WO2022260001A1 - Électrolyte solide polymère, élément de stockage d'énergie et dispositif de stockage d'énergie - Google Patents

Électrolyte solide polymère, élément de stockage d'énergie et dispositif de stockage d'énergie Download PDF

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WO2022260001A1
WO2022260001A1 PCT/JP2022/022777 JP2022022777W WO2022260001A1 WO 2022260001 A1 WO2022260001 A1 WO 2022260001A1 JP 2022022777 W JP2022022777 W JP 2022022777W WO 2022260001 A1 WO2022260001 A1 WO 2022260001A1
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positive electrode
electrode active
active material
negative electrode
solid electrolyte
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Japanese (ja)
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栄人 渡邉
雄也 伊丹
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株式会社Ｇｓユアサ
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    • 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
    • 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

Definitions

  • the present invention relates to solid polymer electrolytes, power storage elements, and power storage devices.
  • Non-aqueous electrolyte secondary batteries typified by lithium-ion secondary batteries
  • the non-aqueous electrolyte secondary battery generally has a pair of electrodes electrically isolated by a separator and a non-aqueous electrolyte interposed between the electrodes, and transfers ions between the electrodes. It is configured to be charged and discharged by Capacitors such as lithium ion capacitors and electric double layer capacitors are also widely used as storage elements other than non-aqueous electrolyte secondary batteries.
  • Patent Document 1 has both lithium ion conductivity and oxidation resistance.
  • An object of the present invention is to provide a polymer solid electrolyte that has both lithium ion conductivity and oxidation resistance, and an electric storage element and an electric storage device comprising the same.
  • An embodiment according to one aspect of the present invention which has been made to solve the above problems, is a polymer material containing a carbonate structure represented by the following general formula (1) as a structural unit, and lithium bis (trifluoromethanesulfonyl) imide Alternatively, it is a polymer solid electrolyte containing a salt containing lithium bis(fluorosulfonyl)imide as a main component, wherein the concentration of the salt is 1.0 mol/kg or more. (Wherein R 1 and R 2 are independently H, F, or an alkyl group.)
  • Another aspect of the present invention is a power storage device comprising the polymer solid electrolyte according to one aspect of the present invention.
  • Another aspect of the present invention is a power storage device including two or more power storage elements and one or more power storage elements according to the other aspect of the present invention.
  • the solid polymer electrolyte according to one aspect of the present invention can achieve both ionic conductivity and oxidation resistance.
  • a power storage device can achieve both ionic conductivity and oxidation resistance of the polymer solid electrolyte included in the power storage device.
  • a power storage device can achieve both ionic conductivity and oxidation resistance of the polymer solid electrolyte included in the power storage device.
  • FIG. 1 is a schematic cross-sectional view of a power storage device (all-solid-state battery) according to one embodiment of the present invention.
  • FIG. 2 is a schematic diagram showing a power storage device configured by assembling a plurality of power storage elements according to one embodiment of the present invention.
  • FIG. 3 is a diagram showing the results of LSV (Linear Sweep Voltage) measurement according to Example 1.
  • FIG. 4 is a diagram showing the results of LSV measurement according to Comparative Example 4.
  • a polymer solid electrolyte according to one aspect of the present invention comprises a polymer material containing a carbonate structure represented by the general formula (1) as a constituent unit, and lithium bis(trifluoromethanesulfonyl)imide or lithium bis(fluorosulfonyl) ) and a salt containing imide as a main component, wherein the concentration of the salt is 1.0 mol/kg or more.
  • the polymer solid electrolyte according to one embodiment of the present invention is a carbonate structure represented by the general formula (1) having high oxidation resistance, and a high concentration of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) or By containing lithium bis(fluorosulfonyl)imide (LiFSI), both ionic conductivity and oxidation resistance can be achieved.
  • LiTFSI lithium bis(trifluoromethanesulfonyl)imide
  • LiFSI lithium bis(fluorosulfonyl)imide
  • the above salt is contained in the polymer solid electrolyte at a high concentration of 1.0 mol / kg or more. It is possible to Therefore, in a polymer solid electrolyte containing a polymer material containing the carbonate structure as a structural unit, the TFSI ion or FSI ion is preferentially coordinated to the lithium ion rather than the carbonate structure. Conductive paths are formed and ionic conductivity is increased.
  • the polymer solid electrolyte according to one embodiment of the present invention can achieve both ionic conductivity and oxidation resistance. is assumed to be possible.
  • lithium bis(pentafluoroethanesulfonyl)imide LiBETI
  • LiBETI lithium bis(pentafluoroethanesulfonyl)imide
  • lithium difluoro(oxalato)borate LiDFOB
  • LiDFOB lithium difluoro(oxalato)borate
  • LiFSI lithium bis(fluorosulfonyl)imide
  • Solid electrolyte refers to an electrolyte that is substantially composed only of solid components.
  • a solid component refers to a component that is solid at 20°C.
  • the expression that the electrolyte is substantially composed only of solid components means that the content of solid components in the electrolyte is 99% by mass or more.
  • a power storage device includes the polymer solid electrolyte according to one aspect of the present invention. Since the electric storage device includes the solid polymer electrolyte, it can achieve both ionic conductivity and oxidation resistance. Therefore, for example, even when a positive electrode active material having a high oxidation-reduction potential is used, good ion conductivity is exhibited.
