WO2022220186A1 - 固体電解質用支持体及びそれを含む固体電解質シート - Google Patents
固体電解質用支持体及びそれを含む固体電解質シート Download PDFInfo
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- WO2022220186A1 WO2022220186A1 PCT/JP2022/017200 JP2022017200W WO2022220186A1 WO 2022220186 A1 WO2022220186 A1 WO 2022220186A1 JP 2022017200 W JP2022017200 W JP 2022017200W WO 2022220186 A1 WO2022220186 A1 WO 2022220186A1
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- WIPO (PCT)
- Prior art keywords
- solid electrolyte
- support
- layer
- nonwoven fabric
- fiber diameter
- Prior art date
Links
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 95
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 57
- 238000011084 recovery Methods 0.000 claims abstract description 15
- 239000000835 fiber Substances 0.000 claims description 78
- 229920001410 Microfiber Polymers 0.000 claims description 20
- 229920000728 polyester Polymers 0.000 claims description 10
- 229920002994 synthetic fiber Polymers 0.000 claims description 7
- 239000012209 synthetic fiber Substances 0.000 claims description 7
- 239000010410 layer Substances 0.000 description 61
- 239000003792 electrolyte Substances 0.000 description 32
- 238000000034 method Methods 0.000 description 27
- 238000012360 testing method Methods 0.000 description 16
- 239000004744 fabric Substances 0.000 description 14
- 229920000139 polyethylene terephthalate Polymers 0.000 description 12
- 239000005020 polyethylene terephthalate Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 11
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- 238000005259 measurement Methods 0.000 description 6
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- 238000004519 manufacturing process Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- -1 polypropylene Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 239000004734 Polyphenylene sulfide Substances 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
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- 239000000463 material Substances 0.000 description 3
- 239000003658 microfiber Substances 0.000 description 3
- 229920000069 polyphenylene sulfide Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000004049 embossing Methods 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002203 sulfidic glass Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229910005839 GeS 2 Inorganic materials 0.000 description 1
- 229910018091 Li 2 S Inorganic materials 0.000 description 1
- 229910018111 Li 2 S-B 2 S 3 Inorganic materials 0.000 description 1
- 229910010920 LiLaTiO3 Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000004750 melt-blown nonwoven Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
- D04H3/16—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic filaments produced in association with filament formation, e.g. immediately following extrusion
-
- 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
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- 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
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/005—Synthetic yarns or filaments
- D04H3/009—Condensation or reaction polymers
- D04H3/011—Polyesters
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
- D04H3/12—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with filaments or yarns secured together by chemical or thermo-activatable bonding agents, e.g. adhesives, applied or incorporated in liquid or solid form
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
-
- 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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
-
- 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
- D10B2401/00—Physical properties
- D10B2401/18—Physical properties including electronic components
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- 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 support and a solid electrolyte sheet including the same.
- the corresponding lithium-ion secondary battery consists of a positive electrode active material, a negative electrode active material, and an electrolytic solution. , various improvements are underway. In addition, the use of batteries in automobiles and other products that are directly linked to human life is progressing, and safety and reliability are required at the same time as the functionality of the batteries is improved.
- the battery that is currently attracting attention is the all-solid-state battery.
- conventional lithium-ion secondary batteries use an organic electrolyte as an electrolyte, there is a risk of ignition due to an internal short circuit due to overcharge or overdischarge, and there is also the problem of liquid leakage.
- all-solid-state batteries use a solid electrolyte and are very superior in terms of safety and reliability.
- solid electrolytes sulfide- and oxide-based inorganic electrolytes and polymer-based organic electrolytes are widely used.
- the solid electrolyte In order to achieve high energy density and high capacity, which are the required characteristics of batteries, the solid electrolyte must be thin and have high ionic conductivity, as well as strength to improve handling.
- a support electrolyte is used in which a support is coated with a solid electrolyte, and a fibrous sheet such as a non-woven fabric is used as the support.
- patent document 1 discloses a solid electrolyte sheet having an aromatic liquid crystal polyester nonwoven fabric, and the aromatic liquid crystal polyester nonwoven fabric has a high porosity for the purpose of being filled with a polymer solid electrolyte. Characterized by
- Patent Document 2 discloses a solid electrolyte sheet having a porous substrate made of a fibrous material as a support.
- Patent Document 3 discloses a solid electrolyte sheet using a nonwoven fabric having a specific range of basis weight and thickness as a support.
- Patent Literatures 1 to 3 the flexibility of the interface of the electrolyte sheet is not sufficiently taken into consideration, and there is a problem of an increase in electrical resistance due to insufficient followability and contact with the electrode interface as the electrolyte sheet. there were.
- the problem to be solved by the present invention is to provide a solid electrolyte support suitable for obtaining an electrolyte sheet with low electrical resistance, and a solid electrolyte sheet including the same.
- the present invention is as follows.
