FESTELEKTROLYT

Abstract

Solid electrolyte comprising a molecular crystal and an inorganic filler, wherein: the molecular crystal comprises a sulfolane-based compound and 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide lithium (LiCFSA) as the lithium salt; the inorganic filler is SiO2; and assuming that a mass of the inorganic filler per g of the solid electrolyte W (g / g SE ) is and that a specific surface area of ​​the inorganic filler A (m 2 / g) is a normalized surface WA (m 2 / G SE ) of the inorganic filler 15 to 900 m 2 / G SE .

Description

BACKGROUND OF THE INVENTION 1. Field of the invention

[0001] The invention relates to a solid electrolyte. 2. Description of the state of the art

[0002] Several battery technologies have been proposed, such as one disclosed in Japanese patent application 2013-214510 (JP 2013-214510 A). SUMMARY OF THE INVENTION

[0003] In JP 2013-214510 A, a molecular crystalline solid electrolyte is disclosed which contains an electron-donating sulfur-based organic compound and a lithium salt, but there is still room for improvement in ionic conductivity, as this solid electrolyte has a high crystallinity and therefore low ion mobility.

[0004] The present invention was developed taking into account the circumstances, and a main objective is to provide a solid electrolyte that can improve ionic conductivity.

[0005] The present invention particularly comprises the following aspects.

[0006] <1> A solid electrolyte containing a molecular crystal and an inorganic filler, wherein: The molecular crystal contains a sulfolane-based compound and 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide lithium (LiCFSA) as a lithium salt; the inorganic filler SiO2 is; and assuming that a mass of inorganic filler per g of solid electrolyte W (g / g SE ) is and that a specific surface area of ​​the inorganic filler A (m 2 / g) is a normalized surface WA (m 2 / G SE ) of the inorganic filler 15 to 900 m 2 / G SE is.

[0007] <2> The solid electrolyte after <1> , wherein the molar ratio of the sulfolane-based compound to the lithium salt contained in the molecular crystal is 2.0 or more and 3.1 or less.

[0008] <3> Solid electrolyte according to <1> or <2> , wherein the ratio of the inorganic filler contained in the solid electrolyte is 3.6 vol% to 69.4 vol%

[0009] <4> Solid electrolyte after one of the points <1> until <3> , wherein the ratio of the inorganic filler contained in the solid electrolyte is 27.4 vol% to 60.1 vol%.

[0010] <5> Battery, comprising the solid electrolyte according to one of the points <1> until <4> .

[0011] The solid electrolyte of the present invention can improve ionic conductivity. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Features, advantages, and technical and industrial significance of exemplary embodiments of the invention are described below with reference to the accompanying drawings, in which the same reference numerals denote the same elements, and wherein: Fig. Figure 1 is a diagram illustrating the relationship between a normalized surface WA of an inorganic filler and the ionic conductivity of a solid electrolyte at room temperature (25°C). DETAILED DESCRIPTION OF THE EXECUTION FORMS

[0013] The embodiments of the present invention are now described. It should be noted that aspects not specifically described here, but necessary for the implementation of the present invention (e.g., a general structure and a manufacturing process for a solid electrolyte that do not characterize the present invention), can be understood by those skilled in the art as design aspects based on the prior art in this field. The present invention can be put into practice based on the content disclosed herein and the general technical knowledge in this field.

[0014] Herein, a mean particle size of a particle is a median diameter (D50), i.e., a particle size that corresponds to 50% of the cumulative volume-based particle size distribution measured by laser diffraction / scattering particle size distribution measurement, unless otherwise specified. 1. Solid electrolyte

[0015] The present invention provides a solid electrolyte comprising a molecular crystal and an inorganic filler, wherein: The molecular crystal contains a sulfolane-based compound and 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide lithium (LiCFSA) as a lithium salt; the inorganic filler SiO2 is; and assuming that a mass of inorganic filler per g of solid electrolyte W (g / g SE ) is and that a specific surface area of ​​the inorganic filler A (m 2 / g) is a normalized surface WA (m 2 / G SE ) of the inorganic filler 15 to 900 m 2 / G SE is.

[0016] The solid electrolyte of the present invention contains a molecular crystal and an inorganic filler.

[0017] The molecular crystal used in the present invention has, in addition to a melting point (solid-liquid phase transition), a solid-solid phase transition in the vicinity of -3 °C.