  • the power storage device has a positive electrode potential of 4.7 V vs. 4.7 V when fully charged by a charging method during normal use. It is preferably Li/Li + or more. Since the electric storage element includes the polymer solid electrolyte with good oxidation resistance, even in a usage pattern in which the positive electrode potential is high when fully charged by the charging method during normal use, good ion conduction is achieved. It is possible to obtain a power storage element having a high energy density.
  • the positive electrode potential in a fully charged state is the positive electrode potential in a state in which the battery is not energized after being fully charged.
  • a power storage device includes two or more power storage elements, and one or more power storage elements according to another aspect of the present invention.
  • the power storage device includes the solid polymer electrolyte, it can achieve both ionic conductivity and oxidation resistance.
  • a polymer solid electrolyte, a structure of an electric storage element, a structure of an electric storage device, a method for manufacturing an electric storage element, and other embodiments according to one embodiment of the present invention will be described in detail. Note that the name of each component (each component) used in each embodiment may be different from the name of each component (each component) used in the background art.
  • the polymer solid electrolyte is mainly composed of a polymer material containing a carbonate structure represented by the above general formula (1) as a structural unit, and lithium bis(trifluoromethanesulfonyl)imide or lithium bis(fluorosulfonyl)imide. and a salt having a concentration of 1.0 mol/kg or more.
  • a polymeric material according to one embodiment of the present invention contains a carbonate structure represented by the general formula (1) as a structural unit.
  • R 1 and R 2 in general formula (1) are independently H, F, or alkyl groups. At least one of R 1 and R 2 is preferably H.
  • R 1 and R 2 are alkyl groups, the number of carbon atoms is not particularly limited, but is preferably 20 or less, more preferably 10 or less, and even more preferably 8 or less.
  • the polymer material may contain the carbonate structure represented by the general formula (1) as a structural unit, and may be a homopolymer having only the carbonate structure represented by the general formula (1) as a structural unit.
  • the content of the carbonate structure represented by the general formula (1) in the polymer material is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and 40% by mass or more. Even more preferably, 60% by mass or more is even more preferable, and 80% by mass or more is even more preferable.
  • the lower limit of the number average molecular weight of the polymer material is preferably 5,000, more preferably 10,000.
  • the upper limit of the number average molecular weight is preferably 500,000, more preferably 100,000.
  • a salt according to one embodiment of the present invention is based on lithium bis(trifluoromethanesulfonyl)imide or lithium bis(fluorosulfonyl)imide.
  • the “main component” means the component with the highest content in the salt contained in the polymer solid electrolyte, preferably 50% by mass or more, more preferably 90% by mass or more, and further 100% by mass. preferable.
  • the concentration of the salt is 1.0 mol/kg or more relative to the polymer solid electrolyte. When the concentration of the salt is equal to or higher than the lower limit, it is possible to increase not only the ionic conductivity but also the lithium ion transference number.
  • salts 1 type of these salts may be used individually, and 2 types may be mixed and used.
  • the above salts may further contain salts other than lithium bis(trifluoromethanesulfonyl)imide or lithium bis(fluorosulfonyl)imide.
  • the polymer solid electrolyte is mainly composed of a polymer material containing a carbonate structure represented by the above general formula (1) as a structural unit, and lithium bis(trifluoromethanesulfonyl)imide or lithium bis(fluorosulfonyl)imide. It may further contain other components other than the salt.
  • Other components include non-aqueous solvents and other additives.
  • additives conventionally known various additives that are added to the electrolyte of a general electric storage element can be used.
  • the content of other additives in the polymer solid electrolyte can be, for example, 0.01% by mass or more and 10% by mass or less, and can be 7% by mass or less, 3% by mass or less, or 1% by mass or less. preferable.
  • the content of solid components in the solid polymer electrolyte is 99% by mass or more, preferably 99.9% by mass or more, and more preferably 100% by mass.
  • the solid polymer electrolyte When the solid polymer electrolyte is applied to a power storage device having a negative electrode containing metallic lithium, for example, it can suppress deposition of dendritic metallic lithium (dendrite) on the surface of the negative electrode.
  • the polymer solid electrolyte can be suitably used as an electrolyte for a storage element such as a lithium ion secondary battery, especially a lithium battery. Moreover, the polymer solid electrolyte can be particularly suitably used as an electrolyte for an all-solid battery.
  • the polymer solid electrolyte can be used for any of the positive electrode layer, isolation layer, negative electrode layer, and the like in the electric storage element.
  • a method for producing a polymer solid electrolyte according to one embodiment of the present invention includes a polymer material containing a carbonate structure represented by the general formula (1) as a structural unit, and lithium bis(trifluoromethanesulfonyl)imide or with a salt based on lithium bis(fluorosulfonyl)imide.
  • This mixing method is not particularly limited. This mixing may be performed under heating by melting the polymer material containing the carbonate structure represented by the general formula (1) as a structural unit, and the carbonate structure represented by the general formula (1) is Even if the polymer material contained as a structural unit and the salt containing lithium bis(trifluoromethanesulfonyl)imide or lithium bis(fluorosulfonyl)imide as a main component are dissolved or dispersed in a liquid solvent, good.
