WO2018150567A1 - Solution électrolytique pour batterie secondaire au lithium-ion, et batterie secondaire au lithium-ion mettant en œuvre celle-ci - Google Patents

Solution électrolytique pour batterie secondaire au lithium-ion, et batterie secondaire au lithium-ion mettant en œuvre celle-ci Download PDF

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WO2018150567A1
WO2018150567A1 PCT/JP2017/006087 JP2017006087W WO2018150567A1 WO 2018150567 A1 WO2018150567 A1 WO 2018150567A1 JP 2017006087 W JP2017006087 W JP 2017006087W WO 2018150567 A1 WO2018150567 A1 WO 2018150567A1
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secondary battery
electrolyte
lithium ion
ion secondary
weight
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PCT/JP2017/006087
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English (en)
Japanese (ja)
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井上　和彦
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日本電気株式会社
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Priority to JP2019500148A priority Critical patent/JP6750723B2/ja
Priority to PCT/JP2017/006087 priority patent/WO2018150567A1/fr
Publication of WO2018150567A1 publication Critical patent/WO2018150567A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to an electrolyte for a lithium ion secondary battery that can be gelled and a lithium ion secondary battery using the same.
  • Lithium ion secondary batteries (lithium polymer batteries) using gel electrolytes can be thinned, the degree of freedom of shape selection, and the electrolyte leakage due to the high electrolyte retention of gel electrolytes Because of its low possibility, it has been attracting attention in a wide range of applications from portable device power supplies to large-scale applications such as automotive driving power supplies and stationary storage batteries.
  • the gel electrolyte suppresses volatilization of the flammable solvent in the electrolytic solution, while holding over the low-boiling solvent bubbles caused by abnormal heat generation during overcharging and / or short-circuiting, thereby blocking ion conduction between the electrodes.
  • the safety of the lithium ion secondary battery can be improved.
  • the life of a lithium ion secondary battery can be improved by preventing the gas generated in charging and discharging from entering the separator by immersing the gel in the pores of the separator.
  • the lithium polymer battery tends to have low cycle characteristics, and further improvement has been demanded.
  • Cited Document 1 describes a gel electrolyte precursor containing a crosslinkable compound having an oxirane ring.
  • Cited Document 2 describes a nonaqueous electrolytic solution containing a polymer having an oxetane group represented by a predetermined formula.
  • the electrolyte precursor of Patent Document 1 uses only a low-molecular compound as a crosslinkable compound, it cannot be gelled, or even if gelled, the crosslinking density becomes too high and phase separation easily occurs in the electrolyte. Furthermore, there is a problem that the storage characteristics are also deteriorated. Moreover, since the electrolytic solution of Patent Document 2 gels the electrolytic solution using only a polymer compound, there is a problem that the increase in viscosity before gelation is large and impregnation is poor.
  • the invention of the present application solves the above problems, an electrolyte solution having a low viscosity before gelation and excellent impregnation properties, a high gel strength after gelation, and a suppression of a decrease in ionic conductivity, and a lithium containing the same
  • An object is to provide an ion secondary battery.
  • One embodiment of the present invention is 0.5 to 3% by weight of (meth) acrylic resin having at least one functional group selected from an oxetane group and an epoxy group; 1 to 6% by weight of a polyfunctional monomer having at least two functional groups selected from oxetane groups and epoxy groups, It is related with the electrolyte solution for lithium ion secondary batteries containing.
  • an electrolyte for a lithium ion secondary battery that has a low viscosity before gelation and excellent in impregnation properties, and can form a strong gel while maintaining sufficient ionic conductivity after gelation, and the same are used.
  • a lithium ion secondary battery can be provided.
  • FIG. 1 is a schematic cross-sectional view showing a structure of a laminated laminate type secondary battery according to an embodiment of the present invention. It is a disassembled perspective view which shows the basic structure of a film-clad battery. It is sectional drawing which shows the cross section of the battery of FIG. 3 typically.
  • the electrolyte for a lithium ion secondary battery of the present embodiment is a (meth) acrylic resin (“crosslinkable polymer” having at least one functional group selected from an oxetane group and an epoxy group. And a polyfunctional monomer having two or more functional groups selected from an oxetane group and an epoxy group (“crosslinking”). 1 "to 6% by weight based on the total weight of the electrolyte solution.
  • the oxetane group and / or the epoxy group of each of the crosslinkable polymer and the crosslinking agent undergo ring-opening polymerization by a gelation treatment such as a heat treatment, whereby these compounds are cross-linked to form a gel ( A crosslinked body).
