath type, eccentric type, side-by-side type, sea island type, orange type, and multiple bimetal type composite fiber.
  • the crimp heat-sealing composite fiber one type of mold may be used, or two or more types of molds may be used.
  • Two or more kinds of resins are used in the composite fiber, but in the crimp heat-sealing composite fiber of the present invention, it is preferable to use a resin having a melting point of 160 ° C. or higher and a resin having a melting point of less than 160 ° C.
  • the core-sheath type crimp heat-sealing composite fiber it is preferable that the core is made of a resin having a melting point of 160 ° C. or higher and the sheath is made of a resin having a melting point of less than 160 ° C.
  • the melting point of the core resin is 160 ° C. or higher, the resin portion can easily maintain the fiber shape, and the melting point of the resin is more preferably 163 ° C. or higher.
  • the melting point is a value measured in accordance with JIS K7121: 2012.
  • Resins having a melting point of 160 ° C. or higher include polyester, acrylic, polypropylene polymer (PP), total aromatic polyester, total aromatic polyesteramide, polyamide, semi-aromatic polyamide, total aromatic polyamide, and total aromatic polyether.
  • polyester, acrylic, polypropylene-based polymers, total aromatic polyesters, total aromatic polyesteramides, polyamides, semi-aromatic polyamides, and total aromatic polyamides are preferable, and polyesters, acrylics, and polypropylene-based polymers are more preferable, and polypropylene is more preferable.
  • the system polymer is particularly preferable from the viewpoint of spinning.
  • a resin having a melting point of less than 160 ° C. for the sheath.
  • the resin having a melting point of less than 160 ° C. include polyethylene-based polymers (PE) such as high-density, medium-density, low-density polyethylene and chain low-density polyethylene, and copolymers of propylene and other ⁇ -olefins.
  • PE polyethylene-based polymers
  • polyester acrylic resin, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate alcohol copolymer, low melting point polyester (modified polyester) and the like can be mentioned.
  • a polyolefin-based polymer having a melting point lower than that of the core is preferable, and a polyethylene-based polymer is particularly preferable from the viewpoint of spinning, adhesiveness, and solvent resistance.
  • the melting point of the resin having a melting point of less than 160 ° C. is preferably 115 ° C. or higher, and the core-sheath type crimp heat-sealing composite fiber is adhered.
  • the melting point of the resin having a melting point of less than 160 ° C. is more preferably 140 ° C. or lower.
  • the ratio of the resin having a melting point of 160 ° C. or higher and the resin having a melting point of less than 160 ° C. in the crimp heat-sealing composite fiber is not particularly limited, but the mass ratio is preferably in the range of 7: 3 to 3: 7.
  • the range of 4 to 4: 6 is more preferable, and 5: 5 or its vicinity (5.5: 4.5 to 4.5: 5.5) is particularly preferable.
  • the crimp heat-sealing composite fiber only one kind may be used, or two or more kinds of resins having a melting point of 160 ° C. or higher and / or a resin having a melting point of less than 160 ° C. may be used in combination.
  • the content of the crimp heat-sealing composite fiber is 60 to 100% by mass, more preferably 70 to 95% by mass, and 80 to 80% by mass, based on the total fiber components contained in the non-woven fabric A. It is more preferably 90% by mass.
  • the content of the crimp heat-fused composite fiber is 60 to 100% by mass, the adhesion point between the fibers becomes strong due to the melting of the crimp heat-fused composite fiber, and the tensile strength of the supporting non-woven fabric becomes strong. The effect of improving is obtained.
  • the adhesion of the surface of the supporting non-woven fabric is strengthened, and the effect of suppressing fluff on the surface can be obtained.
  • the adhesiveness between the supporting non-woven fabric and the solid electrolyte is improved by melting the crimp heat-sealing composite fiber in the hot pressing process, and cracks are generated in the solid electrolyte layer.
  • a thinned solid electrolyte sheet can be obtained without causing the problem.
  • the fineness of the crimp heat-sealing composite fiber is preferably 0.9 dtex or less, more preferably 0.06 to 0.5 dtex, still more preferably 0.1 dtex to 0.4 dtex. It is particularly preferably 0.2 to 0.3 dtex.
  • the fineness of the crimp heat-sealing composite fiber is less than 0.06 dtex, the fiber is too thin and the supporting non-woven fabric is easily formed into a film.
  • the fineness of the crimp-heat-fused composite fiber increases beyond 0.9 dtex, the number of fibers per mass decreases, so that the adhesive portion between the fibers decreases and the tensile strength of the supporting non-woven fabric decreases.
  • the supporting non-woven fabric may become thick.
  • the crimping heat-fusing composite fiber having a particularly preferable fineness of 0.2 to 0.3 dtex makes it possible to easily make the supporting non-woven fabric into a desired thinness, and also makes it possible to easily make the denseness sufficient. ,
  • the adhesiveness between the supporting non-woven fabric and the solid electrolyte layer and the impregnation property of the solid electrolyte slurry can be improved.
  • Air permeability of the nonwoven fabric A is preferably from 150 ⁇ 2500cm 3 / cm 2 ⁇ sec, more preferably 200 ⁇ 2000cm 3 / cm 2 ⁇ sec, it is 250 ⁇ 1500cm 3 / cm 2 ⁇ sec More preferred.
  • the air permeability of the non-woven fabric A can be adjusted by adjusting the basis weight, thickness, fiber type and fiber diameter of the non-woven fabric A. When the air permeability of the non-woven fabric A is less than 150 cm 3 / cm 2 ⁇ sec, it may be difficult to fill the solid electrolyte due to the high density of the supporting non-woven fabric.
