WO2024111197A1 - 混合物、シート、電気化学素子および蓄電デバイス - Google Patents

混合物、シート、電気化学素子および蓄電デバイス Download PDF

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WO2024111197A1
WO2024111197A1 PCT/JP2023/031012 JP2023031012W WO2024111197A1 WO 2024111197 A1 WO2024111197 A1 WO 2024111197A1 JP 2023031012 W JP2023031012 W JP 2023031012W WO 2024111197 A1 WO2024111197 A1 WO 2024111197A1
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electrolyte
mixture
oxide
electrode layer
layer
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French (fr)
Japanese (ja)
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裕 渡辺
雄基 竹内
秀俊 水谷
将任 岩崎
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Niterra Co Ltd
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Niterra Co Ltd
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Priority to EP23894213.0A priority Critical patent/EP4625568A1/en
Priority to KR1020257016134A priority patent/KR20250088612A/ko
Priority to CN202380080291.7A priority patent/CN120226181A/zh
Priority to JP2024559853A priority patent/JP7812011B2/ja
Priority to TW112144901A priority patent/TW202422926A/zh
Publication of WO2024111197A1 publication Critical patent/WO2024111197A1/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/64—Liquid electrolytes characterised by additives
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M50/431—Inorganic 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
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H—ELECTRICITY
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    • 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
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • 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 mixture, a sheet, an electrochemical element, and an electricity storage device that contain an oxide and an electrolyte.
  • an electrolyte sheet is formed from a mixture containing an oxide made of silicon dioxide and an electrolyte containing tetraglyme.
  • the present invention was made to solve this problem, and aims to provide a mixture, a sheet, an electrochemical element, and an electricity storage device that can improve the diffusivity of substances at interfaces.
  • a first aspect for achieving this object is a mixture containing an oxide and an electrolyte, the electrolyte being a sulfone compound represented by chemical formula (1) in which an electrolyte salt is dissolved.
  • R 1 and R 2 are each independently an alkyl group, an alkenyl group, or a halogenated alkyl group having 4 or less carbon atoms, or the alkyl groups, the alkenyl groups, or the halogenated alkyl groups are bonded to each other to form a ring structure.
  • the self-diffusion coefficient of one or more components contained in the electrolyte in contact with the oxide, measured by pulsed magnetic field gradient nuclear magnetic resonance spectroscopy, is six or more times the self-diffusion coefficient of the same component contained in the electrolyte not in contact with the oxide, measured at the same temperature as the measurement.
  • the second aspect is the first aspect, in which the oxide is alumina.
  • the third aspect is the first or second aspect, in which the electrolyte salt is a lithium salt.
  • the fourth embodiment is a sheet comprising a mixture of any of the first to third embodiments.
  • the fifth aspect is an electrochemical device that includes a mixture of any of the first to third aspects.
  • the sixth aspect is an electricity storage device comprising a positive electrode layer, a negative electrode layer, and a separator separating the positive electrode layer and the negative electrode layer, and includes a mixture of any of the first to third aspects.
  • the seventh aspect is the sixth aspect, in which at least one of the positive electrode layer, the negative electrode layer, and the separator includes a mixture.
  • the eighth aspect is the sixth aspect, in which at least one of the positive electrode layer and the negative electrode layer includes a current collecting layer, and a protective layer is provided in contact with at least one of the separator and the current collecting layer, and the protective layer includes a mixture.
  • the mixture, sheet, electrochemical element, and electricity storage device of the present invention can improve the diffusivity of materials at the interface between the oxide and the electrolyte.
  • FIG. 2 is a cross-sectional view of an electrochemical device including a mixture according to the first embodiment.
  • FIG. 2 is an enlarged cross-sectional view of the electrochemical device of a portion indicated by II in FIG.
  • FIG. 1 is a diagram illustrating a garnet-type crystal structure.
  • FIG. 11 is a cross-sectional view of an electrochemical element according to a second embodiment.
  • FIG. 11 is a cross-sectional view of an electrochemical element according to a third embodiment.
  • FIG. 1 is a schematic cross-sectional view of an electrochemical element 11 containing a mixture 10 in one embodiment.
  • the electrochemical element 11 is a lithium ion solid-state battery (electricity storage device) in which the power generation element is made of a solid.
  • the power generation element is made of a solid means that the skeleton of the power generation element is made of a solid, and includes a form in which the skeleton is impregnated with a liquid.
  • the electrochemical element 11 includes, in order, a positive electrode layer 12, an electrolyte layer 15, and a negative electrode layer 16.
  • the positive electrode layer 12, the electrolyte layer 15, and the negative electrode layer 16 are housed in a case (not shown).
  • the positive electrode layer 12 is made up of a current collecting layer 13 and an active material layer 14 superimposed on each other.
  • the current collecting layer 13 is a conductive member. Examples of materials for the current collecting layer 13 include metals selected from Ni, Ti, Fe, and Al, alloys containing two or more of these elements, stainless steel, and carbon materials.
  • the active material layer 14 includes a mixture 10 and an active material 20.
  • the mixture 10 includes an oxide 19.
  • the active material layer 14 may include a conductive additive.
  • the conductive additive include carbon black, acetylene black, ketjen black, carbon fiber, Ni, Pt, and Ag.