  • a gelation treatment such as a heat treatment
  • the cationic polymerization initiator for ring-opening polymerization generally known polymerization initiators can be used, but a small amount of acidic substance obtained by hydrolysis of the lithium salt and the anion component of the lithium salt contained in the electrolytic solution is used. It is preferable that the characteristics given to the battery are small.
  • the electrolyte solution of the present embodiment contains 0.5 to 3% by weight of a crosslinkable polymer and 1 to 6% by weight of a crosslinker, so that the pregel electrolyte solution has a low viscosity and high impregnation property, and is gelled. In the later crosslinked state, the gel has high strength, sufficiently high ionic conductivity, and no phase separation of the electrolyte occurs. Therefore, the electrolytic solution of this embodiment can also be used for a large battery having a large distance and area to be impregnated with the electrolytic solution. Moreover, the lithium ion secondary battery containing the crosslinked body which the electrolyte solution of this embodiment gelatinized is excellent in safety
  • (Meth) acrylic resin is a generic term for methacrylic resin and acrylic resin.
  • the crosslinkable polymer in the present embodiment is a (meth) acrylic resin having at least one functional group selected from the group consisting of an oxetane group and an epoxy group. In the same molecule, it may have only one or both of oxetane group and epoxy group.
  • the weight average molecular weight of the crosslinkable polymer is not particularly limited, but is preferably 100,000 or more, preferably 1,000,000 or less, more preferably 500,000 or less. When the weight average molecular weight of the crosslinkable polymer is 100,000 or more, it is easy to form a gel. When the weight average molecular weight is 1,000,000 or less, the viscosity of the pregel electrolyte is prevented from excessively increasing, and the electrolyte has excellent impregnation properties. Can do. In the present specification, the weight average molecular weight or the number average molecular weight was determined as follows.
  • a molecular weight distribution was obtained from a measurement result by gel permeation chromatography (GPC) using a calibration curve of monodisperse molecular weight polystyrene as a standard substance. Subsequently, a weight average molecular weight or a number average molecular weight was calculated from the obtained molecular weight distribution.
  • GPC gel permeation chromatography
  • the (meth) acrylic resin as the crosslinkable polymer is preferably, for example, a polymer of (meth) acrylate containing an oxetane group or an epoxy group, or a copolymer with another monomer copolymerizable therewith.
  • examples of other copolymerizable monomers include acrylic acid esters or derivatives thereof, methacrylic acid esters or derivatives thereof, and acrylonitrile or derivatives thereof.
  • a copolymer it may be a block copolymer or a random copolymer.
  • the crosslinkable polymer preferably includes a (meth) acrylic resin having an oxetane group.
  • the (meth) acrylic resin having an oxetane group is excellent in reactivity and low in toxicity, and further easily suppresses the increase in the viscosity of the pregel electrolyte.
  • the oxetane equivalent of the (meth) acrylic resin having an oxetane group is preferably 300 or more, more preferably 400 or more, and preferably 1000 or less, more preferably 800 or less. If the oxetane equivalent is too small, the crosslinking density becomes too high, and phase separation may occur due to curing shrinkage in the electrolytic solution. If the oxetane equivalent is too large, the electrolytic solution may not be gelled.
  • n satisfies 1800 ⁇ n ⁇ 3000
  • m satisfies 350 ⁇ m ⁇ 600.
  • the methacrylic acid ester polymer represented by the general formula (1) is obtained by radical copolymerization of methyl methacrylate and (3-ethyl-3-oxetanyl) methyl methacrylate.
  • N representing the number of methyl methacrylate units satisfies 1800 ⁇ n ⁇ 3000
  • m representing the number of (3-ethyl-3-oxetanyl) methyl methacrylate units satisfies 350 ⁇ m ⁇ 600.
  • the methacrylic acid ester polymer represented by the general formula (1) may be a block copolymer or a random copolymer.
  • N and m represent average values and may not be integers.
  • the weight average molecular weight of the methacrylic acid ester polymer represented by the general formula (1) is preferably 160,000 to 370,000, and the oxetane equivalent is preferably about 400 to 1,000.
  • the content of the methacrylic ester polymer represented by the general formula (1) with respect to the total amount of the crosslinkable polymer is preferably 50% by weight or more, more preferably 70% by weight or more, and still more preferably. It is 90% by weight or more and may be 100% by weight.
  • the crosslinkable polymer may be a (meth) acrylic resin having an epoxy group.