[0018] By mixing the molecular crystal and the inorganic filler, the solid-solid phase transition temperature of the molecular crystal is shifted to a lower temperature in order to increase the ion mobility of the molecular crystal.

[0019] The solid electrolyte of the present invention can be used in a battery.

[0020] The molecular crystal contains a sulfolane-based compound and 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide lithium (LiCFSA) as a lithium salt.

[0021] The sulfolan-based compound can be sulfolan (SL) and a derivative or the like of sulfolan.

[0022] The molar ratio of the sulfolane-based compound to the lithium salt contained in the molecular crystal can be 2.0 or more and 3.1 or less, or 2.9 or more and 3.0 or less.

[0023] The inorganic filler is SiO2.

[0024] The ratio of the inorganic filler contained in the solid electrolyte can be 3.6 vol% to 69.4 vol%, 7.0 vol% or more, 13.1 vol% or more or 27.4 vol% or more, and 60.1 vol% or less, 53.1 vol% or less or 43.0 vol% or less.

[0025] The specific surface area of ​​the inorganic filler is not particularly limited and can range from 300 to 700 m². 2 / g.

[0026] In this context, the term "specific surface" means a specific surface according to BET.

[0027] Assuming that the mass of the inorganic filler per g of solid electrolyte is W (g / g SE) and the specific surface area of ​​the inorganic filler A (m²) 2 / g), the normalized surface area WA (m²) is 2 / G SE ) of the inorganic filler 15 to 900 m 2 / G SE . Mass W (g / gSE) of the inorganic filler per solid electrolyte × specific surface area A (m² / g) of the inorganic filler

[0028] If the normalized surface WA (m 2 / G SE ) of the inorganic filler 15 to 900 m 2 / G SE If the surface area WA of the inorganic filler exceeds 900 m², the ionic conductivity of the solid electrolyte is improved. 2 / G SE The conductivity of the solid electrolyte is reduced due to the percolation loss of the molecular crystal (ionically conductive part) caused by the inorganic filler. 2nd battery

[0029] A battery of the present invention may comprise the solid electrolyte of the present invention.

[0030] The battery of the present invention comprises a positive electrode, an electrolyte layer and a negative electrode in the specified order.

[0031] The battery of the present invention can comprise a positive electrode current collector, a positive electrode layer, an electrolyte layer, a negative electrode layer and a negative electrode current collector in the specified order.

[0032] The battery of the present invention can contain the solid electrolyte of the present invention in at least one layer selected from a positive electrode layer, an electrolyte layer and a negative electrode layer. Positive electrode

[0033] A positive electrode contains a positive electrode layer and also includes a positive electrode current collector, if required.

[0034] The positive electrode layer contains an active material for the positive electrode and may, if required, contain a solid electrolyte, a conductive material, a binder, a thickening agent, and the like.

[0035] The positive electrode layer can be formed by applying a positive electrode slurry to at least one surface of a support, such as a current collector for the positive electrode, and drying the result.

[0036] The positive electrode slurry contains a positive electrode active material and a solvent and may, if required, contain a solid electrolyte, a conductive material, a binder, a thickener, a solvent and the like.

[0037] There are no particular restrictions regarding the method for applying the positive electrode slurry, and examples of the method include a doctor blade process, a metal mask printing process, an electrostatic coating process, a dip coating process, a spray coating process, a roller coating process, an engraving coating process, and a screen printing process.

[0038] The support is not particularly limited, and those that have a self-supporting property can be suitablely selected for use; for example, a metal foil made of Cu or Al can be used.

[0039] An example of the active material for the positive electrode is an active oxide material. Examples of active oxide materials include LiNi. 0,8 Co 0,15 Al 0,05 O2, LiCoO2 LiMnO2, LiNiO2, LiVO2, LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2, LiMn2O4, Li(Ni0,5 Mn 1,5 )O4, LiFePO4, LiMnPO4, LiNiPO4 and LiCuPO4.

[0040] The active material of the positive electrode can be a particle of the active material of the positive electrode.

[0041] The mean particle size of the active material particle of the positive electrode is not particularly limited and can range from 1 nm to 100 µm.

[0042] The ratio of the active material of the positive electrode to the positive electrode layer is not particularly limited and can be 50.00 to 99.00 percent by mass.

[0043] The active material of the positive electrode can be coated with a lithium-ion conductive compound on at least part of its surface.

