WO2022168845A1 - 非水電解質蓄電素子、及び蓄電装置 - Google Patents

非水電解質蓄電素子、及び蓄電装置 Download PDF

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WO2022168845A1
WO2022168845A1 PCT/JP2022/003949 JP2022003949W WO2022168845A1 WO 2022168845 A1 WO2022168845 A1 WO 2022168845A1 JP 2022003949 W JP2022003949 W JP 2022003949W WO 2022168845 A1 WO2022168845 A1 WO 2022168845A1
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positive electrode
aqueous electrolyte
lithium
negative electrode
compound
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PCT/JP2022/003949
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English (en)
French (fr)
Japanese (ja)
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祐輝 酒井
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株式会社Ｇｓユアサ
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    • 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
    • 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
    • H01M10/0566—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
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers

Definitions

  • the present invention relates to non-aqueous electrolyte 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 non-aqueous electrolyte storage elements other than non-aqueous electrolyte secondary batteries.
  • Patent Document 1 discloses a lithium secondary battery using a lithium metal foil as a negative electrode.
  • the lithium secondary battery using lithium metal for the negative electrode disclosed in the above patent document has a high energy density, but there is a risk that the internal resistance will increase with charge-discharge cycles, and the surface of the negative electrode during charging.
  • Lithium metal may be deposited in a dendritic form (hereinafter, lithium metal in a dendritic form is referred to as "dendrite”), and this dendrite deposition may cause an internal short circuit.
  • An object of the present invention is to provide a non-aqueous electrolyte storage element and a storage device that have high energy density, can suppress an increase in internal resistance due to charge/discharge cycles, and can delay the occurrence of an internal short circuit. It is to be.
  • a non-aqueous electrolyte storage element includes a positive electrode having a positive electrode mixture containing a phosphorus element, a negative electrode containing lithium metal, and a non-aqueous electrolyte containing a compound a, wherein the compound a is an oxygen element. , elemental fluorine, and at least one of elemental phosphorus and elemental boron.
  • Another aspect of the present invention is a power storage device including two or more non-aqueous electrolyte storage elements and one or more non-aqueous electrolyte storage elements according to another aspect of the present invention.
  • the non-aqueous electrolyte power storage element and the power storage device according to one aspect of the present invention have high energy density, can suppress an increase in internal resistance due to charge-discharge cycles, and can delay the occurrence of an internal short circuit. be.
  • FIG. 1 is a see-through perspective view showing one embodiment of a non-aqueous electrolyte storage element.
  • FIG. 2 is a schematic diagram showing an embodiment of a power storage device configured by assembling a plurality of non-aqueous electrolyte power storage elements.
  • a non-aqueous electrolyte storage element includes a positive electrode having a positive electrode mixture containing a phosphorus element, a negative electrode containing lithium metal, and a non-aqueous electrolyte containing a compound a, wherein the compound a is an oxygen element. , elemental fluorine, and at least one of elemental phosphorus and elemental boron.
  • the non-aqueous electrolyte storage element has a high energy density, can suppress an increase in internal resistance due to charge-discharge cycles, and can delay the occurrence of an internal short circuit.
  • the reason for this is presumed to be as follows. Since the non-aqueous electrolyte storage element includes a negative electrode containing lithium metal, the energy density is high. In a conventional non-aqueous electrolyte storage element having a negative electrode containing lithium metal, the decomposition of the non-aqueous electrolyte is significantly accelerated on the surface of the negative electrode, so that the ionic conductivity of the non-aqueous electrolyte is greatly reduced.
  • the decomposition tends to increase the thickness of the film formed on the surface of the negative electrode, and the ionic conductivity of the surface of the negative electrode decreases. As a result, the internal resistance tends to increase. In addition, the film is unevenly formed, causing localized current concentration at the negative electrode, which facilitates dendrite deposition of lithium metal on the surface of the negative electrode during charging, and as a result, tends to cause an internal short circuit.
  • the compound a contained in the non-aqueous electrolyte reacts with the lithium metal of the negative electrode preferentially over other components of the non-aqueous electrolyte, and the negative electrode surface is derived from the compound a.
  • the coating film derived from compound a in the negative electrode can suppress decomposition of other components of the non-aqueous electrolyte.
  • the film derived from compound a has relatively high ionic conductivity because it is derived from compound a having the composition described above.
  • the film derived from the compound a is easily formed uniformly, and local current concentration in the negative electrode can be suppressed.
  • the positive electrode of the non-aqueous electrolyte storage element has a positive electrode mixture containing phosphorus element, the positive electrode film is formed from the phosphorus element by the reaction between the positive electrode mixture and the non-aqueous electrolyte.
  • the phosphorus element-derived film on the positive electrode suppresses the decomposition of the non-aqueous electrolyte on the positive electrode surface and contributes to the selective reaction of the compound a contained in the non-aqueous electrolyte on the negative electrode surface. Therefore, the presence of the film derived from phosphorus on the positive electrode facilitates the formation of the film derived from the compound a on the negative electrode more uniformly and satisfactorily.