  • the polymer solid electrolyte can be obtained by removing the solvent after mixing. During this mixing, the above other components can be further mixed as necessary. Moreover, after mixing, the polymer solid electrolyte obtained may be formed into a predetermined shape.
  • vinylene carbonate which is a precursor of polyvinylene carbonate (PVCA), and a salt containing lithium bis(trifluoromethanesulfonyl)imide or lithium bis(fluorosulfonyl)imide as a main component are mixed and dissolved in advance.
  • a precursor solution is prepared by mixing a polymerization initiator such as a radical polymerization initiator, and after the precursor solution is injected into the storage element, the storage element is heated to convert vinylene carbonate in the storage element.
  • a polymer solid electrolyte can also be obtained by polymerizing to produce polyvinylene carbonate.
  • the electric storage element is an electric storage element including the polymer solid electrolyte.
  • an all-solid-state battery will be described below as a specific example.
  • the storage element 10 in FIG. 1 is an all-solid battery, and is a secondary battery in which a positive electrode layer 1 (positive electrode) and a negative electrode layer 2 (negative electrode) are arranged with an isolation layer 3 interposed therebetween.
  • the positive electrode layer 1 has a positive electrode substrate 4 and a positive electrode active material layer 5 , and the positive electrode substrate 4 is the outermost layer of the positive electrode layer 1 .
  • the negative electrode layer 2 has a negative electrode substrate 7 and a negative electrode active material layer 6 , and the negative electrode substrate 7 is the outermost layer of the negative electrode layer 2 .
  • the negative electrode active material layer 6, the isolation layer 3, the positive electrode active material layer 5, and the positive electrode substrate 4 are laminated on the negative electrode substrate 7 in this order.
  • At least one of the positive electrode layer 1, the negative electrode layer 2, and the isolation layer 3 of the storage element 10 contains the polymer solid electrolyte according to one embodiment of the present invention. More specifically, at least one of the positive electrode active material layer 5, the negative electrode active material layer 6, and the isolation layer 3 contains the polymer solid electrolyte according to one embodiment of the present invention. Since the solid polymer electrolyte according to one embodiment of the present invention has good oxidation resistance, at least one of the positive electrode active material layer 5 and the isolation layer 3 contains the solid polymer electrolyte according to one embodiment of the present invention. It is preferably contained.
  • solid electrolytes than the polymer solid electrolyte according to one embodiment of the present invention may be used together.
  • Other solid electrolytes include sulfide-based solid electrolytes, oxide-based solid electrolytes, polymer solid electrolytes other than the polymer solid electrolyte according to one embodiment of the present invention, and the like.
  • a plurality of different types of solid electrolytes may be contained in one layer in the electric storage element 10, and different solid electrolytes may be contained in each layer.
  • the positive electrode layer 1 includes a positive electrode substrate 4 and a positive electrode active material layer 5 laminated on the surface of the positive electrode substrate 4 .
  • the positive electrode layer 1 may have an intermediate layer between the positive electrode substrate 4 and the positive electrode active material layer 5 .
  • the positive electrode base material 4 has conductivity. Having “conductivity” means having a volume resistivity of 10 7 ⁇ cm or less as measured in accordance with JIS-H-0505 (1975), and “non-conductivity” It means that the volume resistivity is more than 10 7 ⁇ cm.
  • metals such as aluminum, titanium, tantalum, indium, stainless steel, or alloys thereof are used. Among these, aluminum or an aluminum alloy is preferable from the viewpoint of potential resistance, high conductivity, and cost.
  • Examples of the positive electrode substrate 4 include foil, deposited film, mesh, porous material, and the like, and foil is preferable from the viewpoint of cost. Therefore, the positive electrode substrate 4 is preferably aluminum foil or aluminum alloy foil. Examples of aluminum or aluminum alloy include A1085P, A3003P, A1N30, etc. defined in JIS-H-4000 (2014) or JIS-H-4160 (2006).
  • the average thickness of the positive electrode substrate 4 is preferably 3 ⁇ m or more and 50 ⁇ m or less, more preferably 5 ⁇ m or more and 40 ⁇ m or less, even more preferably 8 ⁇ m or more and 30 ⁇ m or less, and particularly preferably 10 ⁇ m or more and 25 ⁇ m or less.
  • the "average thickness" of the positive electrode base material 4 and the negative electrode base material 7, which will be described later, refers to a value obtained by dividing the mass of the base material in a predetermined area by the true density and area of the base material.
  • the intermediate layer is a layer arranged between the positive electrode substrate 4 and the positive electrode active material layer 5 .
  • the intermediate layer reduces the contact resistance between the positive electrode substrate 4 and the positive electrode active material layer 5 by containing a conductive agent such as carbon particles.
  • the composition of the intermediate layer is not particularly limited, and includes, for example, a binder and a conductive agent.
  • the positive electrode active material layer 5 contains a positive electrode active material.
  • the positive electrode active material layer 5 can be formed from a so-called positive electrode mixture containing a positive electrode active material.
  • the positive electrode active material layer 5 may contain optional components such as a polymer solid electrolyte, a conductive agent, a binder, a thickener, a filler, and the like, if necessary. One or more of these optional components may not be substantially contained in the positive electrode active material layer 5 .
