WO2023089894A1 - 蓄電デバイス用非水電解液および蓄電デバイス - Google Patents

蓄電デバイス用非水電解液および蓄電デバイス Download PDF

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WO2023089894A1
WO2023089894A1 PCT/JP2022/031990 JP2022031990W WO2023089894A1 WO 2023089894 A1 WO2023089894 A1 WO 2023089894A1 JP 2022031990 W JP2022031990 W JP 2022031990W WO 2023089894 A1 WO2023089894 A1 WO 2023089894A1
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component
isocyanate
lithium
group
storage device
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French (fr)
Japanese (ja)
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仁志 西谷
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to JP2023562143A priority Critical patent/JPWO2023089894A1/ja
Priority to CN202280077337.5A priority patent/CN118302884A/zh
Priority to US18/709,675 priority patent/US20250006950A1/en
Publication of WO2023089894A1 publication Critical patent/WO2023089894A1/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/06—Electrodes for primary cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/64—Liquid electrolytes characterised by additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates to a non-aqueous electrolyte for an electricity storage device and an electricity storage device.
  • Electricity storage devices such as lithium primary batteries, lithium ion secondary batteries, and lithium secondary batteries (sometimes called lithium metal secondary batteries) are increasingly being used outdoors. Therefore, power storage devices are required to maintain stable characteristics even when exposed to various environments such as high-temperature environments or extremely low-temperature environments such as sub-zero temperatures.
  • Patent Document 1 discloses a non-aqueous organic electrolyte solution for a lithium primary battery using manganese dioxide as a positive electrode active material and lithium metal or a lithium alloy as a negative electrode active material, which is added to a basic electrolyte solution comprising an organic solvent and a supporting salt.
  • a non-aqueous organic electrolyte for lithium primary batteries to which an organic compound belonging to dicarboxylic acid esters having a chain structure is added as an agent.
  • Patent Document 2 discloses a non-aqueous electrolytic solution in which a lithium salt is dissolved in a non-aqueous organic solvent, and the non-aqueous electrolytic solution contains a chain carboxylic acid ester in an amount of 5 to 70% by mass with respect to the weight of the non-aqueous electrolytic solution. and a non-aqueous electrolytic solution containing a compound having two or more isocyanate groups.
  • Patent Document 3 discloses a non-aqueous electrolytic solution in which a lithium salt is dissolved in a non-aqueous organic solvent, wherein the non-aqueous electrolytic solution contains at least one chain-like compound selected from a group of compounds represented by a specific formula.
  • the output voltage may drop in a low-temperature environment.
  • the equipment equipped with the power storage device may not operate properly.
  • a first aspect of the present disclosure is a solute; a non-aqueous solvent; an isocyanate component;
  • the present invention relates to a non-aqueous electrolyte used in an electricity storage device, containing a phenolic component.
  • a second aspect of the present disclosure includes a pair of electrodes and a non-aqueous electrolyte,
  • the non-aqueous electrolyte is a solute; a non-aqueous solvent; an isocyanate component; and a phenolic component.
  • FIG. 1 is a front view of a partial cross-section of an electricity storage device according to an embodiment of the present disclosure
  • the output of an electricity storage device is greatly affected by the progress of the battery reaction at the interface between the electrode and the non-aqueous electrolyte.
  • the diffusibility of ions in the non-aqueous electrolyte decreases, and the battery reaction at the interface between the electrode and the non-aqueous electrolyte becomes difficult to proceed. Therefore, in a low-temperature environment, the output characteristics of the electricity storage device are degraded, and the drop in output voltage tends to be significant. If the drop in output voltage is large, it may not be possible to secure a sufficient voltage to operate the device in which the power storage device is mounted.
  • Electricity storage devices include, for example, batteries and capacitors that utilize non-aqueous electrolytes.
  • Electricity storage devices include, for example, non-aqueous electrolyte batteries and capacitors that use lithium ions as charge carriers (also referred to as carrier ions).
  • Examples of such power storage devices include lithium primary batteries, lithium ion secondary batteries, lithium secondary batteries, and lithium ion capacitors.
  • a smart meter for example, is an example of a device that is prevalent in ICT.
  • a smart meter is a device that transmits data such as gas or electricity usage. Devices used for such applications are required to continue to operate maintenance-free for a long period of time. For example, lithium primary batteries are suitable for long-term use due to their high energy density and low self-discharge.
  • the equipment used for the above purposes is often used outdoors and exposed to various environments such as high and low temperature environments. Therefore, power storage devices such as lithium primary batteries mounted in such equipment are required to have a stable output voltage even when exposed to harsh environments such as high or low temperatures.
  • the high reactivity of the isocyanate group acts on the electrode surface to form a film derived from the isocyanate component. Since the electrode surface is protected by the film, side reactions between the electrode and the non-aqueous solvent are likely to be suppressed, but the resistance increases. The increase in resistance is believed to be due to the rapid growth of the coating, which forms a thick coating on the electrode during or even in the early stages after assembly of the battery. Since such a coating inhibits the charge-discharge reaction, the effect of improving the output in a low-temperature environment is limited.
  • the non-aqueous electrolyte according to the first aspect of the present disclosure includes a solute, a non-aqueous solvent, an isocyanate component, and a phenol component. Such non-aqueous electrolytes are used in power storage devices.
  • the present disclosure also includes (2) an electricity storage device including a pair of electrodes and a non-aqueous electrolyte.
  • the non-aqueous electrolyte contains a solute, a non-aqueous solvent, an isocyanate component, and a phenol component.
  • the reaction between the isocyanate component and the phenol component can be used to suppress rapid film formation on the electrode surface.
  • a film with excellent film quality derived from both the isocyanate component and the phenol component is appropriately formed, so that the resistance of the film can be kept low while ensuring the effect of protecting the surface of the electrode.
  • high ionic conductivity can be ensured.
  • Phenolic hydroxy groups correspond to tertiary alcohols and are less reactive towards isocyanate groups than primary or secondary alcohols due to steric hindrance of the aromatic ring. Therefore, the reaction between the phenol component and the isocyanate component proceeds relatively gently. Therefore, it is considered that by using a phenol component, it is possible to form a protective film having excellent film quality while ensuring a certain degree of reactivity of the isocyanate group on the electrode.
  • the non-aqueous electrolyte solution B1 that does not contain either an isocyanate component or a phenol component
  • the non-aqueous electrolyte solution B2 that contains an isocyanate component and does not contain a phenol component is used.
  • the output voltage is improved in low temperature environments, the effect is negligible.
  • the film-forming ability of the phenol component on the electrode is low.
  • the output voltage in a low temperature environment is lower than that in the case. In other words, it can be said that the phenol component itself has no effect of improving the output voltage in a low temperature environment.
  • the combination of the isocyanate component and the phenol component will hardly have the effect of increasing the output voltage in a low temperature environment.