  • the action of the phosphorus element contained in the positive electrode mixture and the compound a contained in the non-aqueous electrolyte It is thought that good coatings are formed on both the positive and negative electrodes, and as a result, dendrite precipitation, which causes an increase in internal resistance and an internal short circuit, is effectively reduced.
  • the compound a may be lithium difluorophosphate (LiDFP) or lithium difluorooxalate borate (LiDFOB).
  • LiDFP lithium difluorophosphate
  • LiDFOB lithium difluorooxalate borate
  • the peak position of P2p may be 135 eV or less.
  • the P2p peak appearing below 135 eV in the above spectrum is the peak of a phosphorus atom derived from a phosphorus oxoacid such as phosphonic acid. That is, it indicates that phosphorus atoms derived from the oxoacid of phosphorus are present on the surface of the positive electrode mixture, and that a film containing the phosphorus atoms is formed on the surface of the positive electrode.
  • the film containing the phosphorus atoms is formed on the surface of the positive electrode in this way, the decomposition of the non-aqueous electrolyte on the surface of the positive electrode is further suppressed.
  • the formation of the film containing the phosphorus atom on the positive electrode makes it easier for the compound a to react more selectively on the surface of the negative electrode than on the surface of the positive electrode, so that the film derived from the compound a on the negative electrode is more uniform and good. easy to form.
  • a sample used for measuring the spectrum of the positive electrode mixture by X-ray photoelectron spectroscopy (XPS) is prepared by the following method.
  • the non-aqueous electrolyte storage element is discharged with a current of 0.1 C to the final discharge voltage in normal use, and is placed in a discharged state.
  • “during normal use” refers to the case where the non-aqueous electrolyte storage element is used under discharge conditions recommended or specified for the non-aqueous electrolyte storage element.
  • the discharged non-aqueous electrolyte storage element is disassembled, the positive electrode is taken out, the positive electrode is thoroughly washed with dimethyl carbonate, and then dried under reduced pressure at room temperature.
  • the dried positive electrode is cut into a predetermined size (for example, 2 ⁇ 2 cm 2 ) and used as a sample for spectrum measurement by XPS.
  • the work from the dismantling of the non-aqueous electrolyte storage element to the preparation of the sample for spectral measurement by XPS was performed in an argon atmosphere with a dew point of -60°C or less, and the sample was enclosed in a transfer vessel and was not exposed to the atmosphere.
  • the equipment used and the measurement conditions in XPS spectrum measurement of the positive electrode mixture are as follows.
  • the P2p peak position in the above spectrum is a value obtained as follows. First, the binding energy of the sp2 carbon peak in C1s is set to 284.8 eV, and all spectra obtained are corrected. Each spectrum is then smoothed by subtracting the background using the linear method. The binding energy showing the highest peak intensity in the range of 130 to 138 eV in the spectrum after flattening is defined as the P2p peak position.
  • the configuration of the non-aqueous electrolyte storage element the configuration of the storage device, the method for manufacturing the non-aqueous electrolyte 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.
  • a non-aqueous electrolyte storage element includes an electrode body having a positive electrode, a negative electrode and a separator, a non-aqueous electrolyte, the electrode body and the non-aqueous electrolyte and a container that houses the
  • the electrode body is usually a laminated type in which a plurality of positive electrodes and a plurality of negative electrodes are laminated with separators interposed therebetween, or a wound type in which positive electrodes and negative electrodes are laminated with separators interposed and wound.
  • the non-aqueous electrolyte exists in a state contained in the positive electrode, the negative electrode and the separator.
  • a non-aqueous electrolyte secondary battery hereinafter also simply referred to as "secondary battery" will be described.
  • the positive electrode has a positive electrode base material and a positive electrode material mixture layer disposed on the positive electrode base material directly or via an intermediate layer.
  • a positive electrode base material has electroconductivity. Whether or not a material has “conductivity” is determined using a volume resistivity of 10 7 ⁇ cm as a threshold measured according to JIS-H-0505 (1975).
  • the material for the positive electrode substrate metals such as aluminum, titanium, tantalum and 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 include foil, deposited film, mesh, porous material, and the like, and foil is preferable from the viewpoint of cost. Therefore, aluminum foil or aluminum alloy foil is preferable as the positive electrode substrate. Examples of aluminum or aluminum alloys include A1085, A3003, A1N30, etc. defined in JIS-H-4000 (2014) or JIS-H4160 (2006).
  • the average thickness of the positive electrode substrate 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 intermediate layer is a layer arranged between the positive electrode substrate and the positive electrode material mixture layer.
  • the intermediate layer contains a conductive agent such as carbon particles to reduce the contact resistance between the positive electrode substrate and the positive electrode mixture layer.
  • the composition of the intermediate layer is not particularly limited, and includes, for example, a binder and a conductive agent.
  • the positive electrode mixture layer is a layer formed of a positive electrode mixture.
  • This positive electrode mixture contains a phosphorus element.