  • the positive electrode active material contained in the positive electrode active material layer 5 can be appropriately selected from known positive electrode active materials commonly used in lithium ion secondary batteries and all-solid-state batteries.
  • a material capable of intercalating and deintercalating lithium ions is usually used as the positive electrode active material. Examples thereof include lithium transition metal composite oxides having an ⁇ -NaFeO 2 type crystal structure, lithium transition metal composite oxides having a spinel crystal structure, polyanion compounds, chalcogen compounds, and sulfur.
  • lithium transition metal composite oxides having an ⁇ -NaFeO 2 type crystal structure examples include Li[Li x Ni (1-x) ]O 2 (0 ⁇ x ⁇ 0.5), Li[Li x Ni ⁇ Co ( 1-x- ⁇ ) ]O 2 (0 ⁇ x ⁇ 0.5, 0 ⁇ 1), Li[Li x Ni ⁇ Mn ⁇ Co (1-x- ⁇ - ⁇ ) ]O 2 (0 ⁇ x ⁇ 0.5, 0 ⁇ , 0 ⁇ , 0.5 ⁇ + ⁇ 1) and the like.
  • lithium transition metal composite oxides having a spinel crystal structure examples include Li x Mn 2 O 4 and Li x Ni ⁇ Mn (2- ⁇ ) O 4 .
  • Examples of polyanion compounds include LiFePO4 , LiMnPO4 , LiNiPO4 , LiCoPO4, Li3V2(PO4)3 , Li2MnSiO4 , Li2CoPO4F and the like.
  • Examples of chalcogen compounds include titanium disulfide, molybdenum disulfide, and molybdenum dioxide.
  • the atoms or polyanions in these materials may be partially substituted with atoms or anionic species of other elements.
  • the surface of the positive electrode active material may be coated with a compound such as lithium niobate, lithium titanate, or lithium phosphate. In the positive electrode active material layer, one kind of these positive electrode active materials may be used alone, or two or more kinds may be mixed and used.
  • positive electrode active materials include lithium transition metal composite oxides having an ⁇ -NaFeO 2 -type crystal structure or spinel-type crystal structure, and polyanion compounds containing nickel, cobalt, or manganese elements (LiMnPO 4 , LiNiPO 4 , LiCoPO 4 , LiCoPO 4 , Li 2 MnSiO 4 , Li 2 CoPO 4 F, etc.) are preferable, and a lithium transition metal composite oxide having an ⁇ -NaFeO 2 type crystal structure is more preferable.
  • the lithium-transition metal composite oxides having the ⁇ -NaFeO 2 type crystal structure those containing one or more of nickel, cobalt and manganese as transition metal elements are more preferable.
  • These positive electrode active materials have a particularly high oxidation-reduction potential, and by using such positive electrode active materials, the energy density and the like of the electric storage element can be increased.
  • the polymer solid electrolyte having good oxidation resistance according to one embodiment of the present invention is used for the storage element 10, even when these positive electrode active materials having a high oxidation-reduction potential are used, good It is possible to maintain good charge and discharge performance.
  • the average particle size of the positive electrode active material is preferably, for example, 0.1 ⁇ m or more and 20 ⁇ m or less. By making the average particle size of the positive electrode active material equal to or more than the above lower limit, manufacturing or handling of the positive electrode active material becomes easy. By setting the average particle diameter of the positive electrode active material to the above upper limit or less, the conductivity of the positive electrode active material layer 5 is improved.
  • the "average particle size" is based on the particle size distribution measured by a laser diffraction/scattering method for a diluted solution in which the particles are diluted with a solvent in accordance with JIS-Z-8825 (2013).
  • Z-8819-2 (2001) means the value at which the volume-based integrated distribution calculated according to 50%.
  • Pulverizers, classifiers, etc. are used to obtain particles in a predetermined shape.
  • Pulverization methods include, for example, methods using a mortar, ball mill, sand mill, vibrating ball mill, planetary ball mill, jet mill, counter jet mill, whirling jet mill, or sieve.
  • wet pulverization in which water or an organic solvent such as hexane is allowed to coexist can also be used.
  • a sieve, an air classifier, or the like is used as necessary, both dry and wet.
  • the content of the positive electrode active material in the positive electrode active material layer 5 is preferably 10% by mass or more and 95% by mass or less, more preferably 30% by mass or more, and further preferably 50% by mass or more. By setting the content of the positive electrode active material within the above range, the electric capacity of the storage element 10 can be increased.
  • the content of the solid electrolyte is preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 70% by mass or less, and further 50% by mass or less. preferable. By setting the content of the solid electrolyte within the above range, the electrical capacity of the storage element 10 can be increased.
  • the content of the solid polymer electrolyte according to one embodiment of the present invention with respect to the total solid electrolyte in the positive electrode active material layer 5 is , preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and even more preferably substantially 100% by mass.
  • the positive electrode active material and the solid electrolyte may form a composite.
  • the conductive agent is not particularly limited as long as it is a conductive material.
  • Examples of such conductive agents include carbonaceous materials, metals, and conductive ceramics.
  • Carbonaceous materials include graphite, non-graphitic carbon, graphene-based carbon, and the like.