  • Examples of the active material 20 include a metal oxide having a transition metal, a sulfur-based active material, and an organic active material.
  • Examples of the metal oxide having a transition metal include a metal oxide containing Li and one or more elements selected from Mn, Co, Ni, Fe , Cr , and V.
  • Examples of the metal oxide having a transition metal include LiCoO2 , LiNi0.8Co0.15Al0.05O4 , LiMn2O4 , LiNiVO4 , LiNi0.5Mn1.5O4 , LiNi1/3Mn1 / 3Co1 / 3O2 , and LiFePO4 .
  • a coating layer can be provided on the surface of the active material 20.
  • the coating layer include Al2O3 , ZrO2 , LiNbO3 , Li4Ti5O12 , LiTaO3 , LiNbO3 , LiAlO2 , Li2ZrO3 , Li2WO4 , Li2TiO3 , Li2B4O7 , Li3PO4 , and Li2MoO4 .
  • sulfur-based active materials include S, TiS 2 , NiS, FeS 2 , Li 2 S, MoS 3 , and sulfur-carbon composites.
  • organic active materials include radical compounds such as 2,2,6,6-tetramethylpiperidinoxyl-4-yl methacrylate and polytetramethylpiperidinoxyl vinyl ether, quinone compounds, radialene compounds, tetracyaquinodimethane, and phenazine oxide.
  • the electrolyte layer 15 is made of a mixture 10.
  • the mixture 10 contains an oxide 19 and an electrolyte solution 22 (see FIG. 2).
  • the mixture 10 may further contain a binder.
  • the electrolyte layer 15 corresponds to a separator that separates the positive electrode layer 12 and the negative electrode layer 16.
  • the negative electrode layer 16 is made up of a current collecting layer 17 and an active material layer 18 superimposed on each other.
  • the current collecting layer 17 is a conductive member. Examples of materials for the current collecting layer 17 include metals selected from Ni, Ti, Fe, Cu, and Si, alloys containing two or more of these elements, stainless steel, and carbon materials.
  • the active material layer 18 includes the mixture 10 and an active material 21.
  • the active material layer 18 may include a conductive additive.
  • the conductive additive include carbon black, acetylene black, ketjen black, carbon fiber, Ni, Pt, and Ag.
  • the active material 21 include Li, Li-Al alloy, Li 4 Ti 5 O 12 , graphite, In, Si, Si-Li alloy, and SiOx (e.g., 0.5 ⁇ X ⁇ 1.5).
  • the active material layers 14 and 18 may include a binder.
  • FIG. 2 is a cross-sectional view of the electrochemical element 11, enlarging the part indicated by II in FIG. 1.
  • the mixture 10 contained in the electrochemical element 11 includes an oxide 19 and an electrolyte solution 22.
  • the oxide 19 is preferably insoluble in the electrolyte solution 22 and does not have electronic conductivity.
  • the shape of the oxide 19 may be granular, spherical, rod-like, needle-like, polygonal, fibrous, or scaly.
  • the oxide 19 is appropriately selected from inorganic compounds such as alumina, silica, ceria, zirconia, and oxide-based solid electrolytes.
  • oxide-based solid electrolytes include those having a perovskite type, NASICON type, LISICON type, and garnet type crystal structure containing Li, La, and Zr .
  • perovskite type oxides include oxides containing at least Li, Ti, and La, such as La2 /3- xLi3xTiO3 .
  • NASICON type oxides include oxides containing at least Li, M (M is one or more elements selected from Ti, Zr, and Ge) and P, such as Li(Al,Ti) 2 ( PO4 ) 3 and Li(Al,Ge) 2 ( PO4 ) 3 .
  • LISICON type oxides include Li14Zn ( GeO4 ) 4 .
  • FIG. 3 is a diagram showing a schematic diagram of a garnet-type crystal structure.
  • the garnet-type crystal structure is expressed by the general formula C 3 A 2 B 3 O 12.
  • the C site Sc is dodecahedrally coordinated with the oxygen atom Oa
  • the A site Sa is octahedrally coordinated with the oxygen atom Oa
  • the B site Sb is tetrahedrally coordinated with the oxygen atom Oa.
  • the oxide 19 is a portion that is octahedrally coordinated with the oxygen atom Oa in a normal garnet-type crystal structure
  • Li may be present in a portion that becomes a gap V.
  • the gap V is, for example, a portion sandwiched between the B site Sb1 and the B site Sb2.
  • the Li present in the gap V is octahedrally coordinated with the oxygen atom Oa that constitutes an octahedron including the face Fb1 of the tetrahedron that forms the B site Sb1 and the face Fb2 of the tetrahedron that forms the B site Sb2.
  • the oxygen atom Oa that constitutes an octahedron including the face Fb1 of the tetrahedron that forms the B site Sb1 and the face Fb2 of the tetrahedron that forms the B site Sb2.
  • La may occupy the C site Sc
  • Zr may occupy the A site Sa
  • Li may occupy the B site Sb and the voids V.
  • An oxide having a garnet-type crystal structure containing Li, La, and Zr has an XRD pattern similar to that of X-ray diffraction file No. 422259 (Li 7 La 3 Zr 2 O 12 ) in the Cambridge Structural Database (CSD).