  • the positive electrode mixture further contains a positive electrode active material, and optionally other optional components such as a conductive agent, a binder (binder), a thickener, and a filler.
  • the positive electrode material mixture layer is usually formed on the surface of the positive electrode substrate by coating and drying a positive electrode material mixture paste.
  • the positive electrode active material can be appropriately selected from known positive electrode active materials.
  • positive electrode active materials for lithium secondary batteries include lithium transition metal composite oxides having a ⁇ -NaFeO 2 type crystal structure, lithium transition metal composite oxides having a spinel crystal structure, polyanion compounds, chalcogen compounds, sulfur etc.
  • 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 Co (1-x) ]O 2 (0 ⁇ x ⁇ 0.5), Li[ Li x Ni ⁇ Mn (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), Li[Li x Ni ⁇ Co ⁇ Al (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 .
  • polyanion compounds include LiFePO4 , LiMnPO4 , LiNiPO4 , LiCoPO4, Li3V2(PO4)3 , Li2MnSiO4 , Li2CoPO4F and the like.
  • 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. These materials may be coated with other materials on their surfaces. In the positive electrode mixture layer, one kind of these materials may be used alone, or two or more kinds may be mixed and used.
  • the positive electrode active material is usually particles (powder).
  • 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 diameter of the positive electrode active material equal to or more than the above lower limit, the production or handling of the positive electrode active material becomes easy. By making the average particle size of the positive electrode active material equal to or less than the above upper limit, the electron conductivity of the positive electrode mixture layer is improved. Note that when a composite of a positive electrode active material and another material is used, the average particle size of the composite is taken as the average particle size of the positive electrode active material.
  • Average particle size is based on JIS-Z-8825 (2013), based on the particle size distribution measured by a laser diffraction / scattering method for a diluted solution in which particles are diluted with a solvent, JIS-Z-8819 -2 (2001) means a value at which the volume-based integrated distribution calculated according to 50%.
  • Pulverizers, classifiers, etc. are used to obtain powder with a predetermined particle size.
  • 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 mixture layer is preferably 50% by mass or more and 99% by mass or less, more preferably 70% by mass or more and 98% by mass or less, and even more preferably 80% by mass or more and 95% by mass or less.
  • the elemental phosphorus contained in the positive electrode mixture is preferably present in the positive electrode mixture in the form of a phosphorus oxoacid or a derivative obtained from the phosphorus oxoacid. That is, the positive electrode mixture preferably contains a phosphorus oxoacid or a derivative thereof.
  • Examples of the phosphorus oxoacid include phosphoric acid (H 3 PO 4 ), phosphonic acid (H 3 PO 3 ), phosphinic acid (H 3 PO 2 ), pyrophosphoric acid (H 4 P 2 O 7 ), polyphosphoric acid, and the like. Among these, phosphonic acid is more preferable.
  • Derivatives obtained from the above phosphorus oxoacids include phosphorus oxoacid salts and phosphorus oxoacid esters. In this way, when the positive electrode mixture contains the oxoacid of phosphorus or a derivative thereof, a favorable film containing phosphorus atoms is easily formed on the surface of the positive electrode. In addition, the formation of the film containing the phosphorus atoms on the surface of the positive electrode promotes uniform and favorable film formation derived from the compound a on the negative electrode.
  • the peak position of P2p is preferably 135 eV or less.
  • the peak position is preferably 131 eV or higher, more preferably 132 eV or higher, and even more preferably 133 eV or higher.
  • the P2p peaks appearing in the above range are peaks of phosphorus atoms derived from phosphorus oxoacids such as phosphonic acid. That is, the P2p peak indicates that phosphorus atoms derived from the oxoacid of phosphorus exist on the surface of the positive electrode mixture, and the phosphorus atoms form a film on the surface of the positive electrode.
  • the film containing the phosphorus atoms on the surface of the positive electrode in this way, decomposition of the non-aqueous electrolyte on the surface of the positive electrode is further suppressed.
  • the formation of such a coating promotes uniform and good coating formation on the negative electrode.
  • a P2p peak outside the above range may be present.
  • the P2p peak appearing in the range of binding energy of 135 eV or more is the peak of phosphorus atoms derived from, for example, fluoride of phosphorus.
  • 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 electron conductivity and coatability
  • acetylene black is particularly preferable
  • the content of the conductive agent in the positive electrode mixture layer 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, for example, fluorine resins (polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), etc.), thermoplastic resins such as polyethylene, polypropylene, polyacryl, and polyimide; ethylene-propylene-diene rubber (EPDM), sulfone Elastomers such as modified EPDM, styrene-butadiene rubber (SBR) and fluororubber; polysaccharide polymers and the like.
  • fluorine resins polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), etc.
  • thermoplastic resins such as polyethylene, polypropylene, polyacryl, and polyimide
  • EPDM ethylene-propylene-diene rubber
  • SBR styrene-butadiene rubber
  • fluororubber polysaccharide polymers and the like.
  • the content of the binder in the positive electrode mixture layer 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.