  • the output voltage is greatly improved in a low temperature environment. This is believed to be due to the moderate interaction between the isocyanate component and the phenol component, which forms a protective film of excellent film quality on the electrode surface derived from both components, synergistically increasing the output voltage.
  • the concentration of the phenol component in the non-aqueous electrolyte may be 10 ppm or less on a mass basis.
  • the concentration of the isocyanate component in the non-aqueous electrolytic solution may be 10% by mass or less.
  • the isocyanate component may include an isocyanate compound having two or more isocyanate groups.
  • the isocyanate component may include an isocyanate compound containing a ring structure.
  • the phenol component comprises an aromatic ring, at least one phenolic hydroxy group directly bonded to the aromatic ring, and directly bonded to the aromatic ring. and at least one selected from the group consisting of a hydrocarbon group and an alkoxy group.
  • the phenol compound may have at least an alkyl group as the hydrocarbon group.
  • the solute may include a lithium salt.
  • the power storage device may be a lithium primary battery including a pair of electrodes.
  • One electrode of the pair of electrodes may contain at least one of metallic lithium and a lithium alloy, and the other electrode may contain a positive electrode mixture containing manganese dioxide.
  • non-aqueous electrolytic solution and the electricity storage device of the present disclosure including the above (1) to (11), will be more specifically described below.
  • At least one of the above (1) to (11) may be combined with at least one of the elements described below within a technically consistent range.
  • the isocyanate component includes an isocyanate compound having an isocyanate group.
  • a compound that dissolves in a non-aqueous solvent is usually used as the isocyanate compound.
  • the isocyanate compound may be an isocyanate compound having one isocyanate group (sometimes referred to as a monoisocyanate compound), and an isocyanate compound having two or more isocyanate groups (sometimes referred to as a polyisocyanate compound). . Some of the isocyanate groups of the polyisocyanate compound react with the phenol component, and the remaining isocyanate groups act on the electrode, thereby easily forming a protective film derived from the isocyanate component and the phenol component on the electrode surface. Therefore, the isocyanate component preferably contains at least a polyisocyanate compound. A polyisocyanate compound and a monoisocyanate compound may be used in combination.
  • the upper limit of the number of isocyanate groups in the polyisocyanate compound is, for example, 5 or less, and may be 4 or less or 3 or less.
  • the isocyanate component may contain at least one selected from the group consisting of a diisocyanate compound having two isocyanate groups and a triisocyanate compound having three isocyanate groups (particularly a diisocyanate compound). According to the present disclosure, even if the concentration of the phenol component in the non-aqueous electrolyte is extremely low, the output voltage can be improved in a low-temperature environment.
  • the use of at least one diisocyanate compound and triisocyanate compound makes it easier to balance the reaction with the phenolic component and the action on the electrode, making it easier to form a protective coating with excellent film quality.
  • the ratio of the diisocyanate compound to the isocyanate component may be, for example, 50% by mass or more, 75% by mass or more, or 90% by mass or more.
  • the ratio of the diisocyanate compound to the isocyanate component is 100% by mass or less.
  • the isocyanate compound may be linear or may contain a ring structure.
  • the chain isocyanate compound may be linear or branched.
  • the ring structure may be a hydrocarbon ring or a heterocyclic ring.
  • the ring structure may be an aromatic ring or a non-aromatic ring.
  • the aromatic ring is, for example, 6-membered or more and 20-membered or less, or may be 6-membered or more and 10-membered or less.
  • multiple aromatic rings such as biphenyl, bisphenylalkane, and bisphenyl ether are linked by a single bond or a first linking group (alkylene group (including alkylidene group), ether bond (—O—), etc.).
  • structures also referred to as bisarene structures
  • the ring structure containing an aromatic ring also includes a ring structure having an aromatic ring and a non-aromatic ring condensed to this aromatic ring.
  • Non-aromatic rings include aliphatic hydrocarbon rings, non-aromatic heterocycles, and the like.
  • the non-aromatic ring may be a bridged ring.
  • Aliphatic hydrocarbon rings also include ring structures corresponding to hydrogenated bisarene structures.
  • An isocyanate compound containing an aromatic or aliphatic hydrocarbon ring, a chain isocyanate compound, or the like may be used from the standpoint of being relatively inexpensive and readily available and unlikely to cause side reactions.
  • the isocyanate group may be directly bonded to the ring or may be bonded to the ring via the second linking group.
  • the second linking group include alkylene groups (including alkylidene groups), oxydialkylene groups, —NH—R— groups (where R is an alkylene group), and the like. In -NH-R- groups, the isocyanate group is attached to R.
  • Each alkylene group constituting the alkylene of the first linking group and the second linking group, the oxydialkylene group of the second linking group, and the alkylene group represented by R each have, for example, 1 to 12 carbon atoms. , 1-10 or 1-6.
  • a heterocyclic ring is a ring containing a heteroatom (eg, at least one selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom) as a ring-constituting atom.
  • Heterocycles can be either aromatic or non-aromatic.
  • Aromatic isocyanate compounds tend to increase the film formation rate because the reactivity of the isocyanate group increases due to the resonance structure of the aromatic ring. Therefore, the isocyanate component preferably contains at least one selected from the group consisting of linear isocyanate compounds (such as aliphatic isocyanate compounds) and isocyanate compounds having an aliphatic ring (such as an aliphatic hydrocarbon ring).
  • linear isocyanate compounds such as aliphatic isocyanate compounds
  • isocyanate compounds having an aliphatic ring such as an aliphatic hydrocarbon ring
  • the isocyanate component contains at least an isocyanate compound containing a ring structure.
  • the isocyanate component may include an isocyanate compound containing a ring structure and a chain isocyanate compound.
  • the isocyanate compound containing a ring structure as described above, at least one selected from isocyanate compounds having an aliphatic ring (such as an aliphatic hydrocarbon ring) is preferable.
  • the ratio of the isocyanate compound containing a ring structure (e.g., an aliphatic ring such as an aliphatic hydrocarbon ring) to the isocyanate component may be 30% by mass or more, or 50% by mass or more, or 70% by mass or more. good too.
  • the ratio of the isocyanate compound containing a ring structure (for example, an aliphatic ring such as an aliphatic hydrocarbon ring) to the isocyanate component is 100% by mass or less.
  • the isocyanate compound also includes an isocyanate compound having a substituent.
  • the isocyanate compound may have a substituent on its main chain, a side chain, or a ring structure.
  • Each of the alkyl group and the alkoxy group may have 1 to 6 carbon atoms, 1 to 4 carbon atoms, or 1 or 2 carbon atoms.
  • the alkoxycarbonyl group may have 2 to 7 carbon atoms, 2 to 5 carbon atoms, or 2 to 4 carbon atoms.
  • the isocyanate compound may have one substituent or may have two or more substituents. When the isocyanate compound has two or more substituents, at least two substituents may be the same or all may be different.