[0044] The lithium-ion conductive compound can be coated on at least part of the surface of the active material of the positive electrode or on the entire surface of the active material of the positive electrode.

[0045] Examples of lithium-ion conductive compounds include B₂O₃, Li₂B₄O₇, LiBPO₄, Li₃PO₄, LiPO₃, and LiNbO₃. The coating film thickness of the lithium-ion conductive compound can be, for example, 0.1 nm or more, and may be 1 nm or more. Alternatively, the coating film thickness of the lithium-ion conductive compound can be, for example, 100 nm or less, and may be 20 nm or less. The coating rate of the lithium-ion conductive compound used to coat the active material of the positive electrode can be, for example, 70% or more, and may be 90% or more, or 100%. A coating process for the lithium-ion conductive compound is not particularly restricted, and any conventionally known method can be used appropriately.

[0046] The solid electrolyte used in the positive electrode layer can be the solid electrolyte of the present invention, and another example comprises a solid electrolyte other than the solid electrolyte of the present invention contained in the electrolyte layer described below.

[0047] The ratio of solid electrolyte to the positive electrode layer is not particularly limited.

[0048] Examples of conductive materials include carbon materials, metal particles, and conductive polymers. Examples of carbon materials include granular carbon materials such as acetylene carbon black (AB) and chain carbon black (KB), and fibrous carbon such as carbon fiber, carbon nanotubes (CNT), and carbon nanofibers (CNF).

[0049] The ratio of conductive material in the positive electrode layer is not particularly limited.

[0050] Examples of the binder include acrylonitrile butadiene rubber (ABR), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), and styrene butadiene rubber (SBR).

[0051] The ratio of the binding agent in the positive electrode layer is not particularly limited.

[0052] Examples of thickening agents include polysaccharides such as carboxymethylcellulose (CMC) and methylcellulose.

[0053] Examples of solvents include aqueous solvents and organic solvents. An aqueous solvent is either water or a mixture containing water and a polar organic solvent. A suitable solvent can be selected based on factors such as the active material of the positive electrode, the binder, and so on.

[0054] Water can be used as an aqueous solvent due to its ease of handling. Examples of polar organic solvents that can be used in the mixed solvent include alcohols such as methanol, ethanol, and isopropyl alcohol, ketones such as acetone, and ethers such as tetrahydrofuran.

[0055] Examples of organic solvents include 1,2,3,4-tetrahydronaphthalene, n-heptane, butyl butyrate, diisobutyl ketone and N-methyl-2-pyrrolidone (NMP).

[0056] The material of the positive electrode current collector can be, for example, a metal such as aluminum, copper, SUS, or nickel. The thickness of the positive electrode current collector can be, for example, 0.1 µm or more and 100 µm or less. The positive electrode current collector can have the shape of a sheet or similar. The positive electrode current collector can have a structure in which a buffer layer, an elastic layer, or a PTC thermistor layer (PTC = positive temperature coefficient) is arranged on its surface. Negative electrode

[0057] The negative electrode contains a negative electrode layer and also includes, if required, a current collector for the negative electrode.

[0058] The negative electrode layer contains an active material of the negative electrode. If necessary, the negative electrode layer may contain at least a solid electrolyte, a conductive material, and a binder.

[0059] The layer of negative electrode can contain, for example, a lithium-based active material, a carbon-based active material, an oxide-based active material, a silicon-based active material, or the like as the active material of the negative electrode.

[0060] Examples of lithium-based active material include metallic lithium and lithium alloys. Examples of a metallic element included in addition to lithium in a lithium alloy include Mg, Ag, In, Sn, Si, Ga, Au, and Pt.

[0061] Examples of carbon-based active materials include graphite, hard carbon, and soft carbon.

[0062] An example of the oxide-based active material is lithium titanate.

[0063] Examples of Si-based active materials include simple Si, a Si alloy, and silicon oxide.

[0064] The active material of the negative electrode, for example, has the form of a particle. The average particle size of a particle made of active material from the negative electrode is not particularly limited and can range from 1 nm to 100 µm.

[0065] The solid electrolyte used in the negative electrode layer can be the solid electrolyte of the present invention, and another example comprises a solid electrolyte other than the solid electrolyte of the present invention contained in the electrode layer described below.

[0066] Examples of the conductive material and binder used in the negative electrode layer include those listed above as conductive material and binder in the positive electrode layer.