  • 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, alumina, titanium dioxide, calcium oxide, strontium oxide, barium oxide, magnesium oxide and aluminosilicate, magnesium hydroxide, calcium hydroxide, hydroxide Hydroxides such as aluminum, carbonates such as calcium carbonate, poorly soluble ionic crystals such as calcium fluoride, barium fluoride, and barium sulfate, nitrides such as aluminum nitride and silicon nitride, talc, montmorillonite, boehmite, zeolite, Mineral resource-derived substances such as apatite, kaolin, mullite, spinel, olivine, sericite, bentonite, and mica, or artificial products thereof may be used.
  • the positive electrode mixture layer contains typical nonmetallic elements such as B, N, F, Cl, Br, and I, and typical elements such as Li, Na, Mg, Al, K, Ca, Zn, Ga, Ge, Sn, Sr, and Ba.
  • Metal elements, transition 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, and phosphorus elements (for example, phosphorus oxoacids or derivatives thereof) , a conductive agent, a binder, a thickener, and a component other than a filler.
  • the negative electrode has a negative electrode active material layer.
  • the negative electrode may further include a negative electrode substrate and an intermediate layer interposed between the negative electrode substrate and the negative electrode active material layer.
  • the structure of the intermediate layer is not particularly limited, and can be selected from, for example, the structures exemplified for the positive electrode.
  • the negative electrode base material has conductivity.
  • materials for the negative electrode substrate metals such as copper, nickel, stainless steel, nickel-plated steel, alloys thereof, carbonaceous materials, and the like are used. Among these, stainless steel, copper, or copper alloys are preferred.
  • negative electrode substrates include foils, deposited films, meshes, porous materials, and the like, and foils are preferable from the viewpoint of cost. Therefore, stainless steel foil, 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 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 contains lithium metal.
  • Lithium metal is a component that functions as a negative electrode active material.
  • Lithium metal may exist as pure lithium metal consisting essentially of the lithium element, or may exist as a lithium alloy containing other metal elements. Together they are called "lithium metal".
  • Lithium alloys include lithium gold alloys, lithium tin alloys, 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 the lithium element.
  • the negative electrode active material layer may be a layer consisting essentially of lithium metal.
  • the lithium metal content in the negative electrode active material layer may be 90% by mass or more, 99% by mass or more, or 100% by mass.
  • the energy density of the secondary battery can be further increased.
  • the negative electrode active material layer may be lithium metal foil (including lithium alloy foil).
  • the negative electrode active material layer may be a non-porous layer (solid layer).
  • the average thickness of the negative electrode active material layer is preferably 5 ⁇ m or more and 600 ⁇ m or less, more preferably 10 ⁇ m or more and 400 ⁇ m or less, and even more preferably 30 ⁇ m or more and 200 ⁇ m or less. By setting the average thickness of the negative electrode active material layer within the above range, it is possible to achieve both high energy density and manufacturability of the negative electrode active material layer.
  • the separator can be appropriately selected from known separators.
  • a separator consisting of only a substrate layer, a separator having a heat-resistant layer containing heat-resistant particles and a binder formed on one or both surfaces of a substrate layer, or the like can be used.
  • Examples of the shape of the base layer of the separator include woven fabric, nonwoven fabric, and porous resin film. Among these shapes, a porous resin film is preferred from the viewpoint of strength, and a non-woven fabric is preferred from the viewpoint of non-aqueous electrolyte retention.
  • polyolefins such as polyethylene and polypropylene are preferable from the viewpoint of shutdown function, and polyimide, aramid, and the like are preferable from the viewpoint of oxidative decomposition resistance.
  • a material obtained by combining these resins may be used as the base material layer of the separator.
  • the heat-resistant particles contained in the heat-resistant layer preferably have a mass loss of 5% or less when the temperature is raised from room temperature to 500 ° C. in an air atmosphere of 1 atm, and the mass loss when the temperature is raised from room temperature to 800 ° C. is more preferably 5% or less.
  • An inorganic compound can be mentioned as a material whose mass reduction is less than or equal to a predetermined value. Examples of inorganic compounds include oxides such as iron oxide, silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, calcium oxide, strontium oxide, barium oxide, magnesium oxide, and aluminosilicate; nitrides such as aluminum nitride and silicon nitride.
  • carbonates such as calcium carbonate
  • sulfates such as barium sulfate
  • sparingly soluble ionic crystals such as calcium fluoride, barium fluoride, and barium titanate
  • covalent crystals such as silicon and diamond
  • Mineral resource-derived substances such as zeolite, apatite, kaolin, mullite, spinel, olivine, sericite, bentonite, and mica, or artificial products thereof.
  • the inorganic compound a single substance or a composite of these substances may be used alone, or two or more of them may be mixed and used.
  • silicon oxide, aluminum oxide, or aluminosilicate is preferable from the viewpoint of the safety of the electric storage device.
  • the porosity of the separator is preferably 80% by volume or less from the viewpoint of strength, and preferably 20% by volume or more from the viewpoint of discharge performance.
  • the "porosity” is a volume-based value and means a value measured with a mercury porosimeter.