  • monoisocyanate compounds examples include linear monoisocyanate compounds (alkyl isocyanate, alkoxycarbonyl isocyanate, etc.), monoisocyanate compounds containing aliphatic hydrocarbon rings (cyclohexyl isocyanate, cyclohexylmethyl isocyanate, etc.), aromatic hydrocarbon rings, etc. Monoisocyanate compounds containing (phenyl isocyanate, fluorophenyl isocyanate, benzyl isocyanate, etc.).
  • Alkyl isocyanates include alkyl isocyanates having 1 to 10 carbon atoms (e.g., methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, pentyl isocyanate, hexyl isocyanate, heptyl isocyanate, octyl isocyanate) and heterocycles. monoisocyanate compounds and the like.
  • alkoxycarbonyl isocyanate include alkoxycarbonyl isocyanates having 2 to 10 (eg, 2 to 6) carbon atoms (eg, methoxycarbonyl isocyanate).
  • diisocyanate compounds include chain diisocyanate compounds (e.g., alkylene diisocyanate, alkylene diisocyanate having an alkoxycarbonyl group (lysine diisocyanate, etc.)), diisocyanate compounds containing aliphatic hydrocarbon rings, diisocyanate compounds containing aromatic hydrocarbon rings, and the like. mentioned.
  • alkylene diisocyanate examples include alkylene diisocyanates having 2 to 12 (preferably 4 to 10) carbon atoms (eg, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, peptamethylene diisocyanate, octamethylene diisocyanate, 2, 2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate) and the like.
  • alkylene diisocyanates having 2 to 12 (preferably 4 to 10) carbon atoms eg, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, peptamethylene diisocyanate, octamethylene diisocyanate, 2, 2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate
  • Diisocyanate compounds containing an aliphatic hydrocarbon ring include isophorone diisocyanate, bisisocyanatoalkylcyclohexane [for example, 1,2-bis(isocyanatomethyl)cyclohexane, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4 -bis(isocyanatomethyl)cyclohexane, 1,2-bis(isocyanatoethyl)cyclohexane, 1,3-bis(isocyanatoethyl)cyclohexane, 1,4-bis(isocyanatoethyl)cyclohexane], dicyclohexylmethane-4 ,4′-diisocyanate, bicyclo[2.2.1]heptane-2,5-diylbis(methylisocyanate), bicyclo[2.2.1]heptane-2,6-diylbis(methylisocyanate) and the like.
  • Diisocyanate compounds containing aromatic hydrocarbon rings include diisocyanavantne [e.g., phenylene diisocyanate, toluene diisocyanate (2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, etc.), diisocyanatonaphthalene], di isocyanatoalkylarene (eg, xylylene diisocyanate), isocyanatobisarene [eg, bis(4-isocyanatophenyl)methane, 4,4'-diisocyanato-3,3'-dimethylbiphenyl], and the like.
  • diisocyanavantne e.g., phenylene diisocyanate, toluene diisocyanate (2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, etc.
  • diisocyanatonaphthalene di isocyanatoalkylaren
  • triisocyanate compounds examples include chain triisocyanate compounds (1,6,11-triisocyanatoundecane, lysine triisocyanate, tris(isocyanatohexyl) biuret, etc.), triisocyanate compounds containing aliphatic hydrocarbon rings, non-aromatic and triisocyanate compounds containing a heterocyclic ring.
  • triisocyanate compounds containing non-aromatic heterocycles include triisocyanate compounds having a skeleton derived from isocyanuric acid (compounds in which an isocyanatoalkyl group is bonded to the nitrogen atom of isocyanuric acid, etc.).
  • the alkyl group of the isocyanatoalkyl group corresponds to the alkylene group of the second linking group.
  • specific examples of such compounds include 1,3,5-tris(6-isocyanatohex-1-yl)-1,3,5-triazine-2,4,6(1H,3H,5H)- trione, 1,3,5-tris(6-isocyanatotetr-1-yl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5- Tris(6-isocyanatopent-1-yl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-tris(6-isocyanatotetra- 1-yl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-tris(6-isocyanatohept-1-yl)-1
  • the isocyanate component may contain one or more isocyanate compounds.
  • the concentration of the isocyanate component in the non-aqueous electrolyte is, for example, 15% by mass or less, and may be 12% by mass or less.
  • the concentration of the isocyanate component is preferably 11% by mass or less or 10% by mass or less from the viewpoint of easily ensuring a higher output voltage in a low-temperature environment.
  • concentration of the isocyanate component in the non-aqueous electrolyte may be 0.1% by mass or more, or 0.2% by mass or more.
  • the concentration of the isocyanate component in the non-aqueous electrolyte is preferably 0.5% by mass or more or 1% by mass or more, and 2% by mass or more or 3% by mass. % or more. These upper and lower limits can be combined arbitrarily.
  • the concentration of the isocyanate component in the non-aqueous electrolyte may be 0.1% by mass or more (or 0.2% by mass or more) and 15% by mass or less, or 0.5% by mass or more and 11% by mass or less ( or 10% by mass or less), or 2% by mass or more and 11% by mass or less (or 10% by mass or less).
  • the concentration of such an isocyanate component is the value (in other words, the initial value) in the non-aqueous electrolyte used for assembling the electricity storage device.
  • the isocyanate component concentration required for the non-aqueous electrolyte sampled from the electricity storage device may be within the above range.
  • the isocyanate component is consumed for film formation, so the concentration of the isocyanate component in the non-aqueous electrolytic solution changes, for example, during storage or use. Therefore, when analyzing the non-aqueous electrolyte sampled from the electricity storage device, it is sufficient that the isocyanate component remains in the non-aqueous electrolyte at a concentration equal to or higher than the detection limit. Therefore, the upper limit of the concentration of the isocyanate component is within the above range, and the lower limit may be equal to or higher than the detection limit.
  • GC-MS gas chromatography-mass spectrometry
  • Phenolic components include phenolic compounds containing an aromatic ring and at least one phenolic hydroxy group directly attached to the aromatic ring (in other words, aromatic hydroxy compounds).
  • aromatic hydroxy compounds a compound that dissolves in a non-aqueous solvent is usually used.
  • the aromatic ring may be an aromatic heterocyclic ring, but is preferably an aromatic hydrocarbon ring.
  • Aromatic hydrocarbon rings include arene rings, bisarene rings and the like.
  • the arene ring includes, for example, arene rings having 6 to 20 carbon atoms (benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, etc.).
  • the bisarene ring includes, for example, a ring structure in which the above arene rings (among them, benzene ring, naphthalene ring, etc.) are bonded via a single bond or a third linking group.
  • the third linking group is selected, for example, from the groups exemplified for the second linking group.
  • An aromatic ring also includes a condensed ring of an aromatic ring and a non-aromatic ring (alicyclic hydrocarbon ring, hetero ring, etc.).