  • the air permeability of the supporting non-woven fabric exceeds 2500 cm 3 / cm 2 ⁇ sec
  • the denseness of the supporting non-woven fabric is lowered, and uneven coating or through holes of the solid electrolyte are generated, or the solid electrolyte layer. May impair the uniformity of.
  • the tensile strength of the supporting non-woven fabric is lowered, the process runnability when filling the solid electrolyte is deteriorated, and wrinkles may be generated in the supporting non-woven fabric during running.
  • thermoforming composite fibers As a method of applying crimping to the heat-sealing composite fiber, there is a method of mechanically pushing in by mechanically buckling with a pair of pushing rollers and a stuffer box to give crimping.
  • asymmetrical heat-sealing composite fibers such as bimetal type and eccentric type are self-crimped by heat treatment.
  • the number of crimps of the heat-sealing composite fiber is preferably 6 to 25 pieces / inch, more preferably 8 to 22 pieces / inch, and further preferably 10 to 18 pieces / inch. ..
  • the number of crimps is less than 6 pieces / inch, the supporting non-woven fabric is unlikely to be bulky, so that the effect of increasing the air permeability and the effect of increasing the tensile strength may not be observed.
  • the number of crimps exceeds 25 pieces / inch, the basis weight of the supporting non-woven fabric becomes non-uniform and formation defects are likely to occur, or the supporting non-woven fabric becomes too thick and supports a solid electrolyte. After that, it may be difficult to thin the film by hot pressing.
  • the non-woven fabric A may contain fibers other than the crimp heat-sealing composite fiber.
  • the fiber other than the crimp heat-sealing composite fiber include a fiber having no crimp, a so-called straight type fiber.
  • Fibers without crimp include polyolefin, polyester, polyvinyl acetate, ethylene-vinyl acetate copolymer, polyamide, acrylic resin, polyvinyl chloride, polyvinylidene chloride, polyvinyl ether, polyvinyl ketone, polyether, polyvinyl alcohol.
  • the non-woven fabric A can contain fibers other than the crimp heat-sealing composite fiber.
  • the fibers other than the crimp heat-sealing composite fibers may be fibers made of a single resin (single fibers) or composite fibers made of two or more kinds of resins. Further, the fibers other than the crimp heat-sealing composite fiber may be used alone or in combination of two or more. Examples of the composite fiber include a core sheath type, an eccentric type, a side-by-side type, a sea island type, an orange type, and a multiple bimetal type.
  • the fineness of the fibers other than the crimp heat-sealing composite fiber is preferably 0.01 dtex or more and 0.6 dtex or less, and more preferably 0.02 dtex or more and 0.3 dtex or less.
  • the fineness exceeds 0.6 dtex the number of fibers in the thickness direction is reduced, so that the pore size distribution of the supporting nonwoven fabric is widened, and as a result, the coatability of the solid electrolyte slurry is likely to deteriorate, and the supporting non-woven fabric is used.
  • the adhesiveness between the non-woven fabric and the solid electrolyte layer may also deteriorate.
  • the fineness is less than 0.01 dtex, the fiber becomes very expensive and stable production of the fiber becomes difficult, or when the non-woven fabric for carrying is produced by the wet papermaking method, the productivity may decrease. ..
  • the fiber length of the crimp heat-sealing composite fiber is preferably 1 mm or more and 10 mm or less, and more preferably 1 mm or more and 5 mm or less. If the fiber length exceeds 10 mm, the formation may be poor. On the other hand, when the fiber length is less than 1 mm, the tensile strength of the supporting nonwoven fabric becomes low, and the supporting nonwoven fabric may be damaged when the solid electrolyte layer is formed.
  • the preferable fiber lengths of fibers other than the crimp heat-sealing composite fibers are also in the same range as described above.
  • the non-woven fabric for supporting the solid electrolyte of the present invention may contain fibers exemplified below in addition to the crimp heat-fused composite fibers and the fibers other than the above-mentioned crimp heat-fused composite fibers.
  • fibers exemplified below in addition to the crimp heat-fused composite fibers and the fibers other than the above-mentioned crimp heat-fused composite fibers.
  • examples thereof include cellulose fibers, pulped and fibrils of cellulose fibers, fibrid made of synthetic resin, pulped material made of synthetic resin, and inorganic fibers.
  • the inorganic fiber include glass, alumina, silica, ceramics, and rock wool.
  • the cellulose fiber include natural cellulose and regenerated cellulose.
  • the thickness of the non-woven fabric A is preferably 10 ⁇ m or more, more preferably 15 ⁇ m or more, still more preferably 20 ⁇ m or more. Further, 35 ⁇ m or less is preferable, 33 ⁇ m or less is more preferable, and 30 ⁇ m or less is further preferable. Even when the thickness is within the above range, the non-woven fabric A can maintain the tensile strength required in the coating process of the solid electrolyte slurry, so that the workability in each process including the manufacturing process of the non-woven fabric A is impaired. There is no.