- the nonwoven fabric includes a layer (I layer) containing one ultrafine fiber having a fiber diameter of 0.1 to 5.0 ⁇ m and a layer (II layer) containing one fiber having a fiber diameter of more than 5.0 ⁇ m and 30 ⁇ m or less. And, the solid electrolyte support according to the above [10]. [12] The solid electrolyte support according to any one of [1] to [11], wherein the nonwoven fabric is thermally bonded over the entire surface.
- the nonwoven fabric includes a layer (I layer) containing ultrafine fibers with a fiber diameter of 0.1 to 5.0 ⁇ m and a layer (II layer) containing fibers with a fiber diameter of more than 5.0 ⁇ m and 30 ⁇ m or less,
- the solid according to any one of [1] to [12] above, wherein the support has an elastic recovery of 45 to 99% and a compressibility of 0.1 to 9.7%.
- a solid electrolyte sheet comprising the solid electrolyte support according to any one of [1] to [13] and a solid electrolyte.
- the solid electrolyte support of the present invention is suitable for obtaining an electrolyte sheet with low electrical resistance.
- the solid electrolyte sheet of the present invention has low electrical resistance.
- One embodiment of the present invention is a solid electrolyte support containing a non-woven fabric, wherein the support has an elastic recovery rate of 30 to 99%.
- the solid electrolyte support (hereinafter also simply referred to as "support") of the present embodiment includes a non-woven fabric.
- the type of nonwoven fabric is not particularly limited, and for example, spunbond nonwoven fabrics and meltblown nonwoven fabrics can be used.
- the elastic recovery rate of the support of the present embodiment is 30 to 99%, preferably 45% or more, more preferably 50% or more, and preferably 98% or less, more preferably 97% or less. .
- the elastic recovery rate greatly affects the followability of the electrolyte sheet to the electrode interface. That is, the higher the elastic recovery rate, the more the sheet follows the electrode interface, and the electrical resistance between the surface of the electrolyte sheet and the electrode is reduced.
- the porosity of the support of the present embodiment is preferably 30-95%, more preferably 35-90%, still more preferably 40-85%. If the porosity is 30% or more, the amount of solid electrolyte retained is large, so that the solid electrolytes are in sufficient contact with each other, and the electric resistance inside the sheet is reduced. On the other hand, if the porosity is 95% or less, the strength as a support can be ensured, and the occurrence of a short circuit in the electrode reaction of the active material can be suppressed.
- the compressibility of the support of the present embodiment is preferably 0.1% or more, more preferably 0.5% or more, still more preferably 1% or more, and preferably 40% or less, more preferably 35%. 30% or less, and most preferably 9.7% or less.
- the manufacturing process of the electrolyte sheet includes press molding, and the higher the compressibility of the support, the thinner the sheet. Further, if the compressibility is high, a large amount of solid electrolyte can be filled inside the sheet, the contact area between the electrolytes increases, and the electrical resistance decreases.
- the nonwoven fabric contained in the support of the present embodiment preferably contains synthetic fibers.
- Synthetic fibers are chemically stable, and are easy to obtain good quality electrolyte sheets.
- the synthetic fiber material polyolefins such as polypropylene and polyethylene, polyesters such as polystyrene, polyphenylene sulfide, aramid, polyamideimide, polyimide, nylon, and polyethylene terephthalate (PET) can be used, and polyester is particularly preferred. Since polyester has higher heat resistance than other resins, a support including a nonwoven fabric containing it has excellent dimensional stability.
- polyester is chemically stable without causing reactions such as corrosion even when it comes into contact with a solid electrolyte such as sulfide or lithium metal.
- polyester has electrical insulation properties, which leads to suppression of short circuiting of the electrode active material.
- the support of the present embodiment preferably has a thickness of 5 to 200 ⁇ m, more preferably 7 to 180 ⁇ m, still more preferably 10 to 150 ⁇ m under a load of 100 g/m 2 .
- the thickness is 5 ⁇ m or more under a load of 100 g/m 2 , the tensile strength can be easily increased and the handleability during coating is improved.
- the thickness is 200 ⁇ m or less under a load of 100 g/m 2 , the thickness after press molding is suppressed and the electrical resistance of the electrolyte sheet is lowered.
- the nonwoven fabric contained in the support of the present embodiment preferably contains fibers having a fiber length of 51 mm or longer, more preferably 100 mm or longer, and even more preferably 150 mm or longer. If the fiber length is 51 mm or more, tensile properties, tear properties, and puncture properties required for the support are excellent. In addition, if the fiber length is 51 mm or more, it is easy to produce an electrolyte sheet with less fibers falling off and excellent shape retention.
- the basis weight of the support of this embodiment is preferably 5 to 50 g/m 2 , more preferably 8 to 40 g/m 2 , still more preferably 10 to 30 g/m 2 . If the basis weight is 5 g/m 2 or more, it can be handled with good handleability in the coating process, and if it is 50 g/m 2 or less, it will be sufficiently thin after press molding, so that the electric resistance can be easily lowered as an electrolyte sheet.