  • the phenol component preferably contains a phenol compound having a benzene ring as an aromatic ring.
  • the phenol component preferably contains phenol or a derivative thereof (such as phenol having a substituent) as the phenol compound.
  • the phenolic compound may have one phenolic hydroxy group, or may have two or more.
  • the number of phenolic hydroxy groups may be 4 or less, or 3 or less, depending on the number of members of the aromatic ring.
  • the phenolic component may include phenolic compounds having one or two phenolic hydroxy groups.
  • the phenol compound may have a substituent directly bonded to the aromatic ring.
  • substituents include hydrocarbon groups, alkoxy groups, alkoxycarbonyl groups, and the like.
  • hydrocarbon group an aliphatic hydrocarbon group having no ethylenically unsaturated bond (such as an alkyl group or a cycloalkyl group), an aralkyl group such as a phenylalkyl group, and the like are preferable.
  • the number of carbon atoms in each of the alkyl group and the alkoxy group is, for example, 1-10, and may be 1-6 or 1-5.
  • the number of carbon atoms in the alkoxycarbonyl group is, for example, 2-12, and may be 2-7.
  • the number of carbon atoms in the cycloalkyl group is, for example, 5-10, and may be 5-8.
  • alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, neopentyl group, sec-pentyl group and 3-pentyl group. , tert-pentyl groups.
  • alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and tert-butoxy groups.
  • alkoxycarbonyl groups include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl and butoxycarbonyl groups.
  • the aralkyl group includes a phenylalkyl group having 1 to 4 carbon atoms (benzyl group, phenethyl group, ⁇ -methylbenzyl group, ⁇ , ⁇ -dimethylbenzyl group, etc.).
  • the phenolic component is a phenolic compound having an aromatic ring, at least one phenolic hydroxy group directly bonded to the aromatic ring, and at least one selected from the group consisting of a hydrocarbon group and an alkoxy group directly bonded to the aromatic ring. preferably included.
  • the phenol component contains such a phenol compound, moderate reactivity with the isocyanate component is likely to be obtained, and a protective film having excellent film quality is likely to be formed on the electrode surface.
  • the ratio of such phenol compounds in the phenol component is, for example, 50% by mass or more, and may be 75% by mass or more.
  • the ratio of the above phenol compounds shown in the phenol component is 100% by mass or less.
  • the above phenol compound preferably has at least an alkyl group as the hydrocarbon group.
  • the phenol compound may have, for example, a hindered alkyl group, a hindered group such as a phenylalkyl group in which alkyl is branched alkyl, and the like.
  • hindered alkyl groups include hindered alkyl groups having 4 to 10 or 4 to 6 carbon atoms (tert-butyl group, tert-pentyl group, etc.).
  • phenylalkyl groups include phenylalkyl groups in which alkyl is a branched alkyl group having 2 to 4 carbon atoms ( ⁇ -methylbenzyl group, ⁇ , ⁇ -dimethylbenzyl group, etc.).
  • the phenol compound may have a hindered group and other substituents (for example, at least one selected from the group consisting of linear alkyl groups and alkoxy groups).
  • a preferable phenol compound is represented, for example, by the following formula (1).
  • R 1 to R 5 are each independently a hydrogen atom, a hydroxy group, or a substituent.
  • the substituents in formula (1) correspond to the substituents described above. At least two of R 1 to R 5 may be the same, or all may be different. At least one of R 1 to R 5 is preferably a substituent (such as a substituent selected from the group consisting of alkyl groups and alkoxy groups). Among them, at least one of R 1 to R 5 is preferably a hindered alkyl group. At least one of the remaining four of R 1 to R 5 may be at least one selected from the group consisting of linear alkyl groups and alkoxy groups.
  • the number of carbon atoms in the linear alkyl group can be selected from the range of carbon numbers described for the alkyl group of the substituent, preferably 1 to 4, and may be 1 to 3.
  • a linear alkyl group may be at least one of a methyl group and an ethyl group.
  • the number of carbon atoms in the alkoxy group can be selected from the range of carbon numbers described for the alkoxy group of the substituent, preferably 1 to 4, and may be 1 to 3.
  • An alkoxy group may be at least one of a methoxy group and an ethoxy group.
  • the number of hydroxy groups is, for example, 1 to 4, may be 1 to 3, or may be 1 or 2.
  • phenolic compounds include, for example, monophenolic compounds having one phenolic hydroxy group [eg, dibutylhydroxytoluene (also referred to as 2,6-di-tert-butyl-p-cresol), butylhydroxyanisole (2-tert-butyl-4-methoxyphenol, 3-tert-butyl-4-methoxyphenol, or mixtures thereof), mono-, di- or tri-( ⁇ -methylbenzyl)phenol, sesamol, etc.], two or more Examples include phenol compounds having a phenolic hydroxy group (bisphenol compounds, polyphenol compounds having a plurality of hydroxy groups in one aromatic ring, etc.).
  • phenolic hydroxy group eg, dibutylhydroxytoluene (also referred to as 2,6-di-tert-butyl-p-cresol), butylhydroxyanisole (2-tert-butyl-4-methoxyphenol, 3-tert-butyl-4-methoxyphenol, or mixtures thereof), mono
  • Bisphenol compounds include 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol) and the like.
  • Polyphenol compounds include hydroquinone, resorcinol, catechol, pyrogallol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, propyl gallate and the like.
  • the phenol component may contain one type of phenol compound, or two or more types.
  • the phenol component preferably contains at least a monophenol compound from the viewpoints of easily obtaining an appropriate reactivity with the isocyanate component and easily forming a protective film having excellent film quality on the electrode surface.
  • a monophenol compound is specifically a monophenol compound in which the aromatic ring is a benzene ring.
  • Monophenolic compounds are preferred.
  • the ratio of the monophenol compound in the phenol component is, for example, 30% by mass or more, may be 50% by mass or more, or may be 75% by mass or more.
  • the proportion of monophenol compounds in the phenol component is 100% by mass or less.
  • the phenol component acts on the isocyanate component even when it is contained at a very low concentration in the non-aqueous electrolyte, forming a protective film with excellent film quality on the electrode surface.
  • the concentration of the phenol component in the non-aqueous electrolyte is, for example, 200 ppm or less, and may be 150 ppm or less on a mass basis. From the viewpoint of easily ensuring a higher output voltage in a low-temperature environment, the concentration of the phenol component is preferably 30 ppm or less or 20 ppm or less, more preferably 10 ppm or less, and may be 8 ppm or less on a mass basis.
  • concentration of the phenol component When the concentration of the phenol component is within such a range, it is easy to ensure a higher output voltage in a low temperature environment after high temperature storage.
  • concentration of the phenol component in the non-aqueous electrolyte may be 0.001 ppm or more, or may be 0.01 ppm or more on a mass basis. These upper and lower limits can be combined arbitrarily.