  • the thickness of the non-woven fabric A exceeds 35 ⁇ m, it becomes difficult to fill the inside of the supporting non-woven fabric with the solid electrolyte slurry, or it is difficult to thin the solid electrolyte layer in the hot pressing process after coating, and the lithium of the solid electrolyte layer is difficult to thin. Ion conductivity may decrease. In addition, it may not be possible to increase the capacity of the battery. If the thickness of the non-woven fabric A is less than 10 ⁇ m, the tensile strength of the supporting non-woven fabric becomes too weak, which may cause damage during handling of the supporting non-woven fabric or coating of the solid electrolyte slurry, resulting in deterioration of process runnability. In some cases. In addition, the supporting non-woven fabric may be too dense to be filled with the solid electrolyte slurry.
  • the density of the non-woven fabric A is preferably 0.14 g / cm 3 or more and 0.35 g / cm 3 or less, and 0.15 g / cm 3 or more and 0.32 g / cm 3 or less. More preferably, 0.16 g / cm 3 or more and 0.30 g / cm 3 or less is further preferable. If the density of the non-woven fabric A is less than 0.14 g / cm 3 , the tensile strength of the supporting non-woven fabric becomes too weak, which may cause damage during handling or coating of the supporting non-woven fabric, resulting in deterioration of process runnability. In some cases.
  • the density of the non-woven fabric A exceeds 0.35 g / cm 3 , the supporting non-woven fabric becomes dense, film formation progresses, the impregnation property of the solid electrolyte slurry deteriorates, and as a result, the ionic conductivity of the solid electrolyte sheet becomes poor. It may get worse.
  • the nonwoven fabric A is preferably a wet nonwoven fabric produced by a wet fabrication method having excellent productivity.
  • the wet papermaking method fibers are dispersed in water to form a uniform papermaking slurry, and a wet paper is made from this papermaking slurry with a paper machine and the wet paper is dried to produce a wet non-woven fabric.
  • the paper machine include a circular net paper machine, a long net paper machine, an inclined paper machine, an inclined short net paper machine, and a combination machine thereof.
  • water flow entanglement treatment may be performed if necessary.
  • heat treatment, calendar treatment, thermal calendar treatment and the like may be performed.
  • the wet papermaking method although the frequency of occurrence is low, the constituent fibers adhere to the net of the paper machine or the blanket for papermaking that conveys wet paper, and the wet non-woven fabric has a hole defect (for example, 0.2 to 0.8 mm ⁇ in diameter). ) May occur. Therefore, it is necessary to take measures such as changing the fiber composition, changing the consumable parts for papermaking, and adjusting the manufacturing conditions. As a result of the examination by the present inventor, when the nonwoven fabric A having a basis weight of less than 4 g / m 2 is produced, the time, labor and cost required for these measures tend to be enormous.
  • the solid electrolyte cannot be applied to that part, or even if it can be applied, the solid electrolyte may be missing during each manufacturing process of the all-solid-state battery. Therefore, it is necessary to reduce the hole defects.
  • the supporting non-woven fabric is a supporting non-woven fabric in which a non-woven fabric B made of ultrafine fibers having an average fiber diameter of 2 ⁇ m or less is laminated on at least one surface of the non-woven fabric A.
  • the non-woven fabric B closes the hole defect of the non-woven fabric A, and the solid electrolyte can be supported.
  • the non-woven fabric B made of ultrafine fibers having an average fiber diameter of 2 ⁇ m or less can be filled with a solid electrolyte more densely than the non-woven fabric A, the dendrite of the negative electrode can be suppressed by arranging the non-woven fabric B on the negative electrode side. Is also possible.
  • the non-woven fabric B As a method for producing the non-woven fabric B, a melt blow method or an electrospinning method is preferable, and an electrospinning method is more preferable, because a non-woven fabric having a low basis weight can be produced.
  • a melt blow method or an electrospinning method is preferable, and an electrospinning method is more preferable, because a non-woven fabric having a low basis weight can be produced.
  • the method for producing the nonwoven fabric B by the melt blow method is not particularly limited, and it can be produced by a general melt blow method.
  • a thermoplastic resin, wax, or the like as a raw material is melted using an extruder or the like.
  • the molten thermoplastic resin or the like is introduced into a spinneret connected to the tip of the extruder, and is discharged in a fibrous form from the spinning nozzle of the spinneret. Then, the fibrous discharge material is stretched by the heating gas discharged from the gas nozzle of the spinneret.
  • the heating gas is not particularly limited, but is, for example, air.
  • the resin constituting the non-woven fabric B is usually a thermoplastic resin, and examples thereof include polyethylene-based polymers such as high-density, medium-density, low-density polyethylene and chain low-density polyethylene, propylene and other ⁇ -olefins. Polymers with, specifically, propylene-butene-1 random copolymers, propylene-ethylene-butene-1 random copolymers, non-crystalline polypropylene-based polymers such as soft polypropylene, poly4-methylpentene- Examples thereof include a polyethylene-based polymer such as 1.
  • polyester acrylic resin, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate alcohol copolymer, low melting point polyester (modified polyester), polyvinyl chloride, polystyrene and the like can be mentioned.
  • the non-woven fabric B may contain only one kind of these, or may contain two or more kinds of them.
  • low-density, medium-density, high-density polyethylene, and polypropylene-based polymers are preferable, and spunability, mechanical strength, and chemical resistance are excellent. From the viewpoint, polypropylene-based polymers are preferable.
  • the non-woven fabric B may contain wax together with the above-mentioned thermoplastic resin.
  • waxes include propylene homopolymers, copolymers of propylene and other ⁇ -olefins, and the like.
  • the non-woven fabric B may contain only one type of wax, or may contain two or more types of wax.
  • a propylene homopolymer is particularly preferable from the viewpoint of compatibility with the thermoplastic resin and spinnability. When wax is contained, the average fiber diameter of the non-woven fabric B tends to be thin.