  • Examples of non-graphitic carbon include carbon nanofiber, pitch-based carbon fiber, and carbon black.
  • Examples of carbon black include furnace black, acetylene black, and ketjen black.
  • Graphene-based carbon includes graphene, carbon nanotube (CNT), fullerene, and the like.
  • the shape of the conductive agent may be powdery, fibrous, or the like.
  • As the conductive agent one type of these materials may be used alone, or two or more types may be mixed and used. Also, these materials may be combined for use.
  • a composite material of carbon black and CNT may be used.
  • carbon black is preferable from the viewpoint of conductivity and coatability
  • acetylene black is particularly preferable.
  • the content of the conductive agent in the positive electrode active material layer 5 is preferably 1% by mass or more and 10% by mass or less, more preferably 3% by mass or more and 9% by mass or less.
  • binders include fluororesins (polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), etc.), polyethylene, polypropylene, polyimide, poly(meth)acrylic acid, poly(meth)acrylic acid ester, poly(meth) ) thermoplastic resins such as acrylamide; elastomers such as ethylene-propylene-diene rubber (EPDM), sulfonated EPDM, styrene-butadiene rubber (SBR) and fluororubber; polysaccharide polymers and the like.
  • fluororesins polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), etc.
  • PTFE polytetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • binders include fluororesins (polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), etc
  • the binder content in the positive electrode active material layer 5 is preferably 1% by mass or more and 10% by mass or less, more preferably 3% by mass or more and 9% by mass or less. By setting the content of the binder within the above range, the active material can be stably retained.
  • thickeners examples include polysaccharide polymers such as carboxymethylcellulose (CMC) and methylcellulose.
  • CMC carboxymethylcellulose
  • methylcellulose examples include polysaccharide polymers such as carboxymethylcellulose (CMC) and methylcellulose.
  • the functional group may be previously deactivated by methylation or the like.
  • the filler is not particularly limited.
  • Fillers include polyolefins such as polypropylene and polyethylene, inorganic oxides such as silicon dioxide, aluminum oxide, titanium dioxide, calcium oxide, strontium oxide, barium oxide, magnesium oxide and aluminosilicate, magnesium hydroxide, calcium hydroxide, and water.
  • Hydroxides such as aluminum oxide, carbonates such as calcium carbonate, sparingly soluble ionic crystals such as calcium fluoride, barium fluoride, and barium sulfate, nitrides such as aluminum nitride and silicon nitride, talc, montmorillonite, boehmite, and zeolite , apatite, kaolin, mullite, spinel, olivine, sericite, bentonite, mica, and other mineral resource-derived substances or artificial products thereof.
  • the positive electrode active material layer 5 is composed of typical nonmetallic elements such as B, N, P, F, Cl, Br, I, Li, Na, Mg, Al, K, Ca, Zn, Ga, Ge, Sn, Sr, Ba Typical metal elements such as Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, Zr, Nb, and W are used as positive electrode active materials, solid electrolytes, conductive agents, binders, and thickeners. You may contain as a component other than a sticky agent and a filler.
  • the average thickness of the positive electrode active material layer 5 is preferably 30 ⁇ m or more and 1000 ⁇ m or less, more preferably 60 ⁇ m or more and 500 ⁇ m or less. By setting the average thickness of the positive electrode active material layer 5 to the above lower limit or more, it is possible to obtain the electric storage device 10 having a high energy density. By making the average thickness of the positive electrode active material layer 5 equal to or less than the upper limit, it is possible to reduce the size of the electric storage device 10 . Let the average thickness of the positive electrode active material layer 5 be the average value of the thickness measured at arbitrary five places. The same applies to the average thicknesses of the negative electrode active material layer 6 and the separation layer 3, which will be described later.
  • the negative electrode layer 2 has a negative electrode base material 7 and a negative electrode active material layer 6 disposed on the negative electrode base material 7 directly or via an intermediate layer.
  • the structure of the intermediate layer is not particularly limited, and can be selected from the structures exemplified for the positive electrode layer 1, for example.
  • the negative electrode base material 7 has conductivity.
  • materials for the negative electrode substrate 7 metals such as copper, nickel, stainless steel, nickel-plated steel, and aluminum, alloys thereof, carbonaceous materials, and the like are used. Among these, copper or a copper alloy is preferred.
  • examples of negative electrode substrates include foils and vapor deposition films, and foils are preferred from the viewpoint of cost. Therefore, copper foil or copper alloy foil is preferable as the negative electrode substrate.
  • Examples of copper foil include rolled copper foil and electrolytic copper foil.
  • the average thickness of the negative electrode substrate 7 is preferably 2 ⁇ m or more and 35 ⁇ m or less, more preferably 3 ⁇ m or more and 30 ⁇ m or less, even more preferably 4 ⁇ m or more and 25 ⁇ m or less, and particularly preferably 5 ⁇ m or more and 20 ⁇ m or less.
  • the negative electrode active material layer 6 contains a negative electrode active material.
  • the negative electrode active material layer 6 can be formed, for example, from a so-called negative electrode mixture containing a negative electrode active material.
  • the negative electrode active material layer 6 contains optional components such as a solid electrolyte, a conductive agent, a binder, a thickener, a filler, and the like, if necessary.