  • the concentration of the phenol component in the non-aqueous electrolyte is, on a mass basis, 0.001 ppm or more and 200 ppm or less (or 150 ppm or less), 0.001 ppm or more and 10 ppm or less (or 8 ppm or less), or 0.01 ppm or more and 10 ppm or less ( or 8 ppm or less).
  • the concentration of such a phenol component is the value (in other words, the initial value) in the non-aqueous electrolyte used for assembling the electricity storage device.
  • the concentration of the phenol component required for the non-aqueous electrolyte collected from the electricity storage device may be within the above range.
  • the phenol component is consumed together with the isocyanate component for film formation, so the concentration of the phenol component in the non-aqueous electrolyte changes, for example, during storage or by use. Therefore, when analyzing the non-aqueous electrolyte sampled from the electricity storage device, it is sufficient that the phenol component remains in the non-aqueous electrolyte at a concentration equal to or higher than the detection limit. Therefore, the upper limit of the concentration of the phenol component is within the above range, and the lower limit may be equal to or higher than the detection limit.
  • the mass ratio of the phenol component to the isocyanate component is 2 ⁇ 10 ⁇ 3 or less, and may be 1.5 ⁇ 10 ⁇ 3 or less. From the viewpoint of easily ensuring a higher output voltage in a low temperature environment, the mass ratio of the phenol component / isocyanate component is preferably 1 ⁇ 10 -3 or less, 0.7 ⁇ 10 -3 or less or 0.5 ⁇ 10 -3 or less is more preferable.
  • the mass ratio of phenol component/isocyanate component may be 0.3 ⁇ 10 ⁇ 3 or less. In this case, it is easy to ensure a higher output voltage in a low temperature environment after high temperature storage.
  • the mass ratio of phenol component/isocyanate component may be, for example, 0.001 ⁇ 10 ⁇ 3 or more, or may be 0.002 ⁇ 10 ⁇ 3 or more. These upper and lower limits can be combined arbitrarily.
  • the mass ratio of the phenol component/isocyanate component is, for example, 0.001 ⁇ 10 ⁇ 3 or more and 2 ⁇ 10 ⁇ 3 or less (or 1.5 ⁇ 10 ⁇ 3 or less), 0.001 ⁇ 10 ⁇ 3 or more and 1 ⁇ 10 ⁇ 3 or less (or 0.5 ⁇ 10 ⁇ 3 or less), or 0.001 ⁇ 10 ⁇ 3 or more and 0.3 ⁇ 10 ⁇ 3 or less.
  • Non-aqueous solvents include ethers, esters (such as carboxylic acid esters), carbonate esters, and the like. These may be chain compounds or cyclic compounds. Chain ethers include dimethyl ether and 1,2-dimethoxyethane (DME). Cyclic ethers include 1,3-dioxolane, 4-methyl-1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran and the like.
  • Chain carboxylic acid esters include formate (ethyl formate, etc.), acetate (methyl acetate, ethyl acetate, propyl acetate, etc.), propionate (methyl propionate, ethyl propionate, methyl fluoropropionate, etc.). mentioned. Cyclic carboxylic acid esters include ⁇ -butyrolactone and ⁇ -valerolactone. Chain carbonic acid esters include diethyl carbonate, ethylmethyl carbonate, dimethyl carbonate and the like. Cyclic carbonates include propylene carbonate (PC) and ethylene carbonate (EC). The non-aqueous electrolyte may contain one type of non-aqueous solvent, or may contain two or more types in combination.
  • the non-aqueous solvent preferably contains a cyclic carbonate having a high boiling point and a chain ether having a low viscosity at low temperatures.
  • the cyclic carbonate preferably contains at least one selected from the group consisting of PC and EC.
  • Chain ethers preferably include, for example, DME.
  • solutes examples include salts of cations (carrier ions) that serve as charge carriers in the non-aqueous electrolyte and anions that are counter ions of the cations.
  • solutes include salts of cations (carrier ions) that serve as charge carriers in the non-aqueous electrolyte and anions that are counter ions of the cations.
  • lithium salts are used as solutes in power storage devices (lithium primary batteries, lithium ion secondary batteries, lithium secondary batteries, lithium ion capacitors, etc.) in which lithium ions serve as carrier ions.
  • the solute of the non-aqueous electrolyte may contain a lithium salt.
  • lithium salts examples include LiClO 4 , LiBF 4 , LiPF 6 , LiR a SO 3 (LiCF 3 SO 3 etc.), LiFSO 3 , imide salts (LiN(SO 2 R b ) (SO 2 R c ), LiN ( FSO 2 ) 2, etc.), LiC(SO 2 R d )(SO 2 Re )(SO 2 R f ), LiPO 2 F 2 and oxalate complex salts.
  • R a to R f is a fluorinated alkyl group. The number of carbon atoms in the fluorinated alkyl group is, for example, 1-12, and may be 1-6 or 1-4.
  • R b and R c may be the same (eg LiN(CF 3 SO 2 ) 2 , LiN(C 2 F 5 SO 2 ) 2 ) or different (eg LiN(CF 3 SO 2 ) ( C4F9SO2 ) ) .
  • At least two of R d to R f may be the same, or all may be different.
  • Examples of oxalate complex salts include lithium bisoxalate borate (LiB(C 2 O 4 ) 2 ), LiBF 2 (C 2 O 4 ), LiPF 4 (C 2 O 4 ), LiPF 2 (C 2 O 4 ) 2 is mentioned.
  • Lithium salts include LiAlCl 4 , LiAlF 4 , LiAsF 6 , LiSbF 6 , LiTaF 6 , LiNbF 6 , LiSiF 6 , LiCH 3 BF 3 , LiCN, LiSCN, LiCF 3 CO 2 , LiB 10 Cl 10 , LiNO 3 , LiNO 2 , lithium lower aliphatic carboxylate, lithium halide (LiCl, etc.), borate (bis (1,2-benzenediolate (2-) -O, O') lithium borate, etc.) good.
  • the non-aqueous electrolyte may contain one type of lithium salt, or may contain two or more types in combination.
  • the lithium salt is selected according to, for example, the type of power storage device, components contained in the electrode, and the like.
  • the concentration of solutes (or carrier ions) contained in the non-aqueous electrolyte may be, for example, 0.1 mol/L or more and 3.5 mol/L or less.
  • the solute concentration is selected according to, for example, the type and capacity of the electric storage device.
  • the solute concentration may be within the above range, and may be 0.2 mol/L or more and 2.0 mol/L or less.
  • the non-aqueous electrolyte may contain additives other than the isocyanate component and the phenol component, if necessary.
  • Additives include propane sultone, propene sultone, ethylene sulfate, trimethylsilyl phosphite, trimethylsilyl phosphate, vinylene carbonate, fluoroethylene carbonate, vinylethylene carbonate, adiponitrile, succinonitrile and the like.
  • the total concentration of such additives contained in the non-aqueous electrolyte is, for example, 5 mol/L or less.