  • the oxide may have different diffraction angles and intensity ratios compared to No. 422259 because the types of constituent elements and Li concentrations may be different.
  • Li 7 La 3 Zr 2 O 12 may be either a tetragonal crystal with low ionic conductivity or a cubic crystal with high ionic conductivity.
  • Oxides containing Li, La, and Zr and having a garnet-type or garnet-type-like crystal structure may have some of the constituent elements replaced with other elements, or may have trace amounts of other elements added without replacing the constituent elements.
  • other elements include at least one element selected from the group consisting of Mg, Al, Si, Ca, Ti, V, Ga, Sr, Y, Nb, Sn, Sb, Ba, Hf, Ta, W, Bi, Rb, and lanthanides (excluding La).
  • the oxide 19 is , for example , Li6La3Zr1.5W0.5O12 , Li6.15La3Zr1.75Ta0.25Al0.2O12 , Li6.15La3Zr1.75Ta0.25Ga0.2O12 , Li6.25La3Zr2Ga0.25O12 , Li6.4La3Zr1.4Ta0.6O12 , Li6.5La3Zr1.75Te0.25O12 , Li6.75La3Zr1.75Nb0.25O12 .
  • Li6.9La3Zr1.675Ta0.289Bi0.036O12 Li6.46Ga0.23La3Zr1.85Y0.15O12 , Li6.8La2.95Ca0.05Zr1.75Nb0.25O12 , Li7.05La3.00Zr1.95Gd0.05O12 , Li6.20Ba0.30La2.95Rb0.05Zr2O12 .
  • the oxide having a garnet-type or garnet-type-like crystal structure preferably contains, in addition to Li, La, and Zr, at least one of Mg and element A (A is at least one element selected from the group consisting of Ca, Sr, and Ba), with the molar ratio of each element satisfying all of the following (1) to (3), or contains both Mg and element A, with the molar ratio of each element satisfying all of the following (4) to (6).
  • the element A is preferably Sr in order to increase the ionic conductivity of the oxide 19.
  • the median diameter of the circle-equivalent diameter of the oxide 19 appearing on the cross section of the electrolyte layer 15 is preferably 0.2-10 ⁇ m, and more preferably 0.2-6 ⁇ m. This is to ensure that the surface area of the oxide 19 is of an appropriate size and to increase the diffusivity of the components of the electrolyte solution 22 present on the surface of the oxide 19.
  • the median diameter of the oxides 19 is obtained.
  • an image of the oxides 19 appearing on the cross section of the electrolyte layer 15 (a polished surface, a surface obtained by irradiating a focused ion beam (FIB), or a surface obtained by ion milling) is analyzed using a scanning electron microscope (SEM), and the circle equivalent diameter (the diameter of a circle having the same area as the area of the oxides 19 appearing on the cross section) is calculated from the area of each oxide 19, and a volume-based particle size distribution is obtained.
  • the median diameter is the circle equivalent diameter at which the integrated value of the frequency in the particle size distribution is 50%.
  • the image for obtaining the particle size distribution should have an area of 400 ⁇ m2 or more of the electrolyte layer 15.
  • the electrolyte solution 22 is an organic solvent in which an electrolyte salt is dissolved.
  • the electrolyte salt is a compound used for transferring cations between the positive electrode layer 12 and the negative electrode layer 16.
  • the anion of the lithium salt is a halide ion (I - , Cl - , Br - , etc.), SCN - , BF 4 - , BF 3 (CF 3 ) - , BF 3 (C 2 F 5 ) - , PF 6 - , ClO 4 - , SbF 6 - , N(SO 2 F) 2 - , N(SO 2 CF 3 ) 2 - , N(SO 2 C 2 F 5 ) 2 - , B(C 6 H 5 ) 4 - , B(O 2 C 2 H 4 ) 2 - , C(SO 2 F) 3 - , C(SO 2 CF 3 ) 3 - -
  • SEI highly stable and low-resistance coating
  • N(SO 2 F) 2 - may be abbreviated as [FSI] - : bis(fluorosulfonyl)imide anion
  • N(SO 2 CF 3 ) 2 - may be abbreviated as [TFSI] - : bis(trifluoromethanesulfonyl)imide anion
  • the lithium salt is particularly preferably lithium bis(fluorosulfonyl)imide (LiFSI). This is because LiFSI has little effect on the increase in viscosity of the electrolyte and is effective in forming a good passive film (SEI).
  • the organic solvent of the electrolyte solution 22 contains a sulfone compound represented by chemical formula (1).
  • the organic solvent of the electrolyte solution 22 can be one or more types selected appropriately from the group of materials shown below.
  • R1 and R2 are each independently an alkyl group, an alkenyl group, or a halogenated alkyl group having 4 or less carbon atoms, or the alkyl groups, alkenyl groups, or halogenated alkyl groups are bonded to each other to form a ring structure.
  • R1 and R2 may be a linear hydrocarbon group, or a branched or cyclic hydrocarbon group.
  • alkyl groups having 4 or less carbon atoms include methyl, ethyl, n-propyl, isopropyl, 1-ethylpropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, and 3,3-dimethylbutyl.