  • the device used for the melt blow method is not particularly limited, and is the same as a general melt blow device. Further, the conditions for performing the melt blow method (for example, the temperature of the spinneret, the melting temperature of the thermoplastic resin, the temperature of the heating gas, etc.) are as long as the fibrous resin having the above-mentioned average fiber diameter can be produced. There is no particular limitation. The average fiber diameter can be adjusted by appropriately changing the size of the discharge port of the spinneret, the temperature of the spinneret, the melting temperature, the temperature of the heating gas, the flow rate, and the like.
  • the fibrous resin produced by the melt blow method is collected in a web shape on the non-woven fabric A loaded on the collection plate.
  • the collection method is not particularly limited, and the above-mentioned melt blow method is performed while relatively moving the non-woven fabric A loaded on the collection plate and the spinneret of the above-mentioned melt blow device, and the fibers are continuously or intermittently.
  • Form a resin As a result, the fibrous resin is deposited in a web shape on the non-woven fabric A loaded on the collecting plate, the fibers are fused to each other, and the non-woven fabric B made of ultrafine fibers having an average fiber diameter of 2 ⁇ m or less is integrated on the non-woven fabric A. A non-woven fabric is obtained.
  • the basis weight of the obtained non-woven fabric B changes according to the discharge amount and the moving speed of the non-woven fabric A loaded on the collection plate.
  • the collecting plate is not particularly limited as long as it can support the produced supporting non-woven fabric and does not inhibit the formation of the non-woven fabric B by the melt blow method.
  • Examples include perforated belts (conveyor nets), perforated drums and the like. Air may be sucked from the side opposite to the nozzle side of the melt blow device to promote the collection of the fibrous resin.
  • the electrospinning method is a method of spinning ultrafine fibers by applying a high voltage to a solution of a polymer compound that is a raw material of the ultrafine fibers.
  • the device for performing the electrospinning method consists of a syringe, a high voltage source and a conductive collector.
  • the syringe is equipped with a cylinder, piston, and capillary.
  • the cylinder is a tubular part that can be filled with a solution of a polymer compound that is a raw material for ultrafine fibers, and is provided with a capillary at the end.
  • the inner diameter of the capillary is preferably 10 to 1000 ⁇ m.
  • the piston is a columnar member that fits inside the cylinder. By moving this piston, the cylinder, piston and capillary are combined so as to push the solution of the polymeric compound in the cylinder out of the capillary.
  • the high voltage source is a DC power supply.
  • the positive electrode of this high voltage source is connected to the syringe and conducts with the polymer solution in the syringe.
  • the negative electrode side of the high voltage source is grounded.
  • the conductive collector is a grounded metal plate. The conductive collector is placed at a constant distance from the tip of the capillary in the syringe. The distance between the conductive collector and the tip of the capillary is preferably about 3 to 15 cm.
  • a voltage is applied between the syringe and the conductive collector, and in the electrostatic spinning step, a solution of the polymer compound is solidified to form ultrafine fibers. It has a step of depositing and electrostatically spinning.
  • a voltage is applied between the cylinder and the conductive collector.
  • the voltage applied to the polymer solution during electrostatic spinning is not particularly limited as long as it is a voltage capable of maintaining a state in which spinning is continuously performed. Usually, the range of 0.5 to 50 kV is preferably used.
  • the inside of the syringe is filled with a solution of a polymer compound that is a raw material for ultrafine fibers.
  • the solution of the polymer compound used in the present invention is not particularly limited as long as it can be solvated.
  • the polymer compound include polyvinyl alcohol (PVA) polyacrylonitrile (PAN) and polyvinylidene fluoride (PVDF).
  • PVA polyvinyl alcohol
  • PAN polyacrylonitrile
  • PVDF polyvinylidene fluoride
  • the polymer compound may be used alone or in combination of two or more.
  • the solvent in the solution of the polymer compound is not particularly limited as long as it is a solvent that completely dissolves the polymer compound and does not cause reprecipitation of the polymer compound during the electrostatic spinning process.
  • solvents include N, N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, tetrahydrofuran, acetone, acetonitrile, water and the like.
  • the solvent may be used alone or in combination of two or more.
  • the average fiber diameter of the ultrafine fibers constituting the non-woven fabric B is 2 ⁇ m or less, more preferably 1.5 ⁇ m or less, still more preferably 1.0 ⁇ m or less.
  • the smaller the fiber diameter of the ultrafine fiber the more the hole defect can be closed even if the non-woven fabric A has a hole defect even at a low basis weight.
  • the average fiber diameter of the ultrafine fibers exceeds 2 ⁇ m, it is necessary to increase the basis weight, and in that case, the impregnation property of the solid electrolyte deteriorates. Moreover, when the basis weight is kept low, the hole defect cannot be closed.
  • the average fiber diameter of the ultrafine fibers take a surface photograph of the non-woven fabric B at a magnification of 1000 using an electron microscope, select any 100 of the constituent ultrafine fibers, and select the width (diameter) of the selected fibers. The measurement was performed, and the average of the measurement results was taken as the average fiber diameter.
  • the basis weight of the non-woven fabric B is preferably 1 g / m 2 to 5 g / m 2 , and more preferably 1 g / m 2 to 2 g / m 2 .
  • the basis weight of the non-woven fabric B is less than 1 g / m 2 , even if the non-woven fabric A has a hole defect, the hole defect may not be sufficiently closed or the basis weight may not be controlled.