  • the epoxy equivalent of the (meth) acrylic resin having an epoxy group is preferably 300 or more, more preferably 400 or more, and preferably 1000 or less, more preferably 800 or less. If the epoxy equivalent is too small, the crosslinking density becomes too high, and phase separation may occur due to curing shrinkage in the electrolytic solution. If the epoxy equivalent is too large, the electrolytic solution may not be gelled.
  • the crosslinkable polymer may be a (meth) acrylic resin including both an epoxy group and an oxetane group.
  • the total equivalent of the epoxy group and the oxetane group is preferably 300 or more, more preferably 400 or more, and preferably 1000 or less, more preferably 800 or less.
  • crosslinkable polymers may be used alone or in combination of two or more.
  • the content of the crosslinkable polymer in the electrolytic solution is preferably 0.5% by weight or more, more preferably 1% by weight or more, and preferably 3% by weight or less, more preferably based on the total weight of the electrolytic solution. Is 2% by weight or less.
  • a gel that favorably holds the electrolytic solution can be formed.
  • the cross-linking agent in the present embodiment is a polyfunctional monomer having two or more functional groups selected from oxetane groups and epoxy groups.
  • the molecular weight of the polyfunctional monomer as the crosslinking agent is not particularly limited, but is preferably 5000 or less, more preferably 3000 or less, still more preferably 1000 or less, and preferably 100 or more, more preferably 150 or more.
  • the number of epoxy groups and / or oxetane groups in one molecule of the polyfunctional monomer is 2 or more, preferably 3 or more. As the number of epoxy groups and / or oxetane groups increases, the gel strength after gelation tends to increase.
  • the crosslinking agent preferably contains a polyfunctional monomer having two or more epoxy groups.
  • the polyfunctional monomer having two or more epoxy groups in the total amount of the polyfunctional monomer is preferably contained in an amount of 50% by weight or more, more preferably 80% by weight or more.
  • the epoxy equivalent of the polyfunctional monomer having two or more epoxy groups is not particularly limited, but is preferably 400 or less, more preferably 300 or less, and preferably 100 or more.
  • the polyfunctional monomer having two or more epoxy groups may have an ether bond, a carbonyl group or the like in addition to the epoxy group.
  • the polyfunctional monomer having an epoxy group is preferably an aliphatic epoxy compound, more preferably a compound having an alicyclic epoxy group, and still more preferably a compound having an epoxycyclohexyl group represented by the following structural formula (21). More preferably, it is a compound having two or more epoxycyclohexyl groups represented by the following structural formula (21).
  • the compound having an epoxycyclohexyl group represented by the structural formula (21) is preferably contained in an amount of 50% by weight or more, more preferably 80% by weight or more in the total amount of the polyfunctional monomer. And may be 100% by weight.
  • the above-mentioned compound having an epoxycyclohexyl group has high reactivity, and the inclusion of this compound makes it easy to strengthen the gel after gelation while keeping the viscosity of the pregel electrolyte low.
  • the polyfunctional monomer having an epoxy group is not particularly limited.
  • butanetetracarboxylic acid tetra (3,4-epoxycyclohexylmethyl) modified ⁇ -caprolactone represented by the following formula (2): .92, epoxy equivalent: 197.25
  • 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate compound represented by the following formula (3) (weight average molecular weight: 252.31, epoxy The equivalent is: 126.155).
  • the polyfunctional monomer preferably includes a polyfunctional monomer having two or more oxetane groups.
  • the polyfunctional monomer having two or more oxetane groups in the total amount of the polyfunctional monomer is preferably contained in an amount of 50% by weight or more, more preferably 80% by weight or more.
  • a polyfunctional monomer having an oxetane group is preferred because of low toxicity and excellent reactivity.
  • the electrolytic solution may be colored brown.
  • the electrolytic solution is not colored, and the storage characteristics are excellent.
  • the oxetane equivalent of the polyfunctional monomer having two or more oxetane groups is not particularly limited, but is preferably 400 or less, more preferably 300 or less, and preferably 100 or more.
  • the polyfunctional monomer having two or more oxetane groups may have an ether bond, a carbonyl group or the like in addition to the oxetane group.
  • cross-linking agent having an oxetane group examples include the following compounds.
  • the content of the crosslinking agent in the electrolytic solution is preferably 1% by weight or more, more preferably 2% by weight or more, and preferably 6% by weight or less, more preferably 4% by weight with respect to the total weight of the electrolytic solution. % Or less.
  • the content of the crosslinking agent is 1% by weight or more, the increase in the viscosity of the pregel electrolyte can be suppressed to improve the impregnation property, and the gel strength after gelation can be increased.