  • alkenyl groups having 4 or less carbon atoms include vinyl, 1-propenyl, allyl, 1-butenyl, 2-butenyl, and 3-butenyl.
  • Halogenated alkyl groups having 4 or less carbon atoms are fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, perfluoroethyl, 2,2,3,3-tetrafluoropropyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluoroisobutyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trichloroethyl, 1,1,2,2-tetrachloroethyl, perchloroethyl.
  • chloropropyl group 2,2,3,3-tetrachloropropyl group, perchloropropyl group, perchloroisopropyl group, perchlorobutyl group, perchloroisobutyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, 2,2,2-tribromoethyl group, 1,1,2,2-tetrabromoethyl group, 2,2,3,3-tetrabromopropyl group, iodomethyl group, diiodomethyl group, triiodomethyl group, 2,2,2-triiodoethyl group, 1,1,2,2-tetraiodoethyl group, and 2,2,3,3-tetraiodopropyl group.
  • examples of cyclic compounds in which alkyl groups, alkenyl groups, or halogenated alkyl groups are bonded to each other to form a ring structure include trimethylene sulfone, sulfolane, fluorosulfolane, difluorosulfolane, methylsulfolane, and dimethylsulfolane.
  • the sulfone compounds represented by chemical formula (1) have high oxidation resistance, and are therefore advantageous for increasing the voltage of the electrochemical element 11.
  • the salt concentration (molar concentration) of the electrolyte solution 22 is preferably 1.4 mol/kg or more, and more preferably 1.6 mol/kg or more. This is because, compared to a typical electrolyte solution with a salt concentration of around 1 mol/kg, the number of solvent molecules coordinated to the cations is greater and the amount of uncoordinated solvent is reduced, which allows the transport number of the cations in the electrolyte salt to be increased.
  • the electrolyte solution 22 may contain a solvated ionic liquid.
  • the solvated ionic liquid is composed of cations solvated in a sulfone compound represented by chemical formula (1) and their counterions.
  • the electrolyte solution 22 may be in a state in which all solvent molecules are coordinated to cations and there is no uncoordinated solvent, or in a state in which all solvent molecules are coordinated to cations and there is no uncoordinated solvent, and further in which there is an excess of cations that are not coordinated to solvent molecules.
  • electrolyte solution 22 which has a high salt concentration in which cations are solvated in a sulfone compound, takes on a unique coordination structure when in a solvated ionic liquid state, and the transport speed of lithium ions increases.
  • the mixture 10 may contain other organic solvents.
  • the other organic solvents contribute, for example, to reducing the viscosity of the electrolyte 22 and increasing the ionic conductivity of the electrolyte 22.
  • examples of other organic solvents include propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, trimethyl phosphate, triethyl phosphate, ⁇ -butyrolactone, dimethyl methylphosphonate, acetonitrile, isobutyl methyl ketone, nitromethane, methyl ethyl ketone, tetramethylsilane, siloxane compounds, and organic silicate compounds.
  • One or more other organic solvents that are unlikely to affect the coordination state of cations and solvent molecules are appropriately selected.
  • the mixture 10 may contain various additives used in lithium ion batteries.
  • additives include carbonate compounds containing unsaturated bonds or halogens, such as vinylene carbonate and fluoroethylene carbonate, flame-retardant compounds such as ionic liquids, acid anhydrides, nitrile compounds, anisole derivatives, and other redox shuttle compounds, as well as overcharge inhibitors such as aromatic compounds.
  • the ratio (wt%) of the sulfone compound to the total of the sulfone compound and other organic solvents contained in mixture 10 is preferably 75% or more. This is to ensure the transport number of the cation.
  • the salt concentration of the electrolyte 22 is preferably 4.0 mol/kg or less. If the salt concentration of the electrolyte 22 exceeds 4.0 mol/kg, the ionic conductivity tends to decrease significantly due to an increase in the viscosity of the electrolyte 22.
  • the combination of oxide 19 and electrolyte 22 in mixture 10 is set so that the self-diffusion coefficient of one or more components contained in electrolyte 22 in contact with oxide 19, as measured by pulsed field gradient nuclear magnetic resonance spectroscopy (PFG-NMR), is at least six times the self-diffusion coefficient of the component contained in electrolyte 22 not in contact with oxide 19, as measured at the same temperature.
  • PFG-NMR pulsed field gradient nuclear magnetic resonance spectroscopy
  • the self-diffusion coefficient D M of the component of the electrolyte 22 in contact with the oxide 19 indicates the diffusion rate of the component of the electrolyte 22 in a sample obtained by mixing the oxide 19 and the electrolyte 22.
  • the self-diffusion coefficient D L of the component of the electrolyte 22 not in contact with the oxide 19 indicates the diffusion rate of the component of the electrolyte 22.
  • the self-diffusion coefficients D M and D L are measured at the same temperature. If the difference in temperature when the two are measured is within 1° C., they can be accepted as being at the same temperature.
  • the self-diffusion coefficient D M of the component of the electrolyte 22 in contact with the oxide 19 is six times or more the self-diffusion coefficient D L of the component of the electrolyte 22 not in contact with the oxide 19, which indicates that the diffusivity of the substance at the interface of the oxide 19 in contact with the electrolyte 22 is six times or more larger than when the electrolyte is present alone.