  • the basis weight of the non-woven fabric B is more than 5 g / m 2 , the supporting non-woven fabric becomes too thick and the non-woven fabric B is dense, so that it may be difficult to fill the solid electrolyte.
  • the thickness of the non-woven fabric A is preferably 10 ⁇ m or more, more preferably 12 ⁇ m or more, still more preferably 15 ⁇ m or more. Further, 25 ⁇ m or less is preferable, 23 ⁇ m or less is more preferable, and 20 ⁇ m or less is further preferable. If the thickness of the non-woven fabric A exceeds 25 ⁇ m, it may be difficult to fill the supporting non-woven fabric with the solid electrolyte.
  • the tensile strength of the supporting non-woven fabric becomes too weak, which may cause damage during handling of the supporting non-woven fabric or coating of the solid electrolyte slurry, resulting in deterioration of process runnability. In some cases.
  • the supporting non-woven fabric may be too dense to be filled with the solid electrolyte slurry.
  • the density of the non-woven fabric A is preferably 0.14 g / cm 3 or more and 0.35 g / cm 3 or less, preferably 0.15 g / cm 3 More than 0.32 g / cm 3 or less is more preferable, and 0.16 g / cm 3 or more and 0.30 g / cm 3 or less is further preferable.
  • the density of the non-woven fabric A is less than 0.14 g / cm 3 , the tensile strength of the supporting non-woven fabric becomes too weak and may be damaged during handling or coating of the supporting non-woven fabric, resulting in deterioration of process runnability. In some cases.
  • the density of the non-woven fabric A exceeds 0.35 g / cm 3 , the supporting non-woven fabric becomes dense and the impregnation property of the solid electrolyte slurry deteriorates, and as a result, the ionic conductivity of the solid electrolyte sheet may deteriorate. ..
  • the thickness of the non-woven fabric for supporting the solid electrolyte is preferably 10 ⁇ m or more, more preferably 15 ⁇ m or more, still more preferably 20 ⁇ m or more. Further, 35 ⁇ m or less is preferable, 33 ⁇ m or less is more preferable, and 30 ⁇ m or less is further preferable. Even when the thickness of the supporting nonwoven fabric is within the above range, the supporting nonwoven fabric of the present invention can maintain the tensile strength required in the coating process of the solid electrolyte slurry. It does not impair workability in the process.
  • the thickness of the supporting non-woven fabric exceeds 35 ⁇ m, it may be difficult to fill the inside of the supporting non-woven fabric with the solid electrolyte slurry, or it may be difficult to thin the solid electrolyte layer in the heat pressing step after coating. Lithium ion conductivity may decrease. In addition, it may not be possible to increase the capacity of the battery. If the thickness of the supporting non-woven fabric is less than 10 ⁇ m, the tensile strength of the supporting non-woven fabric becomes too weak and may be damaged when the supporting non-woven fabric is handled or when the solid electrolyte slurry is applied, resulting in poor process runnability. May be done. In addition, the supporting non-woven fabric may be too dense to be filled with the solid electrolyte slurry.
  • the density of the solid electrolyte for supporting nonwoven is preferably 0.14 g / cm 3 or more 0.35 g / cm 3 or less, more preferably 0.15 g / cm 3 or more 0.32 g / cm 3 or less, 0.16 g / cm 3 More preferably 0.30 g / cm 3 or less. If the density of the supporting non-woven fabric is less than 0.14 g / cm 3 , the tensile strength of the supporting non-woven fabric becomes too weak and may be damaged during handling or coating of the supporting non-woven fabric, resulting in poor process runnability. May be done.
  • the density of the supporting nonwoven fabric exceeds 0.35 g / cm 3 , the supporting nonwoven fabric becomes too dense, the film formation progresses, the impregnation property of the solid electrolyte slurry deteriorates, and as a result, the ion conduction of the solid electrolyte sheet Sex may worsen.
  • the coating amount is the dry coating amount.
  • Example 1 ⁇ Manufacturing of supporting non-woven fabric>
  • Crisp heat-sealing composite fiber core sheath type, core: PP, sheath: PE, fineness: 0.2 dtex, fiber length: 3 mm, number of crimps: 14 pieces / inch
  • fiber 20 parts by mass of PP fiber having a length of 3 mm was dispersed in water with a pulper to prepare a uniform papermaking slurry having a concentration of 0.5% by mass, and a wet paper web was obtained using a circular net paper machine to obtain a wet paper web, and the surface temperature was 133.
  • the sheets were obtained by drying with a cylinder dryer at ° C.
  • One roll is a chrome-plated steel roll
  • the other roll is a resin roll having a shore D hardness of 92
  • the obtained sheet is calendar-processed by a calendar device having a surface temperature of the steel roll at room temperature.
  • a non-woven fabric for supporting a solid electrolyte (nonwoven fabric A) having a basis weight of 5.0 g / m 2 and a thickness of 30 ⁇ m was prepared.
  • the tertiary mixed solution and the zirconia balls having a diameter of 5 mm are used so that the space, the mixed solution and the zirconia balls each occupy one third of the total volume of the kneading container. It was put into a kneading container. The quaternary mixture prepared thereby was put into a rotation / revolution mixer and stirred at 3000 rpm for 3 minutes to prepare a solid electrolyte slurry.
  • the non-woven fabric for supporting the solid electrolyte is continuously guided from above through the guide roller into the coating tank containing the above-mentioned solid electrolyte slurry.