  • the content of the cross-linking agent is 6% by weight or less, it is easy to suppress the degree of cross-linking and the electrolyte solution from being phase-separated.
  • the combination of the crosslinkable polymer and the crosslinker is not particularly limited, but in the case where the crosslinkable polymer is an (meth) acrylic resin having an epoxy group, the crosslinker is preferably a polyfunctional monomer having an epoxy group, When the crosslinkable polymer is a (meth) acrylic resin having an oxetane group, the crosslinking agent is preferably a polyfunctional monomer having an epoxy group and / or an oxetane group. In general, the initial reaction rate of the epoxy group tends to be faster than that of the oxetane group. Therefore, if the combination of the crosslinkable polymer and the crosslinking agent is any of the above, the crosslinking reaction by the crosslinking agent can be prevented from being delayed.
  • both the crosslinkable polymer and the crosslinking agent contain a compound having an oxetane group, the toxicity is low, coloring of the electrolyte solution can be suppressed, and storage characteristics are excellent.
  • a preferred embodiment of this embodiment includes a combination of a methacrylic resin represented by the formula (1) as a crosslinkable polymer and a compound represented by the formula (2) as a polyfunctional monomer.
  • the total content of the crosslinkable polymer and the crosslinking agent with respect to the total weight of the electrolytic solution of the present embodiment is not particularly limited, but is preferably 1.5% by weight or more, more preferably 2% by weight or more, and further preferably It is 3% by weight or more, preferably 9% by weight or less, more preferably 7% by weight, and still more preferably 5% by weight or less.
  • the weight ratio between the crosslinkable polymer and the crosslinking agent is not particularly limited, but is preferably about 3: 1 to 1:12.
  • an electrolyte for a lithium ion secondary battery includes a (meth) acrylic resin (crosslinkable polymer) having at least one functional group selected from an oxetane group and an epoxy group, an oxetane group and an epoxy group.
  • the numerical value calculated by is 6000 or less.
  • the lower limit is not particularly limited, but is preferably 100 or more.
  • the electrolyte solution of the present embodiment is not particularly limited, but preferably further contains a nonaqueous solvent, a supporting salt, and the like in addition to the crosslinkable polymer and the crosslinking agent.
  • the support salt used as the electrolyte are not particularly limited, for example, LiPF 6, LiAsF 6, LiAlCl 4, LiClO 4, LiBF 4, LiSbF 6, LiCF 3 SO 3, LiC 4 F 9 SO 3, Examples thereof include lithium salts such as LiN (FSO 2 ) 2 , Li (CF 3 SO 2 ) 2 , and LiN (CF 3 SO 2 ) 2 .
  • the trace amount acidic substance which hydrolyzed the lithium salt and the anion component of lithium salt functions also as a cationic polymerization initiator which starts the crosslinking reaction of a crosslinkable polymer and a crosslinking agent. Thereby, it is not necessary to add a polymerization initiator separately, and there is no adverse effect on the battery.
  • the supporting salt can be used alone or in combination of two or more.
  • the concentration of the supporting salt in the electrolytic solution is preferably 0.5 to 1.5 mol / l. By setting the concentration of the supporting salt within this range, it becomes easy to adjust the density, viscosity, electrical conductivity, and the like to an appropriate range.
  • the non-aqueous solvent is not particularly limited, but an aprotic solvent is preferable.
  • carbonates such as cyclic carbonates and chain carbonates, aliphatic carboxylic acid esters, ⁇ -lactone , Cyclic ethers, chain ethers, and fluorine derivatives thereof. These can be used individually by 1 type or in combination of 2 or more types.
  • cyclic carbonates examples include propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), and vinylene carbonate (VC).
  • chain carbonates examples include dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), and dipropyl carbonate (DPC).
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • EMC ethyl methyl carbonate
  • DPC dipropyl carbonate
  • chain aliphatic monocarboxylic acid esters examples include methyl formate, methyl acetate, and ethyl propionate.
  • ⁇ -lactones examples include ⁇ -butyrolactone.
  • cyclic ethers examples include tetrahydrofuran and 2-methyltetrahydrofuran.
  • chain ethers examples include 1,2-diethoxyethane (DEE), ethoxymethoxyethane (EME), and the like.
  • non-aqueous solvents include, for example, dimethyl sulfoxide, 1,3-dioxolane, formamide, acetamide, dimethylformamide, acetonitrile, propionitrile, nitromethane, ethyl monoglyme, phosphate triester, trimethoxymethane, dioxolane.
  • ⁇ Nonaqueous solvents may be used alone or in combination of two or more.