  • the types and suitable contents of these optional components in the negative electrode active material layer 6 are the same as those of the above-described optional components in the positive electrode active material layer 5 .
  • One or more of these optional components may not be substantially contained in the negative electrode active material layer 6 .
  • the negative electrode active material layer 6 is composed of typical nonmetallic elements such as B, N, P, F, Cl, Br, and I, Li, Na, Mg, Al, K, Ca, Zn, Ga, Ge, Sn, Sr, and Ba.
  • Typical metal elements such as Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, Zr, Ta, Hf, Nb, W, etc. are used as negative electrode active materials, solid electrolytes, and conductive agents. , a binder, a thickener, and a component other than a filler.
  • the negative electrode active material can be appropriately selected from known negative electrode active materials commonly used in lithium ion secondary batteries and all-solid batteries.
  • a material capable of intercalating and deintercalating lithium ions is usually used as the negative electrode active material.
  • the negative electrode active material include metal Li; metals or metalloids such as Si and Sn; metal oxides and metalloid oxides such as Si oxide, Ti oxide and Sn oxide; Li 4 Ti 5 O 12 ; Titanium-containing oxides such as LiTiO 2 and TiNb 2 O 7 ; polyphosphate compounds; silicon carbide; carbon materials such as graphite and non-graphitizable carbon (easily graphitizable carbon or non-graphitizable carbon) be done.
  • the negative electrode active material layer 6 one kind of these materials may be used alone, or two or more kinds may be mixed and used.
  • Graphite refers to a carbon material having an average lattice spacing (d 002 ) of the (002) plane of 0.33 nm or more and less than 0.34 nm as determined by X-ray diffraction before charging/discharging or in a discharged state.
  • Graphite includes natural graphite and artificial graphite. Artificial graphite is preferable from the viewpoint that a material with stable physical properties can be obtained.
  • Non-graphitic carbon refers to a carbon material having an average lattice spacing (d 002 ) of the (002) plane of 0.34 nm or more and 0.42 nm or less as determined by X-ray diffraction before charging/discharging or in a discharged state.
  • Non-graphitizable carbon includes non-graphitizable carbon and graphitizable carbon. Examples of non-graphitic carbon include resin-derived materials, petroleum pitch-derived materials, and alcohol-derived materials.
  • the discharged state means a state in which the carbon material, which is the negative electrode active material, is discharged such that lithium ions that can be inserted and released are sufficiently released during charging and discharging.
  • the open circuit voltage is 0.7 V or higher.
  • non-graphitizable carbon refers to a carbon material having a d 002 of 0.36 nm or more and 0.42 nm or less.
  • Graphitizable carbon refers to a carbon material having a d 002 of 0.34 nm or more and less than 0.36 nm.
  • Metallic lithium is preferable as the negative electrode active material.
  • Metallic lithium may exist as pure metallic lithium consisting essentially of lithium, or may exist as a lithium alloy containing other metal elements.
  • Lithium alloys include lithium silver alloys, lithium zinc alloys, lithium calcium alloys, lithium aluminum alloys, lithium magnesium alloys, lithium indium alloys, and the like.
  • the lithium alloy may contain multiple metal elements other than lithium.
  • the negative electrode active material layer 6 is preferably a layer consisting essentially of metallic lithium.
  • the content of metallic lithium in the negative electrode active material layer 6 is preferably 90% by mass or more, more preferably 99% by mass or more, and even more preferably 100% by mass.
  • the negative electrode active material layer 6 is preferably a pure metal lithium foil or a lithium alloy foil.
  • Particles can be used as the negative electrode active material.
  • the average particle size of the negative electrode active material can be, for example, 1 nm or more and 100 ⁇ m or less.
  • the negative electrode active material is, for example, a carbon material, its average particle size is preferably 1 ⁇ m or more and 100 ⁇ m or less.
  • the negative electrode active material is a metal, a metalloid, a metal oxide, a metalloid oxide, a titanium-containing oxide, a polyphosphate compound, or the like, the average particle size is preferably 1 nm or more and 10 ⁇ m or less.
  • the conductivity of the active material layer is improved.
  • a pulverizer, a classifier, or the like is used to obtain powder having a predetermined particle size.
  • the pulverization method and classification method can be selected from the methods exemplified for the positive electrode layer 1, for example.
  • the content of the negative electrode active material in the negative electrode active material layer 6 is preferably 10% by mass or more and 95% by mass or less, more preferably 30% by mass or more, and further 50% by mass or more. more preferred.
  • the electric capacity of the storage element 10 can be increased.
  • the content of the solid electrolyte is preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 70% by mass or less, and further preferably 50% by mass or less. preferable. By setting the content of the solid electrolyte within the above range, the electric capacity of the electric storage element 10 can be increased.
  • the content of the solid polymer electrolyte according to one embodiment of the present invention with respect to the total solid electrolyte in the negative electrode active material layer 6 is , preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and even more preferably substantially 100% by mass.
  • the average thickness of the negative electrode active material layer 6 is not particularly limited. By making the average thickness of the negative electrode active material layer 6 equal to or greater than the above lower limit, the charge/discharge performance and the like of the storage element 10 can be enhanced. In particular, when the negative electrode active material is metallic lithium, charging/discharging is sufficiently possible even if the average thickness of the negative electrode active material layer 6 is as thin as less than 1 ⁇ m. By making the average thickness of the negative electrode active material layer 6 equal to or less than the above upper limit, it is possible to reduce the size of the storage element 10 .