- the apparent density of the support of the present embodiment is preferably 0.069-0.97 g/cm 3 , more preferably 0.13-0.90 g/cm 3 , still more preferably 0.21-0. .83 g/cm 3 . If the apparent density is 0.69 g/cm 3 or more, the strength as a support can be ensured, and the occurrence of short circuits in the electrode reaction of the active material can be suppressed. On the other hand, if the apparent density is 0.97 g/cm 3 or less, the amount of solid electrolyte retained is large, so the solid electrolytes are in sufficient contact with each other, and the electric resistance inside the sheet is low.
- the nonwoven fabric contained in the support of the present embodiment preferably contains an ultrafine fiber layer with a fiber diameter of 0.1 to 5 ⁇ m.
- an ultrafine fiber layer By including the ultrafine fiber layer, it is easy to form an electrolyte sheet in which the solid electrolyte is uniformly arranged, and the electric resistance can be lowered.
- strike-through during coating of the solid electrolyte is suppressed, and there are no pinholes or defects in the electrolyte sheet, making it easy to obtain a high-quality electrolyte sheet.
- the fiber diameter of the ultrafine fiber layer is 0.1 ⁇ m or more, the fiber strength is sufficiently high, and the strength of the support is ensured, which is preferable.
- the fiber diameter of the ultrafine fiber layer is 5 ⁇ m or less, the distance between the fibers is made uniform, and it is easy to form an electrolyte sheet in which the solid electrolyte is uniformly arranged.
- the fiber diameter of the ultrafine fiber layer is preferably 0.3 to 4.0 ⁇ m, more preferably 0.5 to 3.0 ⁇ m.
- the nonwoven fabric contained in the support of the present embodiment has at least two layers including an ultrafine fiber layer (I layer) having a fiber diameter of 0.1 to 5 ⁇ m and a fiber layer (II layer) having a fiber diameter of more than 5 ⁇ m and 30 ⁇ m or less. It is preferably composed of In this case, the I layer serves as a functional layer, and the II layer serves as a strength layer.
- the I layer serves as a functional layer
- the II layer serves as a strength layer.
- the manufacturing method of the nonwoven fabric contained in the support of this embodiment is not limited.
- the manufacturing method is preferably a spunbond method, a dry method, a wet method, or the like.
- the manufacturing method is preferably a dry method or a wet method using ultrafine fibers, an electrospinning method, a melt-blown method, force spinning, or the like.
- the I layer is preferably formed by the meltblown method.
- the fibers forming the I layer may be split or fibrillated by beating, partial dissolution, or the like, and then used for the production of the nonwoven fabric.
- Examples of the method of integrating an unbonded web and the method of forming a laminated nonwoven fabric having the I layer and the II layer include a method of integration by thermal bonding, a three-dimensional Examples include a method of entangling, a method of integrating with a particulate or fibrous adhesive, and the like. Integration by thermal bonding is preferable in that a laminated nonwoven fabric can be formed without using a binder.
- Methods of integration by thermal bonding include integration by thermal embossing (thermal embossing roll method) and integration by high-temperature hot air (air-through method).
- thermal bonding for example, is performed by thermal bonding using a press roll (flat roll or emboss roll) at a temperature 50 to 120° C. lower than the melting point of the synthetic resin and a linear pressure of 100 to 1000 N/cm. can be done.
- a press roll flat roll or emboss roll
- a linear pressure 100 to 1000 N/cm.
- thermal bonding using a flat roll it is preferable to use a nonwoven fabric that is thermally bonded over the entire surface by thermal bonding using a flat roll.
- the term "thermally bonded over the entire surface” means that the entire surface of the nonwoven fabric is thermally bonded, not the so-called partial thermal bonding (point bonding) in which a portion of the nonwoven fabric is thermally bonded.
- the linear pressure in the heat bonding step is 100 N/cm or more, sufficient bonding can be obtained and sufficient strength can be easily exhibited.
- the linear pressure is 1000 N/cm or less, the deformation of the fibers is small, the apparent density is low, and the porosity is high, making it easier to obtain the desired effects.
- the fabric temperature before pressing is the temperature of the nonwoven fabric (web) 50 cm upstream from the roll nip point.
- the fabric temperature before pressing is the temperature of the nonwoven fabric (web) 50 cm upstream from the roll nip point.
- the temperature of the fabric before pressing within the range of 40 to 120° C.
- the fabric temperature high before pressing the crystallinity of the yarn is promoted in advance, thereby ensuring the minimum amount of amorphous required for bonding between fibers, suppressing excessive pressure bonding, and elastic recovery. It can be a support with a high modulus.
- Another embodiment of the present invention is a solid electrolyte sheet including the solid electrolyte support and a solid electrolyte.
- a solid electrolyte sheet including the support and the solid electrolyte of the present embodiment will be described below.