  • the apparent self-diffusion coefficient value obtained by PFG-NMR measurement may be difficult to judge the accuracy of the apparent self-diffusion coefficient value obtained by PFG-NMR measurement relative to the actual self-diffusion coefficient value. If it is difficult to perform measurements other than PFG-NMR for comparative verification (for example, AC impedance measurements, evaluation of the diffusion coefficient using radioisotopes), the apparent self-diffusion coefficient obtained by PFG-NMR is of course used, but even if measurements other than PFG-NMR can be performed, the apparent self-diffusion coefficient obtained by PFG-NMR is used to standardize the measurement method.
  • the concentration gradient of the desorbed solvent molecules and anions is likely to be alleviated when desolvation of cations and dissociation of ion pairs occur at the interface between the oxide 19 and the electrolyte 22 by passing a current through the mixture 10.
  • the concentration gradient of the ions in the electrolyte 22 that occurs during charging and discharging is also likely to be alleviated, so that the rate characteristics of the electrochemical element 11 are improved, and improvements in rapid charging performance and power density are expected.
  • the diffusion rate of the decomposition products accompanying the charging and discharging of the electrochemical element 11 is also increased, the accumulation of the decomposition products is reduced, and therefore the cycle life is expected to be improved.
  • the nuclides for which NMR signals are observed depend on the type of organic solvent contained in the electrolyte 22 and the type of electrolyte salt material dissolved in the organic solvent, but examples include 1 H, 13 C, 19 F, 6 Li, 7 Li, 11 B, 23 Na, and 31 P.
  • the same self-diffusion coefficient can be obtained even when PF 6 - is observed with 19 F nuclei and 31 P nuclei, or when the 1 H nuclei of the CH 3 and CH 2 ethyl groups, which are observed as two types of signals, are observed. Therefore, even if the electrolyte is a mixture of multiple solvents or components, the self-diffusion coefficient can be obtained for each component as long as there is at least one signal that does not overlap with other components.
  • the concentration of the electrolyte in the electrolyte solution 22 contained in the mixture 10 is specified, for example, as follows.
  • concentration of the lithium salt in the mixture 10 constituting the electrolyte layer 15 will be described, but the concentrations of the mixture 10 constituting the active material layers 14 and 18 and electrolyte salts other than the lithium salt can also be specified in a similar manner.
  • the crushed electrolyte layer 15 is immersed in a solvent, and the electrolyte solution 22 contained in the electrolyte layer 15 is dissolved in the solvent.
  • the electrolyte layer 15 is then separated into a solid component and a liquid component by centrifugation or filtration.
  • the Li content of the separated liquid component is determined by inductively coupled plasma analysis (ICP).
  • the type of organic solvent contained in the electrolyte layer 15 is identified, for example, by gas chromatography-mass spectrometry (GC-MS).
  • GC-MS gas chromatography-mass spectrometry
  • a calibration curve is created using an organic solvent of identified type (hereinafter referred to as a "standard substance"), and the content of the organic solvent contained in the electrolyte layer 15 is identified based on the area of the chromatogram.
  • the standard substance and the electrolyte layer 15 are analyzed by thermogravimetry-differential thermal analysis (TG-DTA), and the analysis results of the standard substance and the analysis results of the electrolyte layer 15 are compared to identify the content of the organic solvent contained in the electrolyte layer 15.
  • the molar mass concentration (mol/kg) of the lithium salt in the electrolyte solution 22 is calculated based on the Li content in the liquid components and the organic solvent content in the electrolyte layer 15.
  • an electrolyte solution having the same composition as the electrolyte solution 22 contained in the electrolyte layer 15 is prepared, and the self-diffusion coefficient of the electrolyte solution is similarly measured to obtain the self-diffusion coefficient D L. If the self-diffusion coefficient D L of each component of the electrolyte solution 22 is known from literature or the like, these values can also be used.
  • the ratio of the volume of the oxide 19 to the total volume of the oxide 19 and the electrolyte 22 is preferably 52% or more and less than 100%, and more preferably 61% or more and less than 100%. It is particularly preferable that the ratio of the volume of the oxide 19 to the total volume of the oxide 19 and the electrolyte 22 is 93% or less.
  • the content (volume %) of oxide 19 and electrolyte solution 22 is obtained by freezing electrolyte layer 15 or embedding electrolyte layer 15 in tetrafunctional epoxy resin or the like and then analyzing a randomly selected 5000x field of view from the cross section of electrolyte layer 15 using a SEM equipped with an energy dispersive X-ray spectrometer (EDS).
  • EDS energy dispersive X-ray spectrometer
  • the analysis identifies the distribution of La, Zr, and S and performs image analysis of the contrast of the reflected electron image to identify the area of oxide 19 and the area of electrolyte solution 22, and the content (volume %) of oxide 19 and electrolyte solution 22 is obtained by regarding the area ratio in the cross section of electrolyte layer 15 as the volume ratio in mixture 10 of electrolyte layer 15.
  • the mixture 10 may contain a binder that binds the oxide 19.
  • a binder that binds the oxide 19.
  • the binder include rubber-like polymers such as fluorinated resins, polyolefins, polyimides, polyvinylpyrrolidone, polyvinyl alcohol, cellulose ether, and styrene-butadiene rubber.