[0067] The thickness of the negative electrode layer can be 0.1 µm or more and 100 µm or less.

[0068] Examples of materials for the negative electrode current collector include SUS, aluminum, copper, nickel, iron, titanium, and carbon. The negative electrode current collector can be in the form of a foil, a plate, or similar. The top-view shape of the negative electrode current collector is not particularly restricted and includes, for example, circular, elliptical, rectangular, and any polygonal shapes. The thickness of the negative electrode current collector varies depending on the shape and can range, for example, from 1 µm to 50 µm and from 5 µm to 20 µm. The negative electrode current collector can have a structure in which a buffer layer, an elastic layer, or a layer of a positive temperature coefficient (PTC) thermistor is arranged on its surface. electrolyte layer

[0069] The electrolyte layer contains at least one electrolyte.

[0070] The electrolyte can be an electrolyte solution or a solid electrolyte.

[0071] The solid electrolyte contained in the electrolyte layer can be the solid electrolyte of the present invention and alternatively be a sulfide solid electrolyte, an oxide solid electrolyte, a halide solid electrolyte or the like.

[0072] Examples of sulfide solid electrolytes include solid electrolytes containing a lithium cell, an magnesium cell (where M is at least one of phosphorus, astronautium, sulfur, silicon, geron, tin, boron, alron, gallium, and inron), and a sulfur cell. Furthermore, the sulfide solid electrolyte may also contain at least one oxygen cell and one halogen cell.

[0073] Examples of sulfide solid electrolytes include Li₂S-P₂S₅, Li₂S-SiS₂, LiX-Li₂S-SiS₂, LiX-Li₂S-P₂S₅, LiX-Li₂O-Li₂S-P₂S₆, LiX-Li₂S-P₂O₅, LiX-Li₃PO₄-P₂S₅, and Li₃PS₄. It should be noted that the term "Li₂S-P₂S₅" refers to a material that uses raw material compositions containing Li₂S and P₂S₅, and the other terms are similarly defined.

[0074] Furthermore, "X" in LiX refers to a halogen element. Examples of halogen elements include fluorine, chloride, bromine, and iodine. One or more LiX elements may be present in a raw material composition containing LiX. If two or more LiX elements are present, the mixing ratio of these two or more LiX elements is not particularly restricted.

[0075] The molar ratio of the respective elements in the sulfide solid electrolyte can be controlled by adjusting the concentration of the respective elements in a raw material. Furthermore, the molar ratio and composition of the respective elements in the sulfide solid electrolyte can be measured, for example, by ICP atomic emission spectroscopy.

[0076] An example of the oxide solid electrolyte comprises a substance with a garnet-like structure containing a Li element, an La element, an A element (where A is at least one of Zr, Nb, Ta, and Al), and an O element. The oxide solid electrolyte could, for example, be Li₂OB₂O₃-P₂O₅, Li₂O-SiO₂, Li₂O-B₂O₃, Li 1,3 Al 0,3 Ti 0,7 (PO4)3, Li5La3Ta2O 12 , Li7La3Zr2O 12 , Li6BaLa2Ta2O 12 , Li 3,6 Si 0,6 P 0,4 O4, Li4SiO4, Li3PO4, Li 3+x PO 4-x N x (1 ≤ x ≤ 3) or the like.

[0077] The halide solid electrolyte can, for example, be a solid electrolyte containing Li, M and X (where M represents at least one of Ti, Al and Y and X represents F, CI or Br).

[0078] From the point of view of good handling, the solid electrolyte can have the form of a particle.

[0079] The mean particle size (D 50 ) of a particle of the solid electrolyte is not particularly limited and can range from 1 nm to 100 µm.

[0080] A single, two, or more solid electrolytes can be used. Furthermore, if two or more solid electrolytes are used, they can be mixed, or layers of each can be formed to obtain a multilayered structure.

[0081] The ratio of solid electrolyte to electrolyte layer is not particularly restricted and may, for example, be 50% by mass or more, in the range of 60% by mass or more and 100% by mass or less, in the range of 70% by mass or more and 100% by mass or less, or be 100% by mass. The solid electrolyte may contain an electrolyte solution in an amount of less than 10% by mass, based on the total electrolyte. It should be noted that the solid electrolyte may be a composite solid electrolyte containing an inorganic solid electrolyte and a polymer electrolyte.