  • the total concentration of additives may be 0.003 mol/L or more.
  • alkanesulfonic anhydrides include, for example, alkanesulfonic anhydrides optionally having fluorine atoms and alkanedisulfonic anhydrides optionally having fluorine atoms.
  • the non-aqueous electrolyte may be a non-fluid gel electrolyte in which a gelling agent or matrix material and a non-aqueous electrolyte are combined, if necessary.
  • a power storage device includes a pair of electrodes and a non-aqueous electrolyte.
  • the non-aqueous electrolyte the above non-aqueous electrolyte is used.
  • configurations other than the non-aqueous electrolyte will be described in more detail below.
  • One of the pair of electrodes can electrochemically dissolve or release carrier ions (lithium ions, etc.), and the other can electrochemically deposit or occlude carrier ions (lithium ions, etc.).
  • carrier ions can be occluded also includes the case where carrier ions can be adsorbed.
  • each electrode is capable of electrochemically dissolving and depositing carrier ions, or electrochemically releasing and absorbing (or desorbing and adsorbing) carrier ions.
  • Each electrode may contain an active material having such a function.
  • the isocyanate component tends to form a film by acting on the active material or conductive agent contained in the electrode.
  • the electrode contains at least one selected from the group consisting of lithium (Li) element, silicon (Si) element, and carbonaceous materials
  • the isocyanate component contained in the non-aqueous electrolyte is Li element in the electrode, Si It acts on elements or carbonaceous materials to easily form a coating with excellent film quality derived from isocyanate components and phenol components.
  • the electrode contains an element of a polyvalent metal having an oxidation number of 2 or more (at least one selected from the group consisting of manganese (Mn), nickel (Ni) and cobalt (Co)), the isocyanate group is Acting on these elements contained in, it is easy to obtain a protective effect.
  • a polyvalent metal having an oxidation number of 2 or more at least one selected from the group consisting of manganese (Mn), nickel (Ni) and cobalt (Co)
  • an electricity storage device using an electrode containing at least one element selected from the group consisting of Li element, Si element, and a carbonaceous material; using an electrode containing at least one element selected from the group consisting of Mn, Ni and Co electricity storage device; or one electrode contains at least one selected from the group consisting of Li element, Si element and carbonaceous material, and the other electrode contains at least one selected from the group consisting of Mn, Ni and Co
  • an electricity storage device containing the element especially when the non-aqueous electrolyte is used, the effect of suppressing a decrease in output voltage in a low-temperature environment can be remarkably obtained.
  • Carbonaceous materials include, for example, graphite materials, carbon black, and activated carbon.
  • Electricity storage devices using such electrodes include lithium primary batteries, lithium ion secondary batteries, lithium secondary batteries, lithium ion capacitors, and the like.
  • the non-aqueous electrolyte of the present disclosure is particularly suitable for use in these power storage devices.
  • the negative electrode may contain only the current collector at the initial stage, but the isocyanate component acts on the metallic lithium deposited on the current collector during charging, resulting in the isocyanate component and the phenol component. A coating with excellent film quality is formed.
  • one electrode In the electricity storage device, one electrode may be, for example, a negative electrode.
  • the other electrode may be, for example, the positive electrode.
  • the configuration of each electrode is determined, for example, according to the type of power storage device.
  • the negative electrode may comprise metallic lithium or a lithium alloy, and may comprise both metallic lithium and lithium metal. Composites of metallic lithium and lithium alloys may also be used.
  • lithium alloys may contain elements such as aluminum, tin, silicon, magnesium, indium, lead, and zinc.
  • Lithium alloys include Li-Al alloys, Li-Sn alloys, Li-Ni-Si alloys, Li-Pb alloys, Li-Mg alloys, Li-Zn alloys, Li-In alloys, Li-Al-Mg alloys, and the like. mentioned.
  • the content of metal elements other than lithium contained in the lithium alloy may be 0.05% by mass or more and 15% by mass or less from the viewpoint of ensuring discharge capacity and stabilizing internal resistance.
  • Metallic lithium, lithium alloys, or composites thereof can be formed into any shape and thickness according to the shape, dimensions, standard performance, etc. of the lithium primary battery.
  • hoop-shaped metal lithium, lithium alloy, or the like may be punched out into a disk shape and used as the negative electrode.
  • a sheet of metal lithium, lithium alloy, or the like may be used for the negative electrode. Sheets are obtained, for example, by extrusion.
  • the negative electrode contains a negative electrode active material capable of intercalating and deintercalating lithium ions or dissolving or depositing lithium ions.
  • the negative electrode may include a negative electrode current collector that holds a negative electrode active material.
  • the negative electrode may include, for example, a negative electrode mixture containing a negative electrode active material and a negative electrode current collector holding the negative electrode mixture.
  • negative electrode active materials include lithium metal, lithium alloys, carbonaceous materials (graphite materials, soft carbon, hard carbon, amorphous carbon, etc.), Si-containing materials (si simple substance, Si alloys, and Si compounds (oxides, nitrides, carbides, etc.), Sn-containing materials (Sn simple substance, Sn alloys, Sn compounds, etc.).
  • the negative electrode may contain one type of negative electrode active material, or may contain two or more types. From the viewpoint of easy formation of a film with excellent film quality derived from the isocyanate component and the phenol component, the negative electrode active material containing at least one selected from the group consisting of the Li element, the Si element (such as a Si-containing material), and the carbonaceous material.
  • the negative electrode mixture contains binders (fluororesins, olefin resins, polyamide resins, polyimide resins, acrylic resins, rubber-like polymers, etc.), thickeners (carboxymethylcellulose or its salts, etc.), conductive Agents (carbon black, carbon fiber, etc.) and the like may also be included.
  • the negative electrode can be formed, for example, by applying a paste containing the negative electrode mixture material to the negative electrode current collector.
  • the negative electrode may be formed by depositing a negative electrode active material on a negative electrode current collector.
  • the negative electrode includes a current collector.
  • Current collectors include conductive sheets formed of conductive materials other than lithium metal and lithium alloys.
  • At least one of a negative electrode mixture layer and a layer containing lithium (also referred to as a base layer) may be formed on the surface of the current collector.
  • the negative electrode mixture layer is formed, for example, by applying a paste containing a negative electrode active material to at least part of the surface of the negative electrode current collector.
  • the underlayer is a layer that is provided in advance and contains metallic lithium or a lithium alloy.
  • the lithium alloy may contain, for example, at least one element selected from the group consisting of aluminum, magnesium, indium, and zinc. From the viewpoint of facilitating the formation of a film with excellent film quality derived from the isocyanate component and the phenol component, a negative electrode including an underlying layer containing lithium may be used.
  • the positive electrode contains a positive electrode mixture.
  • the positive electrode may include a positive electrode mixture and a positive electrode current collector that holds the positive electrode mixture.