  • a polymer gel composed of a polymer and a non-aqueous electrolyte may be used as the separator.
  • examples of polymers include polyacrylonitrile, polyethylene oxide, polypropylene oxide, polymethyl methacrylate, polyvinyl acetate, polyvinylpyrrolidone, polyvinylidene fluoride, and the like.
  • the use of polymer gel has the effect of suppressing liquid leakage.
  • a polymer gel may be used in combination with the porous resin film or non-woven fabric as described above.
  • the non-aqueous electrolyte contains compound a.
  • a non-aqueous electrolyte may be used as the non-aqueous electrolyte.
  • the non-aqueous electrolyte contains a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent.
  • the non-aqueous electrolyte may contain additives in addition to the non-aqueous solvent and electrolyte salt.
  • the compound a may be contained as an electrolyte salt or as an additive in the non-aqueous electrolyte. At least one of the electrolyte salt and the additive contains the compound a.
  • the non-aqueous solvent can be appropriately selected from known non-aqueous solvents.
  • Non-aqueous solvents include cyclic carbonates, chain carbonates, carboxylic acid esters, phosphoric acid esters, sulfonic acid esters, ethers, amides, nitriles and the like.
  • the non-aqueous solvent those in which some of the hydrogen atoms contained in these compounds are substituted with halogens may be used.
  • Cyclic carbonates include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylene carbonate (VC), vinylethylene carbonate (VEC), chloroethylene carbonate, fluoroethylene carbonate (FEC), difluoroethylene carbonate. (DFEC), styrene carbonate, 1-phenylvinylene carbonate, 1,2-diphenylvinylene carbonate and the like. Among these, FEC is preferred.
  • chain carbonates examples include diethyl carbonate (DEC), dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), diphenyl carbonate, trifluoroethylmethyl carbonate (TFEMC), bis(trifluoroethyl) carbonate, and the like.
  • DEC diethyl carbonate
  • DMC dimethyl carbonate
  • EMC ethylmethyl carbonate
  • TFEMC trifluoroethylmethyl carbonate
  • bis(trifluoroethyl) carbonate and the like.
  • the non-aqueous solvent it is preferable to use a cyclic carbonate or a chain carbonate, and it is more preferable to use a combination of a cyclic carbonate and a chain carbonate.
  • a cyclic carbonate it is possible to promote the dissociation of the electrolyte salt and improve the ionic conductivity of the non-aqueous electrolyte.
  • a chain carbonate By using a chain carbonate, the viscosity of the non-aqueous electrolyte can be kept low.
  • the volume ratio of the cyclic carbonate to the chain carbonate is preferably in the range of, for example, 5:95 to 50:50.
  • the electrolyte salt can be appropriately selected from known electrolyte salts.
  • electrolyte salts include lithium salts, sodium salts, potassium salts, magnesium salts, onium salts and the like. Among these, lithium salts are preferred.
  • Lithium salts include inorganic lithium salts such as LiPF 6 , lithium difluorophosphate (LiDFP), lithium monofluorophosphate, LiBF 4 , LiClO 4 , LiN(SO 2 F) 2 , and lithium bis(oxalate)borate (LiBOB).
  • LiPF 6 lithium difluorophosphate
  • LiClO 4 lithium monofluorophosphate
  • LiN(SO 2 F) 2 LiN(SO 2 F) 2
  • LiBOB lithium bis(oxalate)borate
  • lithium difluorooxalateborate LiDFOB
  • lithium difluorobis(oxalate)phosphate LiFOP
  • lithium oxalate salts such as lithium tetrafluorooxalate phosphate
  • LiSO3CF3 LiN( SO2CF3 ) 2
  • LiN Halogenated hydrocarbons such as SO2C2F5 ) 2
  • LiN ( SO2CF3 ) ( SO2C4F9 ) LiC ( SO2CF3 ) 3
  • LiC ( SO2C2F5 ) 3 LiC ( SO2C2F5 ) 3
  • lithium salt having a group LiPF6 is more preferred.
  • the lithium difluorophosphate (LiDFP), lithium monofluorophosphate, lithium difluorooxalate borate (LiDFOB), lithium difluorobis(oxalate) phosphate (LiFOP) and lithium tetrafluorooxalate phosphate are compound a as the electrolyte salt.
  • compound a may be used as an electrolyte salt.
  • the content of the electrolyte salt in the non-aqueous electrolyte is preferably 0.1 mol/dm3 or more and 2.5 mol/dm3 or less , and 0.3 mol/dm3 or more and 2.0 mol/dm3 or less at 20 °C and 1 atm. It is more preferably 3 or less, more preferably 0.5 mol/dm 3 or more and 1.7 mol/dm 3 or less, and particularly preferably 0.7 mol/dm 3 or more and 1.5 mol/dm 3 or less.
  • compound a may also be used as an additive.
  • the compound a as an additive contains oxygen element, fluorine element, and at least one of phosphorus element and boron element.