  • the isolation layer 3 preferably contains a solid electrolyte.
  • a solid electrolyte contained in the isolation layer 3
  • various solid electrolytes can be used in addition to the polymer solid electrolyte according to the embodiment of the present invention described above.
  • the content of the solid electrolyte in the isolation layer 3 is preferably 70% by mass or more, more preferably 90% by mass or more, still more preferably 99% by mass or more, and even more preferably substantially 100% by mass.
  • the content of the solid polymer electrolyte according to one embodiment of the present invention in the total solid electrolyte in the isolation layer 3 is It is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and even more preferably substantially 100% by mass.
  • the isolation layer 3 may contain optional components such as fillers in addition to the solid electrolyte.
  • Optional components such as fillers can be selected from the materials exemplified for the positive electrode active material layer 5 .
  • a woven fabric, a non-woven fabric, a porous resin film, or the like may be arranged in the isolating layer 3 in order to increase the mechanical strength.
  • the average thickness of the isolation layer 3 is preferably 1 ⁇ m or more and 200 ⁇ m or less, more preferably 3 ⁇ m or more and 100 ⁇ m or less. By setting the average thickness of the isolation layer 3 to the above lower limit or more, it is possible to reliably insulate the positive electrode layer 1 and the negative electrode layer 2 from each other. By making the average thickness of isolation layer 3 equal to or less than the above upper limit, it is possible to increase the energy density of storage element 10 .
  • the positive electrode potential of the storage element 10 fully charged by the charging method during normal use is, for example, 3.5 V vs. Li/Li + or more, preferably 4.0 V vs. Li/Li + or more is more preferable, and 4.5 V vs. More preferably Li/Li + or more, 4.6 V vs. More preferably Li/Li + or more, 4.7 V vs. More preferably Li/Li + or more, 4.8 V vs. Li/Li + or more is even more preferable.
  • the energy density and voltage of the storage element 10 can be increased by setting the positive electrode potential in a fully charged state by the charging method during normal use to the lower limit or higher.
  • the solid polymer electrolyte having good oxidation resistance according to one embodiment of the present invention is used for the storage element 10, the positive electrode potential in a fully charged state by the charging method during normal use is Even when it is high, good charge/discharge performance can be maintained.
  • the upper limit of the positive electrode potential in a fully charged state by the charging method during normal use of the storage element 10 is, for example, 6.0 V vs. Li/Li + , 5.5V vs. Li/Li + is preferred, 5.2V vs. Li/Li + is more preferred.
  • the power storage device of the present embodiment is a power source for automobiles such as electric vehicles (EV), hybrid vehicles (HEV), and plug-in hybrid vehicles (PHEV), power sources for electronic devices such as personal computers and communication terminals, or power sources for power storage.
  • EV electric vehicles
  • HEV hybrid vehicles
  • PHEV plug-in hybrid vehicles
  • power sources for electronic devices such as personal computers and communication terminals
  • power sources for power storage
  • it can be mounted as a power storage unit (battery module) configured by assembling a plurality of power storage elements.
  • the technology according to one embodiment of the present invention may be applied to at least one power storage element included in the power storage unit.
  • a power storage device according to one embodiment of the present invention includes two or more power storage elements and one or more power storage elements according to one embodiment of the present invention (hereinafter referred to as "second embodiment").
  • the technology according to one embodiment of the present invention is applied to at least one power storage element included in the power storage device according to the second embodiment.
  • One or more energy storage elements not related to one embodiment of the present invention may be provided, or two or more energy storage elements according to one embodiment of the present invention may be included.
  • FIG. 2 shows an example of a power storage device 30 according to the second embodiment, in which power storage units 20 each including two or more electrically connected power storage elements 10 are assembled.
  • the power storage device 30 may include a bus bar (not shown) that electrically connects two or more power storage elements 10, a bus bar (not shown) that electrically connects two or more power storage units 20, and the like.
  • the power storage unit 20 or power storage device 30 may include a state monitoring device (not shown) that monitors the state of one or more power storage elements.
  • the method for producing an electric storage element according to one embodiment of the present invention is generally known except that the polymer solid electrolyte according to one embodiment of the present invention is used to produce at least one of the positive electrode layer, the isolation layer, and the negative electrode layer. It can be done by the method of The production method includes, for example, (1) preparing a positive electrode layer-forming material such as a positive electrode mixture and a positive electrode base material, (2) preparing a separation layer material, and (3) a negative electrode mixture, a negative electrode base material, and the like. and (4) laminating the positive electrode layer, the isolation layer and the negative electrode layer.
  • the above-described forms of the positive electrode layer, the separating layer, and the negative electrode layer provided in the electric storage element can be applied.
  • metallic lithium when metallic lithium is used as the negative electrode active material, metallic lithium foil or the like can be used as an example of the negative electrode layer forming material.
  • the present invention is not limited to the above-described embodiments, and can be implemented in various modified and improved modes in addition to the above-described modes.
  • the power storage device according to the present invention may include layers other than the positive electrode layer, the isolation layer, and the negative electrode layer.