  • the electrolytic solution using an acid generated by hydrolysis of the supporting salt in the electrolytic solution as a polymerization initiator, but a known polymerization initiator may be included separately.
  • the polymerization initiator include cationic polymerization initiators such as quaternary ammonium salts, tertiary amine salts, phosphonium salts, sulfonium salts, diazonium salts, and iodonium salts.
  • the gelation rate can be controlled so as to be compatible with the battery manufacturing process.
  • the electrolytic solution may contain an additive such as a sulfonic acid ester as long as the effects of the present invention are not impaired.
  • the method for producing the electrolytic solution of the present embodiment is not particularly limited, but preferably at room temperature and in a non-aqueous solvent, the above-mentioned crosslinkable polymer, crosslinker, supporting salt, additives as necessary, polymerization initiator. Etc. are added and mixed to produce a pregel electrolyte.
  • the mixing order is not particularly limited. As will be described later, this pregel electrolyte is injected into the outer package of a lithium ion secondary battery, and then the outer package is sealed, and the secondary battery is preferably heated at 30 to 80 ° C. for about 1 to 72 hours. It is preferable to perform a gelation treatment for gelling the electrolytic solution.
  • the lithium ion secondary battery of the present embodiment includes the electrolyte for the lithium ion secondary battery of the present embodiment, and further includes a positive electrode, a negative electrode, and a separator disposed between the positive electrode and the negative electrode.
  • the electrolytic solution may be a pre-gel electrolytic solution before gelation, a crosslinked product after gelation, or a mixture thereof.
  • the positive electrode can have a configuration in which a positive electrode active material layer containing a positive electrode active material is formed on a current collector.
  • the positive electrode of this embodiment has, for example, a positive electrode current collector formed of a metal foil, and a positive electrode active material layer coated on one or both surfaces of the positive electrode current collector.
  • the positive electrode active material layer is formed so as to cover the positive electrode current collector with a positive electrode binder.
  • the positive electrode current collector is configured to have an extension connected to the positive electrode terminal, and the positive electrode active material layer is not coated on the extension.
  • the positive electrode active material in the present embodiment is not particularly limited as long as it is a material capable of occluding and releasing lithium, and can be selected from several viewpoints. From the viewpoint of increasing the energy density, it is preferable to include a high-capacity compound.
  • the high-capacity compound include lithium nickel oxide (LiNiO 2 ) or a lithium nickel composite oxide obtained by substituting a part of Ni of lithium nickelate with another metal element.
  • the layered structure is represented by the following formula (A) Lithium nickel composite oxide is preferred.
  • the Ni content is high, that is, in the formula (A), x is preferably less than 0.5, and more preferably 0.4 or less.
  • x is preferably less than 0.5, and more preferably 0.4 or less.
  • LiNi 0.8 Co 0.05 Mn 0.15 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 , LiNi 0.8 Co 0.15 Al 0.05 O 2, LiNi 0.8 Co 0.1 Al can be preferably used 0.1 O 2 or the like.
  • the Ni content does not exceed 0.5, that is, in the formula (A), x is 0.5 or more. It is also preferred that the number of specific transition metals does not exceed half.
  • LiNi 0.4 Co 0.3 Mn 0.3 O 2 (abbreviated as NCM433), LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiNi 0.5 Co 0.2 Mn 0.3 O 2 (abbreviated as NCM523), LiNi 0.5 Co 0.3 Mn 0.2 O 2 (abbreviated as NCM532), etc. (however, the content of each transition metal in these compounds varies by about 10%) Can also be included).
  • two or more compounds represented by the formula (A) may be used as a mixture.
  • NCM532 or NCM523 and NCM433 range from 9: 1 to 1: 9 (typically 2 It is also preferable to use a mixture in 1).
  • a material having a high Ni content (x is 0.4 or less) and a material having a Ni content not exceeding 0.5 (x is 0.5 or more, for example, NCM433) are mixed. As a result, a battery having a high capacity and high thermal stability can be formed.
  • the positive electrode active material for example, LiMnO 2 , Li x Mn 2 O 4 (0 ⁇ x ⁇ 2), Li 2 MnO 3 , Li x Mn 1.5 Ni 0.5 O 4 (0 ⁇ x ⁇ 2) Lithium manganate having a layered structure or spinel structure such as LiCoO 2 or a part of these transition metals replaced with another metal; Li in these lithium transition metal oxides more than the stoichiometric composition And those having an olivine structure such as LiFePO 4 .
  • any of the positive electrode active materials described above can be used alone or in combination of two or more.