  • the solid electrolyte is immersed in the slurry, and for the purpose of impregnating the inside of the supporting non-woven fabric with the solid electrolyte, it is nipped by a roll press in the coating tank and pulled up through a guide roller.
  • both sides of the supporting nonwoven fabric are smoothed by applying a plastic blade, excess solid electrolyte slurry is scraped off, and the supporting nonwoven fabric impregnated with the solid electrolyte is guided to a hot air dryer and dried from both sides. Then, the obtained solid electrolyte-supporting sheet was hot-pressed at a temperature of 120 ° C. and a load of 5 t / cm 2 to prepare a solid electrolyte sheet.
  • the crimp heat-fused composite fiber is a crimp heat-fused composite fiber (core sheath type, core: PP, sheath: PE, fineness: 0.4 dtex, fiber length: 5 mm, number of crimps: 14 pieces / inch. ),
  • a non-woven fabric for supporting a solid electrolyte having a basis weight of 5.0 g / m 2 and a thickness of 33 ⁇ m was prepared in the same manner as in Example 1.
  • a solid electrolyte sheet was prepared in the same manner as in Example 1.
  • the crimp heat-fused composite fiber is a crimp heat-fused composite fiber (core sheath type, core: PP, sheath: PE, fineness: 0.8 dtex, fiber length: 5 mm, number of crimps: 14 pieces / inch. ),
  • a non-woven fabric for supporting a solid electrolyte having a basis weight of 5.3 g / m 2 and a thickness of 35 ⁇ m was prepared in the same manner as in Example 1.
  • a solid electrolyte sheet was prepared in the same manner as in Example 1.
  • Example 4 The fiber composition is a crimp heat-sealing composite fiber (core sheath type, core: PET, sheath: modified PET resin having a melting point of 110 ° C., fineness: 0.5 dtex, fiber length: 5 mm, number of crimps: 14 pieces / inch. ) 70 parts, fineness 0.6 dtex, except that the 30 parts of the stretched PET fibers of fiber length 5 mm, a basis weight of 5.2 g / m 2 in the same manner as in example 1. the thickness of 30 ⁇ m of the solid electrolyte for supporting a non-woven fabric Made. Next, a solid electrolyte sheet was prepared in the same manner as in Example 1.
  • Example 5 A solid electrolyte sheet was prepared in the same manner as in Example 1 except that a non-woven fabric for supporting a solid electrolyte having a basis weight of 8.0 g / m 2 and a thickness of 27 ⁇ m was prepared.
  • Example 6 A non-woven fabric for supporting a solid electrolyte having a basis weight of 5.0 g / m 2 and a thickness of 25 ⁇ m was produced by the same method as in Example 1 except that the number of crimps of the heat-sealing composite fiber was 6 per inch. .. Next, a solid electrolyte sheet was prepared in the same manner as in Example 1.
  • Example 7 A non-woven fabric for supporting a solid electrolyte having a basis weight of 5.0 g / m 2 and a thickness of 34 ⁇ m was produced by the same method as in Example 1 except that the number of crimps of the heat-sealing composite fiber was 25 per inch. .. Next, a solid electrolyte sheet was prepared in the same manner as in Example 1.
  • Example 8 The basis weight is 5.0 g / m in the same manner as in Example 1 except that the fiber composition is 60 parts of the crimp heat-sealing composite fiber used in Example 1 and 40 parts of the PP fiber used in Example 1. 2.
  • a non-woven fabric for supporting a solid electrolyte having a thickness of 30 ⁇ m was prepared. Next, a solid electrolyte sheet was prepared in the same manner as in Example 1.
  • Example 9 A non-woven fabric for supporting a solid electrolyte having a basis weight of 5.0 g / m 2 and a thickness of 20 ⁇ m was produced by the same method as in Example 1 except that the number of crimps of the heat-sealing composite fiber was set to 5 per inch. .. Next, a solid electrolyte sheet was prepared in the same manner as in Example 1.
  • Example 10 A non-woven fabric for supporting a solid electrolyte having a basis weight of 5.0 g / m 2 and a thickness of 36 ⁇ m was produced by the same method as in Example 1 except that the number of crimps of the heat-sealing composite fiber was 26 per inch. .. Next, a solid electrolyte sheet was prepared in the same manner as in Example 1.
  • Example 11 The fiber composition was the same as in Example 1 except that 100 parts of the crimp heat-sealing composite fiber used in Example 1 was used to prepare a non-woven fabric for supporting a solid electrolyte having a basis weight of 8.5 g / m 2 and a thickness of 27 ⁇ m. A solid electrolyte sheet was prepared by the method of.
  • Comparative Example 1 The basis weight is 5.0 g / m in the same manner as in Example 1 except that 55 parts of the crimp heat-sealing composite fiber used in Example 1 and 45 parts of PP fiber used in Example 1 are blended. 2. A non-woven fabric for supporting a solid electrolyte having a thickness of 30 ⁇ m was prepared. Next, a solid electrolyte sheet was prepared in the same manner as in Example 1.
  • Comparative Example 2 The fiber composition was 5.2 g in the same manner as in Example 1 except that 55 parts of the crimp heat-sealing composite fiber used in Example 4 and 45 parts of the drawn PET fiber used in Example 4 were used. A non-woven fabric for supporting a solid electrolyte having a thickness of / m 2 and a thickness of 38 ⁇ m was prepared. Next, a solid electrolyte sheet was prepared in the same manner as in Example 1.