  • fluorinated resin examples include vinylidene fluoride polymers, polychlorotrifluoroethylene, polyvinyl fluoride, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymers, tetrafluoroethylene-hexafluoropropylene copolymers, ethylene-tetrafluoroethylene copolymers, and ethylene-chlorotrifluoroethylene copolymers.
  • vinylidene fluoride polymers include homopolymers of vinylidene fluoride and copolymers of vinylidene fluoride and copolymerizable monomers.
  • copolymerizable monomers include halogen-containing monomers (excluding vinylidene fluoride) and non-halogen copolymerizable monomers.
  • halogen-containing monomers include chlorine-containing monomers such as vinyl chloride; fluorine-containing monomers such as trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, and perfluoroalkyl vinyl ether.
  • non-halogen copolymerizable monomers examples include olefins such as ethylene and propylene; acrylic monomers such as acrylic acid, methacrylic acid, and esters or salts thereof; and vinyl monomers such as acrylonitrile, vinyl acetate, and styrene.
  • olefins such as ethylene and propylene
  • acrylic monomers such as acrylic acid, methacrylic acid, and esters or salts thereof
  • vinyl monomers such as acrylonitrile, vinyl acetate, and styrene.
  • One or more types of copolymerizable monomers are polymerized to vinylidene fluoride to form a copolymer.
  • the electrochemical element 11 is manufactured, for example, as follows.
  • a mixture 10 which is a mixture of an electrolyte solution 22 in which a lithium salt is dissolved in an organic solvent and an oxide 19, is mixed with a solution in which a binder is dissolved in a solvent to create a slurry. After tape casting, the mixture is dried to obtain a green sheet (electrolyte sheet) for the electrolyte layer 15.
  • the active material 20 is mixed into the mixture 10, which is a mixture of an electrolyte solution 22 in which a lithium salt is dissolved in an organic solvent and an oxide 19, and then a solution in which a binder is dissolved in a solvent is mixed to create a slurry. After tape casting on the current collecting layer 13, it is dried to obtain a green sheet (positive electrode sheet) for the positive electrode layer 12.
  • the active material 21 is mixed into the mixture 10, which is a mixture of an electrolyte solution 22 in which a lithium salt is dissolved in an organic solvent and an oxide 19, and then a solution in which a binder is dissolved in a solvent is mixed to create a slurry. After tape casting on the current collecting layer 17, it is dried to obtain a green sheet (negative electrode sheet) for the negative electrode layer 16.
  • Electrolyte sheet, positive electrode sheet, and negative electrode sheet are cut into a predetermined shape, they are stacked in the order of positive electrode sheet, electrolyte sheet, and negative electrode sheet, and are pressed together to form an integrated unit. Terminals (not shown) are connected to the current collecting layers 13 and 17, respectively, and the sheets are sealed in a case (not shown), to obtain an electrochemical element 11 including a positive electrode layer 12, an electrolyte layer 15, and a negative electrode layer 16.
  • the electrolyte layer 15, and the negative electrode layer 16 by tape casting of a slurry containing the mixture 10
  • FIG. 4 is a cross-sectional view of an electrochemical element 24 (electricity storage device) in the second embodiment.
  • the electrochemical element 24 includes, in that order, a positive electrode layer 12, a separator 25, and a negative electrode layer 16. These are housed in a case (not shown).
  • the separator 25 is made of a porous material that is durable against the active materials 20, 21 and electrolyte contained in the positive electrode layer 12 and the negative electrode layer 16, and that allows lithium ions to pass through but has no electronic conductivity. Examples of the separator 25 include nonwoven fabrics and porous membranes made of cellulose, polypropylene, polyethylene, etc.
  • the electrolyte is the same as that described in the first embodiment, so a description of it will be omitted.
  • the electrochemical element 24 in the second embodiment contains the mixture 10 in the positive electrode layer 12 and the negative electrode layer 16, so that, like the electrochemical element 11 in the first embodiment, the diffusivity of materials between the oxide 19 in the positive electrode layer 12 and the negative electrode layer 16 and the electrolyte 22 can be improved.
  • FIG. 5 is a cross-sectional view of an electrochemical element 26 (electricity storage device) in the third embodiment.
  • the electrochemical element 26 includes, in order, a positive electrode layer 27, a separator 25, and a negative electrode layer 30. These are housed in a case (not shown).
  • the electrochemical element 26 is a liquid-based lithium-ion battery that uses an organic solvent as the electrolyte.
  • the positive electrode layer 27 is formed by stacking the current collecting layer 13 and the active material layer 28.
  • the active material layer 28 contains the active material 20.
  • the active material layer 28 may contain a conductive additive such as carbon black, acetylene black, ketjen black, carbon fiber, Ni, Pt, and Ag.
  • a protective layer 29 is disposed between the separator 25 and the negative electrode layer 30.
  • the protective layer 29 contains the mixture 10.
  • the negative electrode layer 30 is formed by stacking an active material layer 31, a protective layer 32, and a current collecting layer 17 in that order.
  • the active material layer 31 is made of, for example, Li, a Li-Al alloy, a Li-Sn alloy, a Li-Si alloy, a Li-Mg alloy, a Li-Si alloy, or a Si-Li alloy.