  • any of the positive electrode active materials described above can be used singly or in combination of two or more.
  • the positive electrode binder the same materials as those mentioned as the negative electrode binder can be used. Among these, polyvinylidene fluoride is preferable from the viewpoint of versatility and low cost.
  • the amount of the positive electrode binder is preferably 2 to 10 parts by mass with respect to 100 parts by mass of the positive electrode active material.
  • the same materials as those mentioned for the negative electrode current collector can be used.
  • a conductive auxiliary material may be added to the positive electrode active material layer containing the positive electrode active material for the purpose of reducing impedance.
  • the conductive auxiliary material include carbonaceous fine particles such as graphite, carbon black, and acetylene black.
  • the lithium secondary battery of this embodiment includes a negative electrode having a negative electrode active material.
  • the negative electrode active material can be bound on the negative electrode current collector by a negative electrode binder.
  • the negative electrode of this embodiment can be configured to have a negative electrode current collector formed of a metal foil and a negative electrode active material layer coated on one or both surfaces of the negative electrode current collector.
  • the negative electrode active material layer is formed so as to cover the negative electrode current collector with a negative electrode binder.
  • the negative electrode current collector is configured to have an extension connected to the negative electrode terminal, and the negative electrode active material layer is not coated on the extension.
  • the present invention is not particularly limited.
  • lithium metal metal (a) capable of being alloyed with lithium, metal oxide (b) capable of inserting and extracting lithium ions, or lithium Examples thereof include a carbon material (c) that can occlude and release ions.
  • a negative electrode active material can be used individually by 1 type or in combination of 2 or more types.
  • the metal (a) examples include Al, Si, Pb, Sn, In, Bi, Ag, Ba, Ca, Hg, Pd, Pt, Te, Zn, La, or alloys of two or more thereof. It is done. Moreover, you may use these metals or alloys in mixture of 2 or more types. These metals or alloys may contain one or more non-metallic elements. Among these, it is preferable to use silicon, tin, or an alloy thereof as the negative electrode active material. By using silicon or tin as the negative electrode active material, a lithium secondary battery excellent in weight energy density and volume energy density can be provided.
  • the metal oxide (b) examples include silicon oxide, aluminum oxide, tin oxide, indium oxide, zinc oxide, lithium oxide, and composites thereof. Among these, it is preferable to use silicon oxide as the negative electrode active material. Further, the metal oxide (b) can contain, for example, 0.1 to 5% by weight of one or more elements selected from nitrogen, boron and sulfur.
  • Examples of the carbon material (c) include graphite, amorphous carbon, diamond-like carbon, carbon nanotube, or a composite thereof.
  • the negative electrode binder is not particularly limited, and examples thereof include polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, and styrene-butadiene copolymer rubber. , Polytetrafluoroethylene, polypropylene, polyethylene, polyimide, polyamideimide, polyacrylic acid and the like. Of these, polyvinylidene fluoride or styrene-butadiene copolymer rubber may be preferred because of its strong binding properties.
  • the negative electrode binder is preferably polyimide or polyacrylic acid.
  • the electrolyte solution of the present embodiment includes a compound having an epoxy group and / or an oxetane group. These functional groups are combined with carboxyl groups and amino groups contained in polyimide or polyacrylic acid, and a strong gel is formed around the negative electrode active material, improving liquid retention and improving cycle characteristics. It is considered easy.
  • the amount of the negative electrode binder is preferably 0.5 to 25 parts by mass, more preferably 1 to 8 parts by mass, and 1 to 5 parts by mass with respect to 100 parts by mass of the negative electrode active material. It is also preferable.
  • the negative electrode current collector aluminum, nickel, stainless steel, chromium, copper, silver, and alloys thereof are preferable in view of electrochemical stability.
  • the shape include a foil, a flat plate, and a mesh.
  • the negative electrode can be produced by forming a negative electrode active material layer containing a negative electrode active material and a negative electrode binder on a negative electrode current collector.
  • Examples of the method for forming the negative electrode active material layer include a doctor blade method, a die coater method, a CVD method, and a sputtering method. After forming a negative electrode active material layer in advance, a thin film of aluminum, nickel, or an alloy thereof may be formed on the negative electrode active material layer by a method such as vapor deposition or sputtering to produce a negative electrode.
  • the separator is not particularly limited, but may be a separator made of an organic material.
  • the separator made of an organic material include a separator made of polyolefin such as polypropylene and polyethylene, polyethylene terephthalate (PET), aramid, polyimide, polyphenylene sulfide (PPS), cellulose, polyvinylidene fluoride, or an ion conductive polymer electrolyte membrane. Is mentioned.