  • Examples of the compound a include a lithium phosphate containing lithium element, oxygen element and fluorine element, a lithium oxalate containing lithium element, boron element and fluorine element, and lithium element, phosphorus element and fluorine element.
  • the compound a a lithium phosphate containing lithium element, oxygen element and fluorine element is preferable from the viewpoint of delaying the occurrence of an internal short circuit.
  • the non-aqueous electrolyte contains the compound a in this way, a good film derived from the compound a is easily formed on the surface of the negative electrode.
  • the non-aqueous electrolyte may further contain other additives in addition to the compound a.
  • the other additives include halogenated carbonates such as fluoroethylene carbonate (FEC) and difluoroethylene carbonate (DFEC); oxalates such as lithium bis(oxalate)borate (LiBOB); lithium bis(fluorosulfonyl); ) imide salts such as imide (LiFSI); biphenyl, alkylbiphenyl, terphenyl, partially hydrogenated terphenyl, cyclohexylbenzene, t-butylbenzene, t-amylbenzene, diphenyl ether, dibenzofuran and other aromatic compounds; 2- Partial halides of the above aromatic compounds such as fluorobiphenyl, o-cyclohexylfluorobenzene, p-cyclohexylfluorobenzene; 2,4-difluoroanisole, 2,5
  • the content of the compound a contained in the non-aqueous electrolyte is preferably 0.01% by mass or more and 10% by mass or less with respect to the total mass of the non-aqueous electrolyte, and 0.1% by mass or more and 7% by mass or less. is more preferably 0.2% by mass or more and 6% by mass or less, and particularly preferably 0.3% by mass or more and 5% by mass or less.
  • the total content of the compound a and the other additives contained in the non-aqueous electrolyte is preferably 0.01% by mass or more and 10% by mass or less with respect to the total mass of the non-aqueous electrolyte, and 0.1 It is more preferably 0.2% to 8% by mass, and particularly preferably 0.3% to 7% by mass.
  • a solid electrolyte may be used as the non-aqueous electrolyte, or a non-aqueous electrolyte and a solid electrolyte may be used together.
  • the solid electrolyte can be selected from any material that has ion conductivity, such as lithium, sodium, and calcium, and is solid at room temperature (for example, 15°C to 25°C).
  • Examples of solid electrolytes include sulfide solid electrolytes, oxide solid electrolytes, oxynitride solid electrolytes, and polymer solid electrolytes.
  • Examples of sulfide solid electrolytes for lithium secondary batteries include Li 2 SP 2 S 5 , LiI—Li 2 SP 2 S 5 , Li 10 Ge—P 2 S 12 and the like.
  • FIG. 1 shows a non-aqueous electrolyte storage element 1 as an example of a square battery. In addition, the same figure is taken as the figure which saw through the inside of a container.
  • An electrode body 2 having a positive electrode and a negative electrode wound with a separator sandwiched therebetween is housed in a rectangular container 3 .
  • the positive electrode is electrically connected to the positive electrode terminal 4 via a positive electrode lead 41 .
  • the negative electrode is electrically connected to the negative terminal 5 via a negative lead 51 .
  • the non-aqueous electrolyte storage element 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 electric power It can be installed in a power source for storage or the like as a power storage unit (battery module) configured by collecting a plurality of non-aqueous electrolyte power storage elements 1 .
  • the technology of the present invention may be applied to at least one non-aqueous electrolyte storage element included in the storage unit.
  • a power storage device includes two or more nonaqueous electrolyte power storage elements and one or more nonaqueous electrolyte power storage elements according to the above embodiments (hereinafter referred to as "second embodiment"). ). It is sufficient that the technology according to one embodiment of the present invention is applied to at least one non-aqueous electrolyte power storage element included in the power storage device according to the second embodiment.
  • One non-aqueous electrolyte storage element may be provided, and one or more non-aqueous electrolyte storage elements according to the above embodiment may be provided, and two non-aqueous electrolyte storage elements according to the above embodiment may be provided. You may have more. FIG.
  • the power storage device 30 includes a bus bar (not shown) electrically connecting two or more non-aqueous electrolyte power storage elements 1, a bus bar (not shown) electrically connecting two or more power storage units 20, and the like. good too.
  • the power storage unit 20 or the power storage device 30 may include a state monitoring device (not shown) that monitors the state of one or more non-aqueous electrolyte power storage elements.
  • a method for manufacturing the non-aqueous electrolyte storage element of the present embodiment can be appropriately selected from known methods.
  • the manufacturing method includes, for example, preparing a positive electrode having a positive electrode mixture containing elemental phosphorus, preparing a negative electrode containing lithium metal, and preparing a non-aqueous electrolyte containing compound a.
  • Preparing a positive electrode having a positive electrode mixture containing elemental phosphorus may be manufacturing a positive electrode having a positive electrode mixture containing elemental phosphorus.
  • the positive electrode can be produced, for example, by applying the positive electrode material mixture paste directly or via an intermediate layer to the positive electrode base material and drying the paste.
  • the positive electrode mixture paste contains a phosphorus element.