  • the positive electrode mixture contains a positive electrode active material.
  • the positive electrode mixture may further contain a binder, a conductive agent, and the like.
  • the positive electrode active material includes, for example, manganese dioxide.
  • a positive electrode containing manganese dioxide as a positive electrode active material develops a relatively high voltage and has excellent pulse discharge characteristics.
  • Manganese dioxide may be in a mixed crystal state containing a plurality of crystal states.
  • the positive electrode may contain manganese oxides other than manganese dioxide.
  • Manganese oxides other than manganese dioxide include MnO, Mn 3 O 4 , Mn 2 O 3 and Mn 2 O 7 .
  • the main component (for example, 50% by mass or more) of manganese oxide contained in the positive electrode may be manganese dioxide.
  • Part of the manganese dioxide contained in the positive electrode may be doped with lithium. If the doping amount of lithium is small, a high capacity can be secured.
  • Manganese dioxide and manganese dioxide doped with a small amount of lithium can be represented by Li x MnO 2 (0 ⁇ x ⁇ 0.05).
  • Manganese dioxide also includes manganese oxides represented by such formulas.
  • the average composition of all manganese oxides contained in the positive electrode should be Li x MnO 2 (0 ⁇ x ⁇ 0.05).
  • the Li ratio x may be 0.05 or less in the initial discharge state of the lithium primary battery. The ratio x of Li increases as the discharge of the lithium primary battery progresses.
  • the oxidation number of manganese contained in manganese dioxide is theoretically 4 valence, the average oxidation number of manganese is allowed to slightly increase or decrease from 4 valence.
  • the positive electrode can contain other positive electrode active materials used in lithium primary batteries. Fluorinated graphite etc. are mentioned as another positive electrode active material. However, the proportion of manganese dioxide in the entire positive electrode active material is preferably 90% by mass or more.
  • binders examples include fluororesins, rubber particles, and acrylic resins.
  • Examples of conductive agents include conductive carbonaceous materials.
  • Examples of conductive carbonaceous materials include natural graphite, artificial graphite, carbon black, and carbon fiber.
  • Examples of materials for the positive electrode current collector include stainless steel, aluminum, and titanium.
  • the positive electrode may be configured by attaching a ring-shaped positive electrode current collector having an L-shaped cross section to the positive electrode mixture pellet, or the positive electrode may be configured only with the positive electrode mixture pellet.
  • the positive electrode mixture pellets are obtained, for example, by compressing and drying a wet positive electrode mixture prepared by adding an appropriate amount of water to a positive electrode active material and an additive.
  • a positive electrode comprising a sheet-like positive electrode current collector and a positive electrode mixture layer held by the positive electrode current collector can be used.
  • a metal foil may be used, or a perforated current collector may be used. Expanded metals, nets, punching metals and the like are examples of current collectors with pores.
  • the positive electrode mixture layer is obtained, for example, by coating the surface of a sheet-like positive electrode current collector with the positive electrode mixture in a wet state or filling the positive electrode current collector, applying pressure in the thickness direction, and drying. .
  • a composite oxide containing lithium and a transition metal can be used as a positive electrode active material.
  • transition metals include Ni, Co, and Mn.
  • the composite oxide for example, Li a CoO 2 , Li a NiO 2 , Li a MnO 2 , Li a Co b1 Ni 1-b1 O 2 , Li a Co b1 M 1-b1 O c1 , Li a Ni 1- b1 M b1 O c1 , Li a Mn 2 O 4 , and Li a Mn 2-b1 M b1 O 4 .
  • a 0 to 1.2
  • b1 0 to 0.9
  • c1 2.0 to 2.3.
  • M is at least one selected from the group consisting of Na, Mg, Sc, Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Cr, Pb, Sb and B; Note that the value a, which indicates the molar ratio of lithium, increases or decreases due to charging and discharging.
  • Li a Ni b2 M 1-b2 O 2 (0 ⁇ a ⁇ 1.2, 0.3 ⁇ b2 ⁇ 1, M is at least selected from the group consisting of Mn, Co and Al 1 type.) may be used.
  • 1 type of positive electrode active materials may be included, and 2 or more types may be included.
  • a positive electrode containing a positive electrode active material containing a polyvalent metal (among them, at least one selected from the group consisting of Mn, Ni, and Co) may be used.
  • positive electrode active materials include, for example, lithium-containing transition metal oxides, transition metal fluorides, polyanions, fluorinated polyanions, and transition metal sulfides.
  • the transition metal element contained in the lithium-containing transition metal oxide is, for example, at least one selected from the group consisting of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, and W. is mentioned. From the viewpoint of facilitating the formation of a film with excellent film quality derived from the isocyanate component and the phenol component, the lithium-containing transition metal oxide contains at least one selected from the group consisting of Mn, Ni, and Co as a transition metal element. It's okay.
  • Lithium-containing transition metal oxides are typical metals (e.g., at least one selected from the group consisting of Mg, Al, Ca, Zn, Ga, Ge, Sn, Sb, Pb, Bi, etc. (especially at least Al)) may include
  • the positive electrode contains, for example, a carbonaceous material that is an active material as an essential component, and may contain a binder, a conductive agent, etc. as optional components.
  • carbonaceous materials include activated carbon, carbon nanotubes, graphite, and graphene.
  • binders and conductive agents used in positive electrodes of lithium ion secondary batteries, lithium secondary batteries, and lithium ion capacitors include the components exemplified for lithium primary batteries.
  • the positive electrode is produced in the same manner as in the case of the lithium primary battery.
  • the positive electrode is produced by applying a paste or slurry containing the components of the positive electrode mixture to the surface of the positive electrode current collector, and drying and compressing the coating film.
  • the electricity storage device may include a separator interposed between the pair of electrodes.
  • separators include nonwoven fabrics, microporous membranes, and laminates thereof.
  • the thickness of the separator is, for example, 5 ⁇ m or more and 100 ⁇ m or less.
  • Non-woven fabrics are composed of fibers containing, for example, polypropylene, polyphenylene sulfide, polybutylene terephthalate, and the like.
  • Microporous membranes include, for example, polyolefin resins such as polyethylene, polypropylene, and ethylene-propylene copolymers.
  • the structure of the electricity storage device is not particularly limited.
  • the structure may be selected according to the type of electricity storage device.
  • the electricity storage device may be coin-shaped, which is configured by laminating a disk-shaped positive electrode and a disk-shaped negative electrode with a separator interposed therebetween.
  • the electricity storage device may be cylindrical and includes an electrode group formed by spirally winding a strip-shaped positive electrode and a strip-shaped negative electrode with a separator interposed therebetween.
  • FIG. 1 shows a front view of a partial cross section of a cylindrical electricity storage device according to one embodiment.
  • an electrode group in which a positive electrode 1 and a negative electrode 2 are wound with a separator 3 interposed therebetween is housed in a battery case 9 together with a non-aqueous electrolyte (not shown).