  • Examples of the structure of the separator include woven fabric, nonwoven fabric, and microporous membrane. These can be used alone or in combination. Moreover, what laminated
  • the separator which consists of inorganic materials, such as a ceramic and glass, can also be used as a separator.
  • a nonwoven fabric separator made of ceramic short fibers such as alumina, alumina-silica, potassium titanate, or a base material made of a woven fabric, nonwoven fabric, porous film, heat-resistant nitrogen-containing aromatic polymer, and ceramic powder
  • a heat-resistant layer is provided on a part of the surface of the separator, and the heat-resistant layer is a porous thin film layer containing a ceramic powder, a porous thin film layer of a heat-resistant resin, or a ceramic powder.
  • a porous thin film layer separator made of a composite of a heat-resistant resin, or a porous film formed by binding secondary particles obtained by sintering or dissolving and recrystallizing some primary particles of a ceramic material with a binder.
  • a base material layer is a separator provided with a layer, or a separator made of the above organic material or a separator made of an inorganic material.
  • a heat-resistant insulating layer formed on one or both sides of the base material layer is provided, and this heat-resistant insulating layer is formed by combining a separator containing oxidation-resistant ceramic particles and a heat-resistant resin, or a ceramic substance and a binder.
  • Ceramic material including a porous film, silica (SiO 2 ), alumina (Al 2 O 3 ), zirconium oxide (ZrO 2 ), titanium oxide (TiO 2 ), nitride of silicon (Si), aluminum ( Al) hydroxide, zirconium (Zr) alkoxide, separator using titanium (Ti) ketone compound, or polymer substrate, and Al 2 O 3 , MgO, TiO formed on the polymer substrate 2 , a separator including a ceramic-containing coating layer of Al (OH) 3 , Mg (OH) 2 , and Ti (OH) 4 .
  • Separator may be used alone or in combination.
  • the electrolytic solution of the present embodiment includes a compound having an epoxy group or an oxetane group, these functional groups and terminal groups (carboxyl group, amino group, hydroxy group) of materials constituting the separator (for example, aramid, PET, etc.) It is considered that the safety of the secondary battery is improved and the lifetime is improved by forming a strong gel inside the separator.
  • FIG. 1 shows a laminate type secondary battery as an example of the secondary battery according to this embodiment.
  • a separator 5 is sandwiched between a positive electrode composed of a positive electrode active material layer 1 containing a positive electrode active material and a positive electrode current collector 3, and a negative electrode composed of a negative electrode active material layer 2 and a negative electrode current collector 4.
  • the positive electrode current collector 3 is connected to the positive electrode lead terminal 8
  • the negative electrode current collector 4 is connected to the negative electrode lead terminal 7.
  • An exterior laminate 6 is used for the exterior body, and the inside of the secondary battery is filled with an electrolytic solution.
  • the electrode element also referred to as “battery element” or “electrode stack” preferably has a configuration in which a plurality of positive electrodes and a plurality of negative electrodes are stacked via a separator, as shown in FIG.
  • Examples of the laminate resin film used for the laminate mold include aluminum, an aluminum alloy, and a titanium foil.
  • Examples of the material of the heat-welded portion of the metal laminate resin film include thermoplastic polymer materials such as polyethylene, polypropylene, and polyethylene terephthalate.
  • the metal laminate resin layer and the metal foil layer are not limited to one layer, and may be two or more layers.
  • the secondary battery includes a battery element 20, a film outer package 10 that houses the battery element 20 together with an electrolyte, and a positive electrode tab 51 and a negative electrode tab 52 (hereinafter also simply referred to as “electrode tabs”). .
  • the battery element 20 is formed by alternately stacking a plurality of positive electrodes 30 and a plurality of negative electrodes 40 with a separator 25 interposed therebetween.
  • the electrode material 32 is applied to both surfaces of the metal foil 31.
  • the electrode material 42 is applied to both surfaces of the metal foil 41. Note that the present invention is not limited to a stacked battery, and can be applied to a battery of a wound type.
  • the secondary battery in FIG. 2 has electrode tabs pulled out on both sides of the outer package, but the secondary battery to which the present invention can be applied has an electrode tab pulled out on one side of the outer package as shown in FIG. It may be a configuration.
  • each of the positive and negative metal foils has an extension on a part of the outer periphery.
  • the extensions of the negative electrode metal foil are collected together and connected to the negative electrode tab 52, and the extensions of the positive electrode metal foil are collected together and connected to the positive electrode tab 51 (see FIG. 4).