  • the fiber composition was 100 parts of heat-sealing composite fiber (straight type without crimp, core sheath type, core: PP, sheath: PE, fineness: 0.2dtex, fiber length: 3 mm), and the same as in Example 1.
  • a non-woven fabric for supporting a solid electrolyte having a basis weight of 8.0 g / m 2 and a thickness of 22 ⁇ m was prepared by the same method.
  • a solid electrolyte sheet was prepared in the same manner as in Example 1.
  • the fiber composition was 60 parts of drawn PET fiber having a fineness of 0.6 dtex and a fiber length of 5 mm and 40 parts of unstretched PET fiber for a binder having a fineness of 0.2 dtex and a fiber length of 3 mm.
  • a uniform papermaking slurry of mass% was prepared, a wet paper web was obtained using a circular net paper machine, and dried with a cylinder dryer having a surface temperature of 140 ° C. to obtain a sheet.
  • One roll is a chrome-plated steel roll, the other roll is a resin roll having a shore D hardness of 92, and the obtained sheet is calendar-processed by a calendar device having a surface temperature of the steel roll at room temperature.
  • a non-woven fabric for supporting a solid electrolyte having a basis weight of 5.1 g / m 2 and a thickness of 23 ⁇ m was prepared.
  • Non-woven fabric basis weight The basis weight of the non-woven fabric was measured according to JIS P8124: 2011.
  • Non-woven fabric air permeability For each solid electrolyte-supporting non-woven fabric, a sample piece having a flow direction of 100 mm and a width direction of 100 mm was cut out, and the ventilation resistance was measured using a breathability tester (manufactured by Kato Tech Co., Ltd., trade name KES-F8-AP1). The air permeability was calculated from the following formula 1.
  • Air permeability (cm 3 / cm 2 ⁇ sec) 12.5 / ventilation resistance
  • ⁇ No width shrinkage or wrinkles occur in the supporting non-woven fabric during running.
  • ⁇ The width of the supporting non-woven fabric during running shrinks slightly, but wrinkles do not occur.
  • X The width of the supporting non-woven fabric during running shrinks and wrinkles occur.
  • ⁇ The sheet shape can be maintained and the solid electrolyte does not fall off.
  • ⁇ The sheet shape can be maintained, but the solid electrolyte slightly falls off.
  • X The solid electrolyte falls off from the non-woven fabric.
  • the solid electrolyte sheet was wound around a round bar having a diameter of 3 cm, and the solid electrolyte was visually observed for bending and dropping of the solid electrolyte, and evaluated according to the following evaluation criteria.
  • the non-woven fabrics for supporting the solid electrolyte produced in Examples 1 to 11 are the non-woven fabric A using the crimp heat-sealing composite fibers, and the content of the crimp heat-sealing composite fibers. Is 60% by mass or more and 100% by mass or less.
  • the non-woven fabrics for supporting solid electrolytes of Examples 1 to 11 had strong tensile strength and excellent process runnability. Further, the solid electrolyte was excellent in impregnation property, and in the hot pressing step of thinning the solid electrolyte layer, the crimped heat-sealing composite fiber was plastically deformed, so that the solid electrolyte layer was hardly cracked. Further, the solid electrolyte sheets of Examples 1 to 11 were excellent in self-supporting property and flexibility.
  • the crimp heat-sealing composite fiber is composed of a polypropylene-based polymer as a core and a polyolefin-based polymer having a lower melting point than the polypropylene-based polymer used as the core. No cracks were observed in the solid electrolyte layer of the supporting nonwoven fabrics of Examples 1 and 2, which are crimped core-sheath type heat-sealing composite fibers and have a fineness of 0.1 to 0.4 dtex.
  • Example 8 From the comparison between Example 1 and Example 8, the supporting non-woven fabric of Example 1 in which the content of the crimp heat-sealing composite fiber is 60% by mass or more has improved tensile strength and excellent process runnability. rice field.
  • Example 10 Compared to the supporting non-woven fabric of Example 10 in which the number of crimps of the heat-sealing composite fiber exceeds 25 pieces / inch, the texture of the supporting non-woven fabric is improved, the tensile strength is increased, and the process runnability is excellent. Was there.
  • the supporting nonwoven fabric of Example 11 has an air permeability of less than 150 cm 3 / cm 2 ⁇ sec, so that the solid electrolyte slurry permeates the inside of the supporting nonwoven fabric. It was necessary to lower the coating speed as compared with the supporting non-woven fabric of 5. In addition, due to the high density, a slight dropout of the solid electrolyte was observed.
  • the supporting non-woven fabric of Comparative Example 4 which does not contain the crimp heat-sealing composite fiber has excellent air permeability of the supporting non-woven fabric and excellent impregnation property of the solid electrolyte, but the tensile strength is lowered, so that the process runnability is improved. It was lowered, and the solid electrolyte layer was difficult to be thinned and easily cracked in the hot pressing step when thinning.
  • Example 12 ⁇ Preparation of non-woven fabric A> Crunch heat-sealing composite fiber (core sheath type, core: PP, sheath: PE, fineness: 0.2 dtex, fiber length: 3 mm, number of crimps: 14 pieces / inch) 80 parts by mass and 0.3 dtex, fiber 20 parts by mass of PP fiber having a length of 3 mm was dispersed in water with a pulper to prepare a uniform papermaking slurry having a concentration of 0.5% by mass, and a wet paper web was obtained using a circular net paper machine to obtain a wet paper web, and the surface temperature was 133.