  • the positive electrode mixture layer further contains a positive electrode active material and optional components such as a conductive agent, a binder, a thickener, and a filler, which constitute the positive electrode mixture.
  • the form of the phosphorus element contained in the positive electrode mixture paste is preferably a phosphorus oxoacid, and among the phosphorus oxoacids, phosphonic acid is more preferable.
  • a film containing favorable phosphorus atoms is easily formed on the surface of the positive electrode.
  • formation of a uniform and favorable film derived from the compound a on the negative electrode is promoted.
  • the phosphorus oxoacid is preferably 0.1% by mass or more and 1.0% by mass or less, and 0.2% by mass or more and 0.8% by mass or less with respect to the total mass of the positive electrode mixture paste. More preferably 0.25% by mass or more and 0.6% by mass or less.
  • Preparing a negative electrode containing lithium metal may be manufacturing a negative electrode containing lithium metal.
  • the production of the negative electrode may be performed, for example, by adhering a foil-shaped negative electrode active material layer containing lithium metal to the negative electrode base material directly or via an intermediate layer.
  • Preparing the non-aqueous electrolyte containing the compound a may be preparing the non-aqueous electrolyte containing the compound a.
  • the non-aqueous electrolyte can be prepared, for example, by mixing a non-aqueous solvent, an electrolyte salt (which may contain the above compound a), and an additive (which may contain the above compound a). At least one of the electrolyte salt and the additive contains the compound a.
  • the method for manufacturing the non-aqueous electrolyte storage element includes preparing a positive electrode having the above-described positive electrode mixture containing the phosphorus element, preparing a negative electrode containing lithium metal, and preparing a non-aqueous electrolyte containing the compound a.
  • the positive electrode and the negative electrode are laminated or wound with a separator interposed between them to form an alternately stacked electrode body, the positive electrode and the negative electrode (electrode body) are housed in a container, and the container is filled with the above-mentioned non- It may comprise injecting a water electrolyte. After the injection, a non-aqueous electrolyte storage element can be obtained by sealing the injection port.
  • non-aqueous electrolyte storage device of the present invention is not limited to the above embodiments, and various modifications may be made without departing from the gist of the present invention.
  • the configuration of another embodiment can be added to the configuration of one embodiment, and part of the configuration of one embodiment can be replaced with the configuration of another embodiment or a known technique.
  • some of the configurations of certain embodiments can be deleted.
  • well-known techniques can be added to the configuration of a certain embodiment.
  • the nonaqueous electrolyte storage element is used as a chargeable/dischargeable nonaqueous electrolyte secondary battery (for example, a lithium secondary battery). etc. are optional.
  • the present invention can also be applied to capacitors such as various secondary batteries, electric double layer capacitors, and lithium ion capacitors.
  • the electrode body in which the positive electrode and the negative electrode are laminated with a separator interposed therebetween has been described, but the electrode body does not have to be provided with a separator.
  • the positive electrode and the negative electrode may be in direct contact with each other in a state in which a layer having no conductivity is formed on the positive electrode mixture layer or the negative electrode active material layer.
  • Example 1 (Preparation of positive electrode) A lithium-transition metal composite oxide having a molar ratio (Li/Me) of lithium (Li) to a transition metal (Me) of 1.33 as a positive electrode active material, wherein the transition metal (Me) is nickel (Ni) and manganese ( Mn) and a lithium transition metal composite oxide having a Ni:Mn molar ratio of 1:2 was used.
  • the positive electrode paste was applied to one side of an aluminum foil having an average thickness of 15 ⁇ m, which was a positive electrode substrate, dried, and pressed to prepare a positive electrode having a positive electrode mixture layer disposed thereon.
  • the coating amount of the positive electrode mixture layer of the prepared positive electrode was 26.5 mg/cm 2 and the porosity was 40%.
  • the produced positive electrode was made into a rectangular shape with a width of 30 mm and a length of 40 mm.
  • a lithium metal plate having a width of 31 mm, a length of 42 mm, and a thickness of 600 ⁇ m was used as the negative electrode.
  • Non-aqueous electrolyte In a non-aqueous solvent obtained by mixing FEC: TFEMC at a volume ratio of 30:70, LiPF6 is dissolved as an electrolyte salt at a concentration of 1.0 mol/dm3, and lithium difluorophosphate ( LiDFP ), which is compound a, is added as an additive. ) was added at a concentration of about 0.5% by mass with respect to the total mass of the non-aqueous electrolyte to prepare a saturated solution. The above saturated solution was obtained as a non-aqueous electrolyte.
  • LiPF6 lithium difluorophosphate ( LiDFP )
  • a polyolefin microporous film was used as a separator.
  • An electrode body was produced by laminating the positive electrode and the negative electrode with the separator interposed therebetween. This electrode body was placed in a container made of a metal-resin composite film, and after the non-aqueous electrolyte was injected therein, the container was sealed by thermal welding to obtain a non-aqueous electrolyte storage element, which is a pouch cell.