- the electric conductivity of the solid electrolyte sheet containing the support and the solid electrolyte of the present embodiment is preferably 1.0 ⁇ 10 ⁇ 5 to 5.0 ⁇ 10 ⁇ 1 s/m, more preferably 5.0 ⁇ 10 ⁇ 5 s/m. 0 ⁇ 10 ⁇ 5 to 1.0 ⁇ 10 ⁇ 1 s/m, more preferably 1.0 ⁇ 10 ⁇ 4 to 5.0 ⁇ 10 ⁇ 2 s/m.
- the solid electrolyte used in combination with the support of the present embodiment is not particularly limited as long as it has lithium ion conductivity.
- inorganic solid electrolytes such as sulfide solid electrolytes and oxide solid electrolytes, and polymer-based solid electrolytes.
- sulfide-based solid electrolytes include Li 2 SP 2 S 5 , Li 2 S -- Si , Li 2 SP 2 S 5 -GeS 2 , and Li 2 S--B 2 S 3 -based glasses.
- Li 10 GeP 2 S 12 (LGPS system) and Li 6 PS 5 Cl (aldirodite system) can be used.
- an aldirodite-based material having particularly high lithium ion conductivity and high chemical stability is preferably used.
- oxide-based solid electrolytes include Li7La3Zr2012 , LiTi2Z ( PO4) 3 , LiGe02 ( PO4) 3 , LiLaTiO3 and the like.
- the solid electrolyte When the solid electrolyte is applied to the support of the present embodiment, the solid electrolyte can be applied in a slurry state.
- the slurry used for coating can be prepared by adding solid electrolyte particles and a binder to a solvent and mixing them. It is preferable to select a solvent for the slurry that does not easily degrade the solid electrolyte. In particular, it is more preferable to use a super-dehydrated solvent with a water content of 0.001% by mass (10 ppm) or less. After the slurry is filled into the pores of the support, the solvent in the slurry is removed by drying. After applying the slurry and drying the solvent, the composite of the support and the solid electrolyte is press molded.
- the press molding conditions are, for example, a pressure of 5 to 50 MPa, a temperature of 50 to 200° C., and a press time of 1 to 30 minutes.
- the length direction of the nonwoven fabric is the MD direction (machine direction), and the width direction is the direction perpendicular to the length direction in the plane of the nonwoven fabric.
- Metsuke (g/m 2 ) According to the method specified in JIS L-1906, a test piece with a length of 20 cm x width of 25 cm is collected at 9 locations per 1 m x 1 m in total, 3 locations per 1 m in the width direction of the sample and 3 locations per 1 m in the length direction. The weight was determined by converting the average value into mass per unit area.
- Thickness ( ⁇ m) According to the method specified in JIS L-1906, the thickness was measured at 10 locations per 1 m width of the test piece under the condition of a load of 9.8 kPa, and the average value was obtained.
- the field of view at each magnification was 12.7 ⁇ m ⁇ 9.3 ⁇ m at 10000 ⁇ , 21.1 ⁇ m ⁇ 15.9 ⁇ m at 6000 ⁇ , and 31.7 ⁇ m ⁇ 23.9 ⁇ m at 4000 ⁇ . More than 100 fibers were photographed at random, and all fiber diameters were measured. However, fibers fused together in the yarn length direction were excluded from the measurement targets.
- the weight average fiber diameter (Dw) determined by is taken as the average fiber diameter ( ⁇ m).
- Elastic Recovery Rate and Compression Rate were measured using an MCT-50 microcompression tester manufactured by Shimadzu Corporation. The test conditions were measured in a load-unload mode in which the sample was loaded to the maximum test force and then unloaded to the minimum test force. The minimum test force was set to 0.05 mN, and the maximum test force was set to the test force at 10% deformation in compression mode.
- the elastic recovery rate and compressibility were calculated as follows.
- This mixed solution was put into a kneading vessel, and further zirconia balls were put into the kneading vessel so as to occupy 1 ⁇ 3 of the kneading vessel, and the mixture was stirred at 3000 rpm for 5 minutes to prepare an electrolyte slurry.
- the support was impregnated with the electrolyte slurry, nipped by a roll press, and smoothed with a blade to obtain a composite in which the slurry sufficiently permeated the inside of the support.
- An electrolyte sheet was produced by drying this composite with a hot air dryer.
- Examples 1 to 7, 12 As a fiber layer (II layer) having a fiber diameter of more than 5 ⁇ m and 30 ⁇ m or less, polyethylene terephthalate (PET) resin is discharged from a spinneret for spunbonding (V-type nozzle) at a spinning temperature of 290 ° C., and a cooling device is used immediately below the spinneret.
- PET polyethylene terephthalate
- the yarn is symmetrically cooled from both sides (both wind speed 0.5 m/s), pulled by a draw jet to obtain continuous long fibers (fiber diameter 15 ⁇ m), and the fibers are spread and dispersed and deposited on the web conveyor. and formed a web.
- a PET resin was spun at a spinning temperature of 290° C. by a meltblowing method and blown onto the web.