  • the protective layer 32 contains a mixture 10.
  • the protective layers 29, 32 are arranged by laminating sheets, applying to the separator 25 or the current collecting layer 17, or the like. Because the protective layers 29, 32 contain the mixture 10, the diffusibility of the material between the oxide 19 and the electrolyte 22 in the protective layers 29, 32 can be improved.
  • the oxide 19 contained in the protective layers 29, 32 has a garnet-type crystal structure containing Li, La, Zr, and O, it is resistant to reduction by the metallic lithium of the active material layer 31, and therefore the stability of the operation of the electrochemical element 26 is increased. Furthermore, since the protective layer 29 is interposed between the active material layer 31 and the separator 25, it suppresses short circuits caused by dendritic growth of metallic lithium. The protective layer 32 interposed between the active material layer 31 and the current collecting layer 17 suppresses deterioration of the current collecting layer 17.
  • Example 1 Alpha-alumina, which is an oxide, and an electrolyte solution prepared by mixing sulfolane and lithium bis(fluorosulfonyl)imide (LiFSI) in a molar ratio of 3:1 were placed in a mortar in a ratio of 61:39 (volume ratio), and mixed using a pestle to obtain the mixture in Example 1.
  • Example 2 A mixture in Example 2 was obtained in the same manner as in Example 1, except that tetragonal Li 7 La 3 Zr 2 O 12 was mixed into the electrolyte instead of ⁇ -alumina.
  • the median diameter of the volume-based particle size distribution of Li 7 La 3 Zr 2 O 12 measured by a laser diffraction/scattering method was 0.8 ⁇ m.
  • Comparative Example 1 The mixture in Comparative Example 1 was obtained in the same manner as in Example 1, except that an electrolyte solution prepared by mixing N-methyl-N-propylpyrrolidinium bis(fluorosulfonyl)imide (MPPy-FSI) and LiFSI in a molar ratio of 1.46:1 was mixed with ⁇ -alumina instead of the electrolyte solution prepared by mixing sulfolane and LiFSI.
  • MPPy-FSI N-methyl-N-propylpyrrolidinium bis(fluorosulfonyl)imide
  • LiFSI LiFSI
  • Comparative Example 2 The mixture in Comparative Example 2 was obtained in the same manner as in Example 1, except that sulfolane (in which no lithium salt was dissolved) was mixed with ⁇ -alumina at 40° C. instead of the electrolyte prepared by mixing sulfolane and LiFSI.
  • the self-diffusion coefficient D M of each component of the electrolyte contained in the mixture at 25°C was measured using a nuclear magnetic resonance spectrometer (JNM-ECA600II, manufactured by JEOL RESONANCE Co., Ltd.) using a pulsed magnetic field gradient.
  • the mixture (sample) was placed in a symmetrical microsample tube with an outer diameter of 5 mm at a height of 5 mm from the bottom of the outer tube, and then sealed with an inner tube.
  • a diffusion measurement probe was used, the sample was not rotated, and the magnetic field gradient was appropriately set within the range of 0.1-13.5 T/m.
  • the self-diffusion coefficient of the component containing 1 H nuclei was measured at 600 MHz by a stimulated echo pulse series.
  • the self-diffusion coefficient of the component containing 19 F nuclei bis(fluorosulfonyl)imide anion) was measured at 564.73 MHz.
  • the self-diffusion coefficient of the component containing 7 Li nuclei was measured at 233.25 MHz.
  • the magnetic field gradient pulse width, diffusion time, recovery time after the magnetic field gradient pulse, and number of integrations were adjusted for each sample depending on the situation of the signal to be observed.
  • the self-diffusion coefficients D L of sulfolane, [FSI] - and Li + were measured at 25° C. for the electrolytes obtained by removing the oxides from the mixtures in Examples 1 and 2 and Comparative Example 1. Since the sulfolane obtained by removing the oxides from the mixture in Comparative Example 2 does not contain 19 F nuclei and 7 Li nuclei, only 1 H nuclei were measured for the self-diffusion coefficient D L , and since the melting point of sulfolane is 29° C., the self-diffusion coefficient D L was measured at 40° C. The main measurement conditions for the self-diffusion coefficient are shown in Table 1.
  • the D M /D L of the mixture in Example 1 was 10 for sulfolane, [FSI] - was 42, and Li + was 1.
  • the D M /D L of the mixture in Example 2 was 15 for [FSI] - , and 1 for sulfolane and Li + .
  • the D M /D L of the mixture in Comparative Example 1 was 3 for sulfolane, [FSI] - was 5, and Li + was 1.
  • the D M /D L of the mixture in Comparative Example 2 was 0.6 for sulfolane.
  • Example 1 differs in that an electrolyte solution in which an electrolyte salt (LiFSI) is dissolved in a solvent is included, whereas Comparative Example 1 differs in that no electrolyte salt is dissolved in the solvent. Due to this difference, the D M /D L of Example 1 was 10 for sulfolane, whereas the D M /D L of Comparative Example 2 was 0.6 for sulfolane. This result makes it clear that the diffusibility of materials at the oxide interface is improved by the electrolyte in sulfolane, in addition to the oxide and sulfolane.