[0082] If the electrolyte layer is a solid electrolyte layer, the solid electrolyte layer contains a solid electrolyte and further contains a binder and the like, if necessary.

[0083] Examples of the binder include those mentioned above as binders that may be contained in the positive electrode layer.

[0084] If the solid electrolyte layer contains a binder, the binder content can range from 0% to 10% by mass, based on the total amount of the solid electrolyte layer.

[0085] The thickness of the solid electrolyte layer is not particularly limited and can be, for example, 1 µm or more, and can be 100 µm or less from the point of view of reducing the resistance of the battery.

[0086] The battery type is not particularly restricted and includes, for example, a lithium-ion battery. The battery can be a primary or a secondary battery. The battery can be a solid-state battery.

[0087] Here, the term "solid-state battery" refers to a battery containing a solid electrolyte. A solid-state battery can be a semi-solid-state battery, containing both a solid electrolyte and a liquid, or a solid-state battery, containing no liquid. The battery's shape is not particularly restricted; for example, it can be button-shaped, cylindrical, square, leaf-shaped, knob-shaped, flat, or stacked.

[0088] The battery is used, for example, as a power source for vehicles such as hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), battery electric vehicles (BEVs), gasoline vehicles, or diesel vehicles. Specifically, the battery can be used as a power source to drive a hybrid electric vehicle (HEV), a plug-in hybrid electric vehicle (PHEV), or a battery electric vehicle (BEV). Alternatively, the battery can be used as a power source for mobile objects other than vehicles (such as trains, ships, and aircraft) or as a power source for electrical products such as an information processor. Examples 1 to 30 and comparative examples 1 to 10: Production of inorganic filler

[0089] Four inorganic fillers 1 to 4 were produced, which are listed in Table 1.

[0090] In each of examples 1 to 30 and comparison examples 2 and 4 to 10, one of the inorganic fillers 1 to 4 was used, as shown in Tables 2 and 3. No inorganic filler was used in comparison examples 1 and 3. [Table 1] Inorganic filler 1 Inorganic filler 2 Inorganic filler 3 Inorganic filler 4 material SiO2 SiO2 SiO2 SiO2 Manufacturer Nippon Aerosil Stream catalog Stream catalog Sigma Aldrich Model No. AEROSIL 300 KCC-1 M2 KCC-1 L1 SBA-15 Specific gravity [g / cm³] 3 ] 2,2 2,2 2,2 2,2 Specific surface area [m²] 2 / G] 300 600 700 700 form Bullet Fibrous particles Fibrous particles Mesoporous particles Synthesis of molecular crystals

[0091] All experiments were conducted at a temperature corresponding to a dew point of -80 °C or less, in a glovebox in an Ar atmosphere at an oxygen concentration of less than 3 ppm or in an equivalent environment not exposed to air.

[0092] In each of the examples and comparison examples, LiCFSA, as the lithium salt, was added to sulfolane (SL) in the amount specified in Tables 2 and 3. The sulfolane had been melted by heating to 60 °C, and the mixture was stirred while heating to dissolve the lithium salt. After dissolution, the melt was stirred for 2 hours and then cooled to room temperature, resulting in the synthesis of a molecular crystal.

[0093] In each of examples 1 to 11, 20 to 30 and comparison examples 1, 2 and 5 to 10, a molecular crystal was obtained in which the molar ratio of SL to LiCFSA contained in the molecular crystal was 3 (SL:LiCSFA = 3:1).

[0094] In each of examples 12 to 19 and comparison examples 3 and 4, a molecular crystal was obtained in which the molar ratio of SL to LiCFSA contained in the molecular crystal was 2.9 (SL:LiCSFA = 2.9:1). Production of a solid electrolyte

[0095] In each of Examples 1 to 30 and Comparative Examples 2 and 4 to 10, the synthesized molecular crystal and an inorganic filler shown in Table 2 or 3, selected from the inorganic fillers 1 to 4 shown in Table 1, were weighed in the resulting solid electrolyte to a volume ratio shown in Table 2 or 3 for the composition of the SL / LiCSFA molecular crystal in the molten state and the inorganic filler. The composite thus obtained was evaluated as a solid electrolyte. A normalized surface area WA (m²) was determined. 2 / G SE The amount of inorganic filler per gram of solid electrolyte was calculated. The results are listed in Tables 2 and 3.