- the distance from the meltblown nozzle to the web was set to 300 mm
- the suction force on the collecting surface immediately below the meltblown nozzle was set to 0.2 kPa
- the wind speed was set to 7 m/sec.
- continuous long fibers fiber diameter 15 ⁇ m
- the laminated web was integrated with press rolls (calender rolls), and as shown in Table 1 below, a nonwoven fabric was produced so as to have a predetermined thickness by adjusting the calender linear pressure and temperature. was used as a support.
- the position of the heat insulating plate of the heating roll was adjusted so that the fabric temperature before calendering, which is important for controlling the compression characteristics, was 50, 70, or 90°C.
- Example 8 As shown in Table 1 below, the same as in Example 1 except that polyphenylene sulfide (PPS) resin was used as the raw material, and the spinning temperature, calendering temperature, fabric temperature, thickness, and apparent density were adjusted to predetermined values. A non-woven fabric was produced as a support.
- PPS polyphenylene sulfide
- Example 9 As shown in Table 1 below, PET resin short fibers with a fiber diameter of 4 ⁇ m and a fiber length of 5 mm were collected on a net by a papermaking method so as to be 20 g / m 2 , and after dehydration and drying, the fibers were not dispersed. Then, a short fiber nonwoven fabric was obtained by pressing with a flat roll. At the time of crimping, the desired thickness, porosity, and compression characteristics were obtained by adjusting the calendering temperature and the fabric temperature appropriately and performing calendering.
- PET resin is discharged from a spunbond spinneret (V-type nozzle) at a spinning temperature of 290 ° C., and the yarn is spun on both sides by a cooling device immediately below the spinneret. It is cooled symmetrically from both sides (both at a wind speed of 0.5 m/s), pulled by a draw jet to obtain continuous long fibers (fiber diameter 15 ⁇ m), and the fibers are spread and dispersed and deposited on a web conveyor to form a web. did.
- the web was integrated with a calender roll, and a nonwoven fabric having a predetermined thickness was produced by adjusting the calender linear pressure, and this was used as a support.
- the temperature of the fabric before calendering was adjusted to 70°C.
- Example 11 A PET resin was used as the ultrafine fiber nonwoven fabric layer (layer I), spun by the meltblowing method at a spinning temperature of 290° C., and deposited on a web conveyor. At this time, the distance from the meltblown nozzle to the web was set to 300 mm, the suction force on the collection surface immediately below the meltblown nozzle was set to 0.2 kPa, and the wind speed was set to 7 m/sec. Next, as shown in Table 1 below, the web was integrated with a calender roll, and a nonwoven fabric having a predetermined thickness was produced by adjusting the calender linear pressure, and this was used as a support. The temperature of the fabric before calendering was adjusted to 70°C.
- Example 13 As in Example 1, polyethylene terephthalate (PET) resin was discharged from a spunbond spinneret (V-type nozzle) at a spinning temperature of 290 ° C. as a fiber layer (II layer) having a fiber diameter of more than 5 ⁇ m and 30 ⁇ m or less, Directly below the spinneret, the yarn is symmetrically cooled from both sides by a cooling device (both at a wind speed of 0.5 m/s), pulled by a draw jet to obtain continuous long fibers (fiber diameter 15 ⁇ m), and the fibers are spread and dispersed. and deposited on a web conveyor to form a web.
- a cooling device both at a wind speed of 0.5 m/s
- a PET resin was spun at a spinning temperature of 290° C. by a meltblowing method and blown onto the web.
- the distance from the meltblown nozzle to the web was set to 300 mm
- the suction force on the collecting surface immediately below the meltblown nozzle was set to 0.2 kPa
- the wind speed was set to 7 m/sec.
- the laminated web was integrated with press rolls (calender rolls), and as shown in Table 1 below, a nonwoven fabric was produced so as to have a predetermined thickness by adjusting the calender linear pressure and temperature. was used as a support.
- the position of the heat retaining plate of the heating roll was adjusted so that the temperature of the fabric before calendering, which is important for controlling the compression characteristics, was 70°C.
- Example 2 As shown in Table 1 below, a nonwoven fabric was produced in the same manner as in Example 10, except that the temperature of the fabric before calendering was set to 23° C., which is the atmospheric temperature, and used as a support.
- the solid electrolyte support of the present invention can be combined with an inorganic solid electrolyte such as a sulfide solid electrolyte or an oxide solid electrolyte, a polymer solid electrolyte, or the like to obtain a solid electrolyte sheet with low electrical resistance. It can be suitably used as a member for an all-solid battery.
- an inorganic solid electrolyte such as a sulfide solid electrolyte or an oxide solid electrolyte, a polymer solid electrolyte, or the like to obtain a solid electrolyte sheet with low electrical resistance. It can be suitably used as a member for an all-solid battery.