  • Example 2 and Comparative Example 1 were prepared in the same manner as in Example 1, except that the mixed amount z of phosphonic acid in the positive electrode mixture paste and the type of the additive, which is the compound a in the non-aqueous electrolyte, were changed as shown in Table 1.
  • a non-aqueous electrolyte storage device 4 was produced from the above.
  • Reference Examples 1 to 4 were prepared in the same manner as in Example 1, except that the type of negative electrode active material, the mixed amount z of phosphonic acid in the positive electrode mixture paste, and the type of additive in the non-aqueous electrolyte were changed as shown in Table 1. A nonaqueous electrolyte storage element was produced.
  • a negative electrode mixture paste containing This negative electrode mixture paste was applied to one side of a copper foil as a negative electrode base material, dried and pressed to prepare a negative electrode.
  • the negative electrode active material layer of the prepared negative electrode had a coating amount of 22 mg/cm 2 and a porosity of 35%.
  • the produced negative electrode had a rectangular shape with a width of 32 mm and a length of 42 mm.
  • the non-aqueous electrolyte storage elements of Examples 1 and 2 and Comparative Examples 1 to 4 were subjected to a charging end voltage of 4.7 V in a temperature environment of 25° C. After constant-current charging at a charging current of 0.1 C, constant-voltage charging was performed. The charging termination condition was until the charging current reached 0.05C. After a rest period of 10 minutes, a constant current discharge was performed at a discharge current of 0.1C with a final discharge voltage of 2.0V.
  • the internal resistance is a value obtained by measuring AC resistance at 1 kHz at room temperature in a discharged state. A 3560 AC milliohm high tester (manufactured by Hioki) was used as a measuring device.
  • Example 1 in which phosphonic acid was mixed in the positive electrode mixture paste and LiDFP was added to the non-aqueous electrolyte, the rate of increase in internal resistance was reduced compared to Comparative Examples 1 to 3. Moreover, the number of cycles until the occurrence of a short circuit increased.
  • Example 2 in which phosphonic acid was mixed in the positive electrode mixture paste and LiDFOB (manufactured by Sigma-Aldrich) was added to the non-aqueous electrolyte, the rate of increase in internal resistance was reduced compared to Comparative Examples 2 to 4. Moreover, the number of cycles until the occurrence of a short circuit increased.
  • LiDFOB manufactured by Sigma-Aldrich
  • the positive electrode mixture contains a phosphorus element
  • the non-aqueous electrolyte contains a compound a containing an oxygen element, a fluorine element, and at least one of the phosphorus element and the boron element
  • the non-aqueous electrolyte storage element has a high energy density, can suppress an increase in internal resistance due to charge-discharge cycles, and can delay the occurrence of an internal short circuit. rice field.
  • the present invention can be applied to electronic devices such as personal computers, communication terminals, non-aqueous electrolyte storage elements and storage devices used as power sources for automobiles and the like.
  • Non-aqueous electrolyte storage element 1 Non-aqueous electrolyte storage element 2 Electrode body 3 Container 4 Positive electrode terminal 41 Positive electrode lead 5 Negative electrode terminal 51 Negative electrode lead 20 Storage unit 30 Storage device

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Citations (6)

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WO2013058224A1 (ja) * 2011-10-17 2013-04-25 宇部興産株式会社 非水電解液及びそれを用いた蓄電デバイス
JP2014053240A (ja) * 2012-09-10 2014-03-20 Toyota Motor Corp 非水リチウム二次電池用電解液、及び、非水リチウム二次電池
JP2015176760A (ja) * 2014-03-14 2015-10-05 三井化学株式会社 リチウム二次電池
JP2016004708A (ja) * 2014-06-18 2016-01-12 パナソニックＩｐマネジメント株式会社 リチウムイオン二次電池用正極活物質およびその製造方法、ならびにそれを用いたリチウムイオン二次電池
WO2019181278A1 (ja) * 2018-03-23 2019-09-26 パナソニックＩｐマネジメント株式会社 リチウム二次電池
JP2020155378A (ja) * 2019-03-22 2020-09-24 積水化学工業株式会社 リチウムイオン二次電池用電解液、及びリチウムイオン二次電池

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013058224A1 (ja) * 2011-10-17 2013-04-25 宇部興産株式会社 非水電解液及びそれを用いた蓄電デバイス
JP2014053240A (ja) * 2012-09-10 2014-03-20 Toyota Motor Corp 非水リチウム二次電池用電解液、及び、非水リチウム二次電池
JP2015176760A (ja) * 2014-03-14 2015-10-05 三井化学株式会社 リチウム二次電池
JP2016004708A (ja) * 2014-06-18 2016-01-12 パナソニックＩｐマネジメント株式会社 リチウムイオン二次電池用正極活物質およびその製造方法、ならびにそれを用いたリチウムイオン二次電池
WO2019181278A1 (ja) * 2018-03-23 2019-09-26 パナソニックＩｐマネジメント株式会社 リチウム二次電池
JP2020155378A (ja) * 2019-03-22 2020-09-24 積水化学工業株式会社 リチウムイオン二次電池用電解液、及びリチウムイオン二次電池

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