[0096] In comparative example 1, the molecular crystal in which the molar ratio of SL to LiCFSA contained in the molecular crystal was 3 (SL:LiCSFA = 3:1) was evaluated as a solid electrolyte.

[0097] In comparative example 3, the molecular crystal in which the molar ratio of SL to LiCFSA contained in the molecular crystal was 2.9 (SL:LiCSFA = 2.9:1) was evaluated as a solid electrolyte. Measurement of ionic conductivity

[0098] In each of the examples and comparative examples, 50 mg of the solid electrolyte was placed in a cylinder with a diameter of 11.28 mm (1 cm). 2The resulting solution was pressed to obtain a solid electrolyte layer. Carbon-coated aluminum foils were placed on both sides of the solid electrolyte layer to collect current and create an evaluation cell. The cell's AC impedance was measured under conditions of 25 °C, 10 mV amplitude, and 1 M to 10 mHz. A resistance value of the solid electrolyte was obtained through ionic conduction, and the ionic conductivity of the solid electrolyte was calculated based on the cell shape. The results are presented in Tables 2 and 3. [Table 2] Molecular crystal Inorganic filler Inorganic filler Inorganic filler Inorganic filler Inorganic filler Solid electrolyte SL / LiCFSA=x / 1 Specific gravity Specific surface volume ratio Normalized surface ionic conductivity [g / cm 3 ] [m 2 / g] [vol.%] [m 2 / gSE] [S / cm@25°C] Comparative example 1 3 none - - 0 0 7,6×10 7 Example 1 3 SiO2 (AEROSIL 300) 2,2 300 3,6 15 2,2×10 -6 Example 2 3 SiO2 (AEROSIL 300) 2,2 300 7,0 30 3,5×10 -6 Example 3 3 SiO2 (AEROSIL 300) 2,2 300 13,1 60 5,5×10 -6 Example 4 3 SiO2 (AEROSIL 300) 2,2 300 18,5 90 7,1×10 -6 Example 5 3 SiO2 (AEROSIL 300) 2,2 300 23,2 120 9,5×10 -6 Example 6 3 SiO2 (AEROSIL 300) 2,2 300 27,4 150 1,3×10 -5 Example 7 3 SiO2 (AEROSIL 300) 2,2 300 37,6 240 2,6×10 -5 Example 8 3 SiO2 (AEROSIL 300) 2,2 300 43,0 300 2,7×10 -5 Example 9 3 SiO2 (AEROSIL 300) 2,2 300 53,1 450 1,9×10 -5 Example 10 3 SiO2 (AEROSIL 300) 2,2 300 60,1 600 1,0×10 -5 Example 11 3 SiO2 (AEROSIL 300) 2,2 300 69,4 900 2,6×10 -6 Comparative example 2 3 SiO2 (AEROSIL 300) 2,2 300 75,1 1200 1,4×10 -7 Comparative example 3 2,9 none - - 0 0 2,4×10 -6 Example 12 2,9 SiO2 (AEROSIL 300) 2,2 300 3,6 15 2,5×10 -6 Example 13 2,9 SiO2 (AEROSIL 300) 2,2 300 7,0 30 3,1×10 -6 Example 14 2,9 SiO2 (AEROSIL 300) 2,2 300 13,1 60 4,4×10 -6 Example 15 2,9 SiO2 (AEROSIL 300) 2,2 300 37,6 240 2,3×10 -5 Example 16 2,9 SiO2 (AEROSIL 300) 2,2 300 43,0 300 3,1×10 -5 Example 17 2,9 SiO2 (AEROSIL 300) 2,2 300 53,1 450 1,6×10 -5 Example 18 2,9 SiO2 (AEROSIL 300) 2,2 300 60,1 600 8,9×10 -6 Example 19 2,9 SiO2 (AEROSIL 300) 2,2 300 69,4 900 2,5×10 -6 Comparative example 4 2,9 SiO2 (AEROSIL 300) 2,2 300 75,1 1200 6,4×10 -7 [Table 3] Molecular crystal Inorganic filler Inorganic filler Inorganic filler Inorganic filler Inorganic filler Solid electrolyte SL / LiCFSA=x / 1 Specific gravity Specific surface volume ratio Normalized surface ionic conductivity [g / cm 3 ] [m 2 / g] [vol.%] [m 2 / g SE ] [S / cm@25°C] Example 20 3 SiO2 (KCC-1 M2) 2,2 600 7,0 60 2,4×10 -6 Example 21 3 SiO2 (KCC-1 M2) 2,2 600 27,4 300 4,6×10 -6 Example 22 3 SiO2 (KCC-1 M2) 2,2 600 43,0 600 4,5×10 -6 Comparative example 5 3 SiO2 (KCC-1 M2) 2,2 600 60,1 1200 4,6×10 -7 Comparative example 6 3 SiO2 (KCC-1 M2) 2,2 600 69,4 1800 8,5×10 -8 Example 23 3 SiO2 (KCC-1 L1) 2,2 700 7,0 90 2,4×10 -6 Example 24 3 SiO2 (KCC-1 L1) 2,2 700 27,4 350 4,1×10 -6 Example 25 3 SiO2 (KCC-1 L1) 2,2 700 43,0 700 2,2×10 -6 Comparative example 7 3 SiO2 (KCC-1 L1) 2,2 700 60,1 1400 1,5×10 -7 Comparative example 8 3 SiO2 (KCC-1 L1) 2,2 700 69,4 2100 2,1×10 -8 Example 26 3 SiO2 (SBA-15) 2,2 700 7,0 70 5,4×10 -6 Example 27 3 SiO2 (SBA-15) 2,2 700 10,2 105 8,3×10 -6 Example 28 3 SiO2 (SBA-15) 2,2 700 17,4 196 2,0×10 -5 Example 29 3 SiO2 (SBA-15) 2,2 700 27,4 350 2,4×10 -6 Example 30 3 SiO2 (SBA-15) 2,2 700 43,0 700 8,4×10 -6 Comparative example 9 3 SiO2 (SBA-15) 2,2 700 60,1 1400 2,0×10 -6 Comparative example 10 3 SiO2 (SBA-15) 2,2 700 69,4 2100 3,4×10 -7