  • Each structure of the positive electrode layer, the isolation layer, and the negative electrode layer is not limited to the above-described structures.
  • the negative electrode layer (negative electrode) may be composed only of the negative electrode base material without the negative electrode active material layer.
  • the electric storage device according to the present invention may contain a liquid in one or more of the layers.
  • the positive electrode, negative electrode, etc. of the storage device according to the present invention may not have a layered structure.
  • the storage element according to the present invention may be a storage element that is a secondary battery, or may be a capacitor or the like.
  • Example 1 After mixing vinylene carbonate and LiTFSI, a precursor was prepared by adding azobisisobutyronitrile (AIBN) as a polymerization initiator. Using a working electrode and a counter electrode made of SUS foil (diameter 26 mm) with a thickness of 12 ⁇ m and a separation layer made of a cellulose nonwoven fabric with a thickness of 35 ⁇ m, the separation layer was sandwiched between the working electrode and the counter electrode, and the precursor was injected and then sealed. By doing so, a cell for ionic conductivity evaluation was manufactured. After that, the ion conductivity evaluation cell is left in a constant temperature bath at 60° C.
  • AIBN azobisisobutyronitrile
  • polyvinylene carbonate PVCA
  • An ionic conductivity evaluation cell comprising the polymer solid electrolyte of Example 1 was obtained.
  • the concentration of salt (LiTFSI) in the polymer solid electrolyte of Example 1 was 1.4 mol/kg.
  • Example 2 to 8 Comparative Examples 1, 2, 3 and 5
  • Examples 2 to 8 and Comparative Examples 1, 2, 3 and 5 were prepared in the same manner as in Example 1 except that the salt, polymer material, and salt concentration were as shown in Tables 1 and 2.
  • An ionic conductivity evaluation cell having a molecular solid electrolyte was obtained.
  • the ionic conductivity of each polymer solid electrolyte was determined by an electrochemical impedance method using an ionic conductivity evaluation cell provided with each polymer solid electrolyte of Examples and Comparative Examples. Under the environment of 25° C., the measurement frequency was set to 7 MHz to 100 mHz, and the ionic conductivity was obtained by a conventional method from the obtained complex impedance.
  • the Young's modulus of the self-supporting membrane composed of each polymer solid electrolyte of Examples 4 to 8 was obtained by the following procedure. As samples for Young's modulus evaluation, two self-supporting membranes of each solid polymer electrolyte having length, width and thickness of 0.5 cm, 0.5 cm and 300 to 500 ⁇ m were prepared. Using a microcompression tester (MCT-211 manufactured by Shimadzu Corporation), the amount of displacement of the obtained self-supporting membrane was measured. The measurement conditions were the maximum test force of 100 mN, the minimum test force of 0.49 mN, the load speed of 9.68 mN/sec, and the load retention time and unload retention time of 0 seconds in the test mode of the load-unload test.
  • Example 1 As shown in Table 1, it was confirmed that the polymer solid electrolytes of Examples 1 to 3 had good oxidation resistance and good ionic conductivity. As shown in FIGS. 3 and 4, the voltage at which the current abruptly increases, that is, the voltage at which the oxidative decomposition of the solid polymer electrolyte occurs is high in Example 1 and low in Comparative Example 4. It can be seen that the molecular solid electrolyte has good oxidation resistance and Comparative Example 4 has poor oxidation resistance.
  • the polymer solid electrolyte according to the present invention is suitably used as an electrolyte for power storage elements such as all-solid batteries.
  • Positive electrode layer positive electrode layer (positive electrode) 2 negative electrode layer (negative electrode) 3 Separation layer 4 Positive electrode substrate 5 Positive electrode active material layer 6 Negative electrode active material layer 7 Negative electrode substrate 10 Power storage element (all-solid battery) 20 power storage unit 30 power storage device

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Abstract

Un électrolyte solide polymère selon un aspect de la présente invention contient : un matériau polymère contenant, en tant qu'unité constitutive, une structure de carbonate représentée par la formule générale suivante (1) ; et un sel ayant du bis(trifluorométhanesulfonyl)imide de lithium ou du bis(fluorosulfonyl)imide de lithium en tant que composant principal. La concentration du sel est égale ou supérieure à 1,0 mol/kg. (Dans la formule, R1 et R2 représentent indépendamment H, F ou un groupe alkyle.)
PCT/JP2022/022777 2021-06-10 2022-06-06 Électrolyte solide polymère, élément de stockage d'énergie et dispositif de stockage d'énergie WO2022260001A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107768717A (zh) * 2017-09-14 2018-03-06 哈尔滨工业大学无锡新材料研究院 一种紫外固化的半互穿网络结构的聚碳酸酯基固态聚合物电解质及其制备方法
CN110518282A (zh) * 2019-09-11 2019-11-29 蜂巢能源科技有限公司 固体聚合物电解质、固态锂离子电池

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107768717A (zh) * 2017-09-14 2018-03-06 哈尔滨工业大学无锡新材料研究院 一种紫外固化的半互穿网络结构的聚碳酸酯基固态聚合物电解质及其制备方法
CN110518282A (zh) * 2019-09-11 2019-11-29 蜂巢能源科技有限公司 固体聚合物电解质、固态锂离子电池

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