  • core sheath type core: PP
  • sheath: PE fineness: 0.2 dtex
  • fiber length 3 mm
  • number of crimps 14 pieces / inch
  • the non-woven fabric A having a basis weight of 3.5 g / m 2 was prepared by drying with a cylinder dryer at ° C. When the non-woven fabric A was observed, there was a hole defect having a diameter of 0.2 to 0.8 mm ⁇ .
  • a polypropylene polymer was discharged using a melt-blown non-woven fabric manufacturing apparatus, and a non-woven fabric B having an average fiber diameter of 1.5 ⁇ m and a basis weight of 1.2 g / m 2 was laminated on one side of the non-woven fabric A.
  • one roll is a chrome-plated steel roll
  • the other roll is a resin roll with Shore A hardness of 70
  • the surface temperature of the steel roll is lightly nipated with a calendar at room temperature to reduce the basis weight.
  • a non-woven fabric for supporting a solid electrolyte having a thickness of 4.7 g / m 2 and a thickness of 30 ⁇ m was prepared.
  • the tertiary mixed solution and the zirconia balls having a diameter of 5 mm are used so that the space, the mixed solution and the zirconia balls each occupy one third of the total volume of the kneading container. It was put into a kneading container. The quaternary mixture prepared thereby was put into a rotation / revolution mixer and stirred at 3000 rpm for 3 minutes to prepare a solid electrolyte slurry.
  • the non-woven fabric for supporting the solid electrolyte is continuously guided from above through the guide roller into the coating tank containing the above-mentioned solid electrolyte slurry.
  • the solid electrolyte is immersed in the slurry, and for the purpose of impregnating the inside of the supporting non-woven fabric with the solid electrolyte, it is nipped by a roll press in the coating tank and pulled up through a guide roller.
  • both sides of the supporting nonwoven fabric are smoothed by applying a plastic blade, excess solid electrolyte slurry is scraped off, and the supporting nonwoven fabric impregnated with the solid electrolyte is guided to a hot air dryer and dried from both sides. Then, the obtained solid electrolyte-supporting sheet was hot-pressed at a temperature of 120 ° C. and a load of 5 t / cm 2 to prepare a solid electrolyte sheet.
  • Example 13 A polymer solution of polyvinyl alcohol was electrostatically spun onto the non-woven fabric A having a basis weight of 3.5 g / m 2 produced in Example 12 using an electrospinning manufacturing apparatus to obtain ultrafine fibers having an average fiber diameter of 0.6 ⁇ m.
  • the non-woven fabric B By spraying on one side of the surface of the non-woven fabric A, the non-woven fabric B having a basis weight of 1.2 g / m 2 was laminated.
  • one roll is a chrome-plated steel roll
  • the other roll is a resin roll with Shore A hardness of 70
  • the surface temperature of the steel roll is lightly nipated with a calendar at room temperature to reduce the basis weight.
  • a non-woven fabric for supporting a solid electrolyte having a thickness of 4.7 g / m 2 and a thickness of 31 ⁇ m was prepared. Subsequently, a solid electrolyte sheet was prepared in the same manner as in Example 12.
  • Example 14 Nonwoven fabric A was prepared in the same manner as in Example 12 except that the basis weight was 3.0 g / m 2. When the non-woven fabric A was observed, there was a hole defect having a diameter of 0.2 to 0.8 mm ⁇ . A polymer solution of polyvinyl alcohol is electrostatically spun onto the non-woven fabric A using an electrospinning manufacturing apparatus, and ultrafine fibers having an average fiber diameter of 0.6 ⁇ m are placed on both sides of the non-woven fabric A with a basis weight of 1.0 g / m 2. Nonwoven fabric B was sprayed and laminated.
  • one roll is a chrome-plated steel roll
  • the other roll is a resin roll with Shore A hardness of 70
  • the surface temperature of the steel roll is lightly nipated with a calendar at room temperature, and the basis weight is 5.
  • a non-woven fabric for supporting a solid electrolyte having a thickness of .0 g / m 2 and a thickness of 34 ⁇ m was prepared.
  • a solid electrolyte sheet was prepared in the same manner as in Example 12.
  • the solid electrolyte-supporting non-woven fabrics produced in Examples 12 to 14 have an average fiber diameter of 2 ⁇ m or less on at least one surface of the non-woven fabric A using the crimp heat-sealing composite fiber.
  • Nonwoven fabric B made of ultrafine fibers is laminated.
  • the non-woven fabric A had hole defects, but the non-woven fabric B closed the hole defects and was able to support the solid electrolyte.
  • the tensile strength was strong and the process runnability was excellent.
  • the solid electrolyte was excellent in impregnation property, and in the hot pressing step of thinning the solid electrolyte layer, the crimped heat-sealing composite fiber was plastically deformed, so that the solid electrolyte layer was hardly cracked. Further, the solid electrolyte sheets of Examples 12 to 14 were excellent in self-supporting property and flexibility.
  • the solid electrolyte supporting non-woven fabric and the solid electrolyte sheet of the present invention can be suitably used for an all-solid-state lithium battery.

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JP2023177489A (ja) * 2022-06-02 2023-12-14 日本バイリーン株式会社 不織布とその製造方法、および、固体電解質シート
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JP2025134017A (ja) * 2022-07-29 2025-09-11 トヨタ自動車株式会社 固体電解質シート及び全固体電池
WO2025258604A1 (ja) * 2024-06-12 2025-12-18 マクセル株式会社 全固体二次電池

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