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Abstract
Description
すなわち、本発明は以下の通りのものである。
[1]不織布を含む固体電解質用支持体であって、該支持体の弾性回復率が30~99%であることを特徴とする、固体電解質用支持体。
[2]前記支持体の空隙率が30~95%である、前記[1]に記載の固体電解質用支持体。
[3]前記支持体の圧縮率が0.1~40%である、前記[1]又は[2]に記載の固体電解質用支持体。
[4]前記不織布が合成繊維を含む、前記[1]~[3]のいずれかに記載の固体電解質用支持体。
[5]前記合成繊維がポリエステルである、前記[4]に記載の固体電解質用支持体。
[6]前記支持体の100g/m2荷重時の厚みが5~200μmである、前記[1]~[5]のいずれかに記載の固体電解質用支持体。
[7]前記不織布が、繊維長51mm以上の繊維を含む、前記[1]~[6]のいずれかに記載の固体電解質用支持体。
[8]前記支持体の目付けが5~50g/m2である、前記[1]~[7]のいずれかに記載の固体電解質用支持体。
[9]前記不織布が、繊維径0.1~5.0μmの極細繊維を含む、前記[1]~[8]のいずれかに記載の固体電解質用支持体。
[10]前記不織布が、繊維径0.1~5.0μmの極細繊維を含む層と、繊維径5.0μm超30μm以下の繊維を含む層と、を含む、前記[1]~[9]のいずれかに記載の固体電解質用支持体。
[11]前記不織布が、1つの繊維径0.1~5.0μmの極細繊維を含む層(I層)と、1つの繊維径が5.0μm超30μm以下の繊維を含む層(II層)と、を含む、前記[10]に記載の固体電解質用支持体。
[12]前記不織布が、面全体で熱接着している、前記[1]~[11]のいずれかに記載の固体電解質用支持体。
[13]前記不織布が、繊維径0.1~5.0μmの極細繊維を含む層(I層)と、繊維径5.0μm超30μm以下の繊維を含む層(II層)と、を含み、前記支持体の弾性回復率が45~99%であり、かつ、前記支持体の圧縮率が0.1~9.7%である、前記[1]~[12]のいずれかに記載の固体電解質用支持体。
[14]前記[1]~[13]のいずれかに記載の固体電解質用支持体と、固体電解質とを含む、固体電解質シート。
[15]前記固体電解質シートの電気伝導率が1.0×10-5~5.0×10-1s/mである、前記[14]に記載の固体電解質シート。
本発明の1の実施形態は、不織布を含む固体電解質用支持体であって、該支持体の弾性回復率が30~99%であることを特徴とする、固体電解質用支持体である。
本実施形態の固体電解質用支持体(以下、単に「支持体」ともいう。)は、不織布を含む。不織布の種類に特に限りはなく、例えば、スパンボンド不織布やメルトブロウン不織布を使用可能である。
以下、本実施形態の支持体と固体電解質とを含む、固体電解質シートについて説明する。
本実施形態の支持体と固体電解質とを含む固体電解質シートの電気伝導率は、1.0×10-5~5.0×10-1s/mであることが好ましく、より好ましくは5.0×10-5~1.0×10-1s/m、さらに好ましくは、1.0×10-4~5.0×10-2s/mである。
スラリーの塗工及び溶媒の乾燥後、支持体と固体電解質の複合体はプレス成形される。プレス成形の条件としては、例えば、圧力が5~50MPa、温度が50~200℃、プレス時間が1~30分である。
JIS L-1906に規定の方法に従い、縦20cm×横25cmの試験片を、試料の幅方向1m当たり3箇所、長さ方向1m当たり3箇所の、計1m×1m当たり9箇所採取して質量を測定し、その平均値を単位面積当たりの質量に換算して目付けを求めた。
JIS L-1906に規定の方法に従い、試験片の幅1m当たり10箇所の厚みを荷重9.8kPaの条件下で測定し、その平均値を求めた。
上記(1)にて測定した目付け(g/m2)、及び上記(2)にて測定した厚み(μm)を用い、単位を調整して以下の式:
見掛け密度=(目付け)/(厚み)
により見掛け密度を算出した。
上記(3)にて計算した見掛け密度(g/cm3)を用いて、以下の式:
空隙率={1-(見掛け密度)/(樹脂密度)}/100
より空隙率を算出した。
不織布を10cm×10cmにカットし、上下60℃の鉄板に0.30MPaの圧力で90秒間プレスした後、白金を蒸着させた。SEM装置(JSM-6510 日本電子株式会社製)を用いて、加速電圧15kV、ワーキングディスタンス21mmの条件で、白金が蒸着された不織布を撮影した。撮影倍率は、平均繊維径が0.5μm未満の糸は10000倍、平均繊維径が0.5μm以上1.5μm未満の糸は6000倍、1.5μm以上の糸は4000倍とした。それぞれの撮影倍率での撮影視野は、10000倍では12.7μm×9.3μm、6000倍では21.1μm×15.9μm、4000倍では31.7μm×23.9μmとした。ランダムに繊維100本以上を撮影し、全ての繊維径を測長した。但し、糸長方向で融着している繊維同士は測定対象から除いた。以下の式:
Dw=ΣWi・Di=Σ(Ni・Di2)/(Ni・Di)
{式中、Wi=繊維径Diの重量分率=Ni・Di/ΣNi・Diであり、Niは繊維径Diの繊維の数である。}
により求められる重量平均繊維径(Dw)を、平均繊維径(μm)とした。
試料(不織布、支持体)の各端部10cmを除き、幅15mm×長さ20cmの試験片を、1m幅につき5箇所切り取った。試験片が破断するまで荷重を加え、MD方向の試験片の最大荷重時の強さの平均値を求めた。
島津製作所製MCT-50微小圧縮試験機を用いて、弾性回復率、圧縮率を測定した。試験条件は、試料に最大試験力まで負荷を与え、その後、最小試験力まで除荷を行う負荷―除荷モードにて測定した。最小試験力は0.05mN、最大試験力は圧縮モードにて10%変型時の試験力を設定した。弾性回復率、及び圧縮率は以下の通り算出した。
弾性回復率(Rr)={L2/(L1-L2)}×100
圧縮率(Cr)=(L1/d)×100
d:不織布(支持体)の厚み
L1:負荷モードでの最大試験力時と最小試験力時の変位差
L2:除荷モードでの最大試験力時と最小試験力時の変位差
測定装置として、HIOKI製Digital Super Megohmmeter、及びHIOKI製平板試料用電極SME-8311を使用した。100mm×100mmの試験片(固体電解質シート)を準備し、電圧10V、及び測定時間60秒の測定条件下で、電気伝導率を測定した。
尚、測定に用いる固体電解質シートは以下の通り作製した。硫化物電解質であるLi2S-P2S5(80:20モル%)の非晶質粉末に、SBR(電解質結着剤)のキシレン溶液を、SBRが非晶質粉末の質量に対して1%となるように添加し、混合液を調整した。さらにこの混合液に、NBR(電解質層結着剤)のキシレン溶液を、NBRが非晶質粉末に対して0.5%となるように添加し、さらに粘度調整のため脱水キシレンを適量添加した。この混合液を混錬容器に投入し、さらに混錬容器の1/3を占めるようにジルコニアボールを投入し、3000rpmで5分攪拌することで電解質スラリーを調合した。上記の電解質スラリーに支持体を含浸させ、さらにロールプレスによりニップし、ブレードにて平滑にすることで、スラリーが支持体内部に十分浸透した複合体を得た。この複合体を熱風乾燥機で乾燥させることで、電解質シートを作製した。
繊維径が5μm超30μm以下の繊維層(II層)として、ポリエチレンテレフタレート(PET)樹脂をスパンボンド用紡糸口金(V型ノズル)から、紡糸温度290℃で吐出し、紡糸口金直下で冷却装置により糸条を両側方から対称に冷却し(共に風速0.5m/s)、ドロージェットで牽引して連続長繊維(繊維径15μm)を得、該繊維を開繊分散してウェブコンベア上に堆積しウェブを形成した。次いで、極細繊維層(I層)として、PET樹脂を用い、紡糸温度290℃の条件下で、メルトブロウン法により紡糸して、上記ウェブ上に吹きつけた。この際、メルトブロウンノズルから上記ウェブまでの距離を300mmとし、メルトブロウンノズル直下の捕集面における吸引力を0.2kPa、風速を7m/secに設定した。また、その上に上記と同様のスパンボンド法で作製した連続長繊維(繊維径15μm)を積層させ、積層ウェブを得た。さらに、プレスロール(カレンダーロール)にて前記積層ウェブを一体化するとともに、以下の表1に示すように、カレンダー線圧、温度の調整により所定の厚みとなるようにして不織布を作製し、これを支持体とした。尚、圧縮特性の制御に重要なカレンダー前の布温度は、50、70、又は90℃となるように、加熱ロールの保温板の位置を調整した。
以下の表1に示すように、原料としてポリフェニレンサルファイド(PPS)樹脂を使用し、紡糸温度、カレンダー温度、布温度、厚み、見掛け密度を所定の値に調整したこと以外は、実施例1と同様にして不織布を作製し、これを支持体とした。
以下の表1に示すように、繊維径4μm、繊維長5mmのPET樹脂短繊維を抄造法にてネット上に20g/m2となるように捕集し、脱水乾燥後、繊維が散逸しない程度に、フラットロールにて圧着して短繊維不織布を得た。圧着時には、カレンダー温度、布温度を適宜調整しカレンダー加工することで、所望の厚み、空隙率、圧縮特性を得た。