[0099] Fig. Figure 1 is a diagram illustrating the relationship between a normalized surface WA of the inorganic filler and the ionic conductivity of the solid electrolyte at room temperature (25 °C).

[0100] As shown in Table 2, it is understood that the ionic conductivity in examples 1 to 11 is improved compared to the comparison examples 1 and 2.

[0101] As shown in Table 2, it is understood that the ionic conductivity in examples 12 to 19 is improved compared to the comparison examples 3 and 4.

[0102] As shown in Table 3, the ionic conductivity is assumed to be improved in examples 20 to 22 compared to the comparison examples 5 to 6.

[0103] As shown in Table 3, the ionic conductivity is assumed to be improved in examples 23 to 25 compared to the comparison examples 7 to 8.

[0104] As shown in Table 3, it is understood that the ionic conductivity in examples 26 to 30 is improved compared to the comparison examples 9 to 10.

[0105] As inFig. As shown in Figure 1 and Tables 2 to 3, it is understood that the ionic conductivity in examples 1 to 30 is improved compared to the comparison examples 1 to 10.

[0106] In this way, it was demonstrated that a solid electrolyte that meets the condition that the normalized surface WA (m²) 2 / G SE ) of an inorganic filler 15 to 900 m 2 / G SE which can improve the ionic conductivity compared to a solid electrolyte that does not meet this condition. QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] JP 2013-214510

[0002]

Claims

[1] Solid electrolyte comprising a molecular crystal and an inorganic filler, where The molecular crystal comprises a sulfolane-based compound and 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide lithium (LiCFSA) as a lithium salt; the inorganic filler SiO2 is; and assuming that a mass of inorganic filler per g of solid electrolyte W (g / g SE ) is and that a specific surface area of ​​the inorganic filler A (m 2 / g) is a normalized surface WA (m 2 / G SE ) of the inorganic filler 15 to 900 m 2 / G SE is. [2] Solid electrolyte according to claim 1, wherein the molar ratio of the sulfolane-based compound to the lithium salt contained in the molecular crystal is 2.0 or more and 3.1 or less. [3] Solid electrolyte according to claim 1, wherein the ratio of the inorganic filler contained in the solid electrolyte is 3.6 vol% to 69.4 vol%. [4] Solid electrolyte according to claim 1, wherein the ratio of the inorganic filler contained in the solid electrolyte is 27.4 vol% to 60.1 vol%. [5] Battery with the solid electrolyte according to claim 1.

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