  • a sealing plate 8 is attached to the opening of the battery case 9 .
  • a positive electrode lead 4 connected to the current collector 1 a of the positive electrode 1 is connected to the sealing plate 8 .
  • a negative electrode lead 5 connected to the negative electrode 2 is connected to a battery case 9 .
  • An upper insulating plate 6 and a lower insulating plate 7 are arranged above and below the electrode group, respectively.
  • Examples 1 to 10 and Comparative Examples 1 to 3>> A lithium primary battery as an electricity storage device was produced by the following procedure.
  • the positive electrode mixture was filled into a positive electrode current collector made of expanded metal with a thickness of 0.1 mm made of stainless steel (SUS444) to prepare a positive electrode precursor.
  • the positive electrode precursor was dried, rolled by a roll press until the thickness became 0.4 mm, and cut into a sheet having a length of 3.5 cm and a width of 20 cm to obtain a positive electrode.
  • part of the filled positive electrode mixture was peeled off, and a lead made of SUS444 was resistance-welded to the exposed portion of the positive electrode current collector.
  • a negative electrode was obtained by cutting a metallic lithium foil having a thickness of 300 ⁇ m into a size of 3.7 cm long and 22 cm wide. A lead made of nickel was connected to a predetermined portion of the negative electrode by welding.
  • An electrode group was produced by winding the positive electrode and the negative electrode so that they faced each other with the separator interposed therebetween.
  • a polypropylene microporous film having a thickness of 25 ⁇ m was used as the separator.
  • the electrode group was accommodated in a cylindrical battery case that also served as a negative electrode terminal.
  • An iron case (outer diameter 17 mm, height 45.5 mm) was used as the battery case.
  • the opening of the battery case was closed using a metal sealing member that also served as a positive electrode terminal.
  • the other end of the positive electrode lead was connected to the sealing body, and the other end of the negative electrode lead was connected to the inner bottom surface of the battery case.
  • a power storage device (lithium primary battery) for testing was produced.
  • the design capacity of the lithium primary battery is 2000mAh.
  • the electricity storage device immediately after assembly was stored at 70°C for 120 days.
  • the battery voltage (open circuit voltage) V after pulse discharge was measured under a low temperature environment in the same manner as in the case of the initial output voltage. This voltage was taken as the output voltage under the low temperature environment after high temperature storage.
  • the output voltage of each electricity storage device was expressed as a relative value when the initial output voltage of the electricity storage device of Comparative Example 1 was set to 100.
  • E1-E10 are the batteries of Examples 1-10
  • C1-C3 are the batteries of Comparative Examples 1-3.
  • C2 using an isocyanate component has an initial output voltage of 1 in a low temperature environment. .7% increase.
  • the initial output voltage in a low temperature environment is reduced by 4.6% compared to C1. In other words, the effect of increasing the output voltage in a low-temperature environment cannot be obtained with only the phenol component, and the output voltage is greatly reduced.
  • the initial output voltage in a low temperature environment is 103.6% (E1), which is improved compared to C1.
  • E1 the initial output voltage in a low temperature environment
  • the output voltage in a low-temperature environment after high-temperature storage shows the same tendency as the initial output voltage.
  • E1 is actually 99.3%, an increase of 9.2% compared to C1, and an increase of 14.3% compared to the expected value.
  • Such excellent effects are believed to be due to the interaction between the isocyanate component and the phenol component, which produces a synergistic effect that cannot be obtained when they are used alone.
  • the mass ratio of the phenol component/isocyanate component in the non-aqueous electrolyte is preferably 1 ⁇ 10 ⁇ 3 or less, and 0.7 ⁇ 10 ⁇ 3 or less or 0.5 ⁇ 10 ⁇ 3 or less is more preferable, and 0.3 ⁇ 10 ⁇ 3 or less is even more preferable (comparison between E1 and E10).
  • the concentration of the phenol component in the non-aqueous electrolyte is preferably 30 ppm or less or 20 ppm or less, more preferably 10 ppm or less (comparison between E1 and E10).
  • the concentration of the isocyanate component in the non-aqueous electrolyte is preferably 10% by mass or less (comparison between E7 and E8).
  • isocyanate compounds containing ring structures tend to yield higher initial output voltages in low-temperature environments (E1 and E5 and E2, E3, and E6 and comparison with E7).
  • the non-aqueous electrolyte of the present disclosure is useful as a non-aqueous electrolyte for power storage devices.
  • An electricity storage device using the non-aqueous electrolyte of the present disclosure is suitably used as, for example, main power sources and memory backup power sources for various meters.
  • Examples of power storage devices include lithium primary batteries, lithium ion secondary batteries, lithium secondary batteries, and lithium ion capacitors.
  • the uses of the non-aqueous electrolyte and the electricity storage device are not limited to these.

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WO2025249625A1 (ko) * 2024-05-30 2025-12-04 삼성에스디아이 주식회사 리튬 이차 전지용 전해액 및 이를 포함하는 리튬 이차 전지

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003217652A (ja) * 2002-01-18 2003-07-31 Mitsubishi Chemicals Corp 非水系電解液及びそれを用いたリチウム二次電池
JP2003223931A (ja) * 2002-01-29 2003-08-08 Tomoegawa Paper Co Ltd ポリマー電解質基材、ポリマー電解質、ポリマー電解質シート及びそれを用いた電気化学素子
JP2013175369A (ja) * 2012-02-24 2013-09-05 Mitsubishi Chemicals Corp 非水系電解液及びそれを用いたリチウム二次電池
JP2014022191A (ja) * 2012-07-18 2014-02-03 Mitsubishi Chemicals Corp 非水系電解液及びそれを用いた非水系電解液電池
JP2021082556A (ja) * 2019-11-22 2021-05-27 三菱ケミカル株式会社 非水系電解液及びエネルギーデバイス

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003217652A (ja) * 2002-01-18 2003-07-31 Mitsubishi Chemicals Corp 非水系電解液及びそれを用いたリチウム二次電池
JP2003223931A (ja) * 2002-01-29 2003-08-08 Tomoegawa Paper Co Ltd ポリマー電解質基材、ポリマー電解質、ポリマー電解質シート及びそれを用いた電気化学素子
JP2013175369A (ja) * 2012-02-24 2013-09-05 Mitsubishi Chemicals Corp 非水系電解液及びそれを用いたリチウム二次電池
JP2014022191A (ja) * 2012-07-18 2014-02-03 Mitsubishi Chemicals Corp 非水系電解液及びそれを用いた非水系電解液電池
JP2021082556A (ja) * 2019-11-22 2021-05-27 三菱ケミカル株式会社 非水系電解液及びエネルギーデバイス

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025249625A1 (ko) * 2024-05-30 2025-12-04 삼성에스디아이 주식회사 리튬 이차 전지용 전해액 및 이를 포함하는 리튬 이차 전지

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