  • LiFSI electrolyte salt
  • the oxide ( ⁇ -alumina) and electrolyte salt (LiFSI) contained in the mixture are the same.
  • the two are different in that the solvent of the electrolyte is sulfolane in Example 1, whereas it is MPPy-FSI in Comparative Example 1. Due to this difference, the D M /D L of Example 1 was 10 for sulfolane and [FSI] - was 42, whereas the D M /D L of Comparative Example 1 was 3 for sulfolane and [FSI] - was 5. From this result, it was revealed that when sulfolane is contained in the electrolyte in addition to the oxide and electrolyte salt, the diffusibility of the substance at the oxide interface is significantly improved.
  • Example 1 Comparing the mixture in Example 1 with the mixture in Example 2, the electrolytes contained in the mixtures are the same. However, the oxides contained in the mixtures are different in that, while ⁇ -alumina is contained in the mixture in Example 1, tetragonal Li 7 La 3 Zr 2 O 12 is contained in the mixture in Example 2. Due to this difference, the D M /D L of Example 1 was 10 for sulfolane and the [FSI] ⁇ was 42, but the D M /D L of Example 2 was 1 for sulfolane and the [FSI] ⁇ was 15.
  • the ionic conductivity of the oxide itself may not necessarily be necessary to improve the diffusivity of the material at the interface between the oxide and the electrolyte. From this, it is presumed that some kind of ionic conduction path is formed at the oxide interface or in the liquid near the interface as a result of the interaction between the oxide and the electrolyte.
  • the ionic conductivity of each ion contained in the electrolyte can be calculated from the value of the self-diffusion coefficient D M of the ion by the Nernst-Einstein equation, and the ionic conductivity of all ionic components contained in the electrolyte can be summed up to estimate the ionic conductivity of the mixture to some extent.
  • the value of the ionic conductivity of the mixture estimated by this method does not necessarily match the value of the ionic conductivity measured at the same temperature as the temperature at which the self-diffusion coefficient D M was measured, for example, obtained by electrochemical impedance measurement.
  • the diffusion coefficient measured by other methods including electrochemical methods based on the change in concentration of the electrolyte, does not necessarily match the value of the self-diffusion coefficient D M.
  • the electrochemical element 11 is described as having a positive electrode layer 12 in which an active material layer 14 is provided on one side of a current collecting layer 13, and a negative electrode layer 16 in which an active material layer 18 is provided on one side of a current collecting layer 17, but this is not necessarily limited to this.
  • each element in the embodiment to an electrochemical element having electrode layers (so-called bipolar electrodes) in which an active material layer 14 and an active material layer 18 are provided on both sides of a current collecting layer 13. If the bipolar electrodes and electrolyte layers 15 are alternately stacked and housed in a case (not shown), an electrochemical element with a so-called bipolar structure is obtained.
  • the electrochemical element 11 in which the active material layers 14, 18 and the electrolyte layer 15 all contain the mixture 10 and the electrochemical element 24 in which both the active material layers 14, 18 contain the mixture 10 have been described, but this is not necessarily limited to this.
  • the electrochemical element may be any element in which at least one of the active material layers 14, 18 and the electrolyte layer 15 contains the mixture 10.
  • an electrochemical element 26 is described in which a protective layer 29 is disposed between the separator 25 and the negative electrode layer 30, and a protective layer 32 is disposed on the current collecting layer 17, but this is not necessarily limited to this. Of course, it is possible to omit one of the protective layers 29, 32.
  • the mixture 10 has been described using electrochemical elements 11, 24, and 26 made of lithium ion batteries (electricity storage devices) as examples, but this is not necessarily limited to this.
  • electrochemical elements that can include the mixture 10 include metal ion batteries other than lithium ion batteries, such as sodium ion batteries and magnesium batteries, redox reactions of electrodes and redox reactions of ions in an electrolyte, electrochemical capacitors that utilize electric double layers, metal-air batteries that use oxygen in the air as the positive electrode active material, fuel cells, and electrolysis devices that chemically decompose compounds or generate substances through chemical decomposition.

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009135076A (ja) * 2007-11-02 2009-06-18 Panasonic Corp 非水電解質二次電池
JP2020113527A (ja) 2018-03-20 2020-07-27 日立化成株式会社 電解質スラリ組成物及びその製造方法、並びに、電解質シート及びその製造方法
JP2020145054A (ja) * 2019-03-05 2020-09-10 株式会社日立製作所 非水電解液、半固体電解質層、二次電池用シート及び二次電池
JP2021089875A (ja) * 2019-12-06 2021-06-10 株式会社日立製作所 非水電解液、半固体電解質層、二次電池用シート及び二次電池

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009135076A (ja) * 2007-11-02 2009-06-18 Panasonic Corp 非水電解質二次電池
JP2020113527A (ja) 2018-03-20 2020-07-27 日立化成株式会社 電解質スラリ組成物及びその製造方法、並びに、電解質シート及びその製造方法
JP2020145054A (ja) * 2019-03-05 2020-09-10 株式会社日立製作所 非水電解液、半固体電解質層、二次電池用シート及び二次電池
JP2021089875A (ja) * 2019-12-06 2021-06-10 株式会社日立製作所 非水電解液、半固体電解質層、二次電池用シート及び二次電池

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