繊維径が5μm超30μm以下の繊維層(II層)として、PET樹脂をスパンボンド用紡糸口金(V型ノズル)から、紡糸温度290℃で吐出し、紡糸口金直下で冷却装置により糸条を両側方から対称に冷却し(共に風速0.5m/s)、ドロージェットで牽引して連続長繊維(繊維径15μm)を得、該繊維を開繊分散してウェブコンベア上に堆積しウェブを形成した。次いで、以下の表1に示すように、カレンダーロールにて前記ウェブを一体化するとともに、カレンダー線圧の調整により所定の厚みとなるようにして不織布を作製し、これを支持体とした。尚、カレンダー前の布温度が70℃となるように調整した。
極細繊維不織布層(I層)として、PET樹脂を用い、紡糸温度290℃の条件下で、メルトブロウン法により紡糸して、ウェブコンベア上に堆積した。この際、メルトブロウンノズルから前記ウェブまでの距離を300mmとし、メルトブロウンノズル直下の捕集面における吸引力を0.2kPa、風速を7m/secに設定した。次いで、以下の表1に示すように、カレンダーロールにて前記ウェブを一体化するとともに、カレンダー線圧の調整により所定の厚みとなるようにして不織布を作製し、これを支持体とした。尚、カレンダー前の布温度が70℃となるように調整した。
実施例1と同様に、繊維径が5μm超30μm以下の繊維層(II層)として、ポリエチレンテレフタレート(PET)樹脂をスパンボンド用紡糸口金(V型ノズル)から、紡糸温度290℃で吐出し、紡糸口金直下で冷却装置により糸条を両側方から対称に冷却し(共に風速0.5m/s)、ドロージェットで牽引して連続長繊維(繊維径15μm)を得、該繊維を開繊分散してウェブコンベア上に堆積しウェブを形成した。次いで、極細繊維層(I層)として、PET樹脂を用い、紡糸温度290℃の条件下で、メルトブロウン法により紡糸して、上記ウェブ上に吹きつけた。この際、メルトブロウンノズルから上記ウェブまでの距離を300mmとし、メルトブロウンノズル直下の捕集面における吸引力を0.2kPa、風速を7m/secに設定した。さらに、プレスロール(カレンダーロール)にて前記積層ウェブを一体化するとともに、以下の表1に示すように、カレンダー線圧、温度の調整により所定の厚みとなるようにして不織布を作製し、これを支持体とした。尚、圧縮特性の制御に重要なカレンダー前の布温度は、70℃となるように、加熱ロールの保温板の位置を調整した。
繊維径4μm、繊維長5mmのPET樹脂からなる短繊維不織布に対して、以下の表1に示すようにカレンダー加工することで、所望の厚み、空隙率、圧縮特性を得た。尚、布温度に関しては特に考慮せず、雰囲気温度である23℃にてカレンダー加工を実施した。
以下の表1に示すように、カレンダー前の布温度を、雰囲気温度である23℃としたこと以外は、実施例10と同様にして不織布を作製し、これを支持体とした。
Claims (15)
- 不織布を含む固体電解質用支持体であって、該支持体の弾性回復率が30~99%であることを特徴とする、固体電解質用支持体。
- 前記支持体の空隙率が30~95%である、請求項1に記載の固体電解質用支持体。
- 前記支持体の圧縮率が0.1~40%である、請求項1又は2に記載の固体電解質用支持体。
- 前記不織布が合成繊維を含む、請求項1又は2に記載の固体電解質用支持体。
- 前記合成繊維がポリエステルである、請求項4に記載の固体電解質用支持体。
- 前記支持体の100g/m2荷重時の厚みが5~200μmである、請求項1又は2に記載の固体電解質用支持体。
- 前記不織布が、繊維長51mm以上の繊維を含む、請求項1または2に記載の固体電解質用支持体。
- 前記支持体の目付けが5~50g/m2である、請求項1又は2に記載の固体電解質用支持体。
- 前記不織布が、繊維径0.1~5.0μmの極細繊維を含む、請求項1または2に記載の固体電解質用支持体。
- 前記不織布が、繊維径0.1~5.0μmの極細繊維を含む層と、繊維径5.0μm超30μm以下の繊維を含む層と、を含む、請求項1又は2に記載の固体電解質用支持体。
- 前記不織布が、1つの繊維径0.1~5.0μmの極細繊維を含む層(I層)と、1つの繊維径が5.0μm超30μm以下の繊維を含む層(II層)と、を含む、請求項10に記載の固体電解質用支持体。
- 前記不織布が、面全体で熱接着している、請求項1又は2に記載の固体電解質用支持体。
- 前記不織布が、繊維径0.1~5.0μmの極細繊維を含む層(I層)と、繊維径5.0μm超30μm以下の繊維を含む層(II層)と、を含み、前記支持体の弾性回復率が45~99%であり、かつ、前記支持体の圧縮率が0.1~9.7%である、請求項1又は2に記載の固体電解質用支持体。
- 請求項1又は2に記載の固体電解質用支持体と、固体電解質とを含む、固体電解質シート。
- 前記固体電解質シートの電気伝導率が1.0×10-5~5.0×10-1s/mである、請求項14に記載の固体電解質シート。
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