  • the portions gathered together in the stacking direction between the extension portions in this way are also called “current collecting portions”.
  • the film outer package 10 is composed of two films 10-1 and 10-2 in this example.
  • the films 10-1 and 10-2 are heat sealed to each other at the periphery of the battery element 20 and sealed.
  • the positive electrode tab 51 and the negative electrode tab 52 are drawn out in the same direction from one short side of the film outer package 10 sealed in this way.
  • FIGS. 3 and 4 show examples in which the cup portion is formed on one film 10-1 and the cup portion is not formed on the other film 10-2.
  • a configuration in which a cup portion is formed on both films (not shown) or a configuration in which neither cup portion is formed (not shown) may be employed.
  • the lithium ion secondary battery according to the present embodiment can be produced according to a normal method. Taking a laminated laminate type lithium ion secondary battery as an example, an example of a method for producing a lithium ion secondary battery will be described. First, in a dry air or an inert atmosphere, an electrode element is formed by arranging a positive electrode and a negative electrode to face each other with a separator interposed therebetween. Next, after this electrode element is accommodated in an exterior body (container), the electrolyte solution (pregel electrolyte solution) of this embodiment is injected and impregnated in the electrode, the opening of the exterior body is sealed.
  • heating conditions are not specifically limited, For example, it is preferable to heat at 30 degreeC or more and 80 degrees C or less for 1 hour or more and 72 hours or less.
  • Examples of the heating method include a method using a thermostatic bath, a hot air circulation dryer, and the like.
  • a plurality of lithium ion secondary batteries according to this embodiment can be combined to form an assembled battery.
  • the assembled battery may have a configuration in which two or more lithium ion secondary batteries according to the present embodiment are used and connected in series, in parallel, or both. Capacitance and voltage can be freely adjusted by connecting in series and / or in parallel. About the number of the lithium ion secondary batteries with which an assembled battery is provided, it can set suitably according to battery capacity or an output.
  • the lithium ion secondary battery or its assembled battery according to this embodiment can be used in a vehicle.
  • Vehicles according to this embodiment include hybrid vehicles, fuel cell vehicles, and electric vehicles (all include four-wheel vehicles (passenger cars, trucks, buses and other commercial vehicles, light vehicles, etc.), motorcycles (motorcycles), and tricycles. ).
  • the vehicle according to the present embodiment is not limited to an automobile, and may be used as various power sources for other vehicles, for example, moving bodies such as trains.
  • crosslinkable polymers and polyfunctional monomers used in Examples and Comparative Examples are as follows.
  • Comparative Example 1-1 to Comparative Example 8-7 1 mol / L of lithium hexafluorophosphate was dissolved in a solution in which ethylene carbonate and diethylene carbonate were mixed at a volume ratio of 3: 7 to obtain a standard electrolytic solution.
  • this standard electrolyte and a crosslinkable polymer (compound 1: poly (methyl methacrylate)-(3-ethyl-3-oxetanyl) methyl methacrylate) and a polyfunctional monomer (compound 2 which is a tetrafunctional alicyclic epoxy compound) : Butanetetracarboxylic acid tetra (3,4-epoxycyclohexylmethyl) modified ⁇ -caprolactone)), and dissolved and mixed using an ultrasonic cleaner in a plugged state, “pre-gel electrolyte” (gel electrolyte precursor) ) Compound 1 and Compound 2 were added in the proportions shown in Tables 1 to 3, respectively. In addition, in the table
  • Examples 5-1 to 5-3> Instead of the polyfunctional monomer of Example 1-1 (Compound 2), a polyfunctional monomer (Compound 3 which is a bifunctional alicyclic epoxy compound) was added at a ratio shown in Table 3.
  • Examples 6-1 to 6-3> instead of the polyfunctional monomer of Example 1-1 (compound 2), a polyfunctional monomer (compound 4: bifunctional oxetane compound 4: 1,4-bis ⁇ [(3-ethyloxetane-3-yl) methoxy] methyl ⁇ Benzene) was added at the rate shown in Table 3.
  • a layered lithium nickel composite oxide (LiNi 0.8 Co 0.15 Al 0.05 O 2 ), a carbon conductive agent, and polyvinylidene fluoride as a binder in a weight ratio of 92: 4: 4, N-methyl- A slurry was prepared by dispersing in 2-pyrrolidone (NMP), applied to a current collector foil made of aluminum, and dried to form a positive electrode active material layer. Similarly, after forming an active material layer on the back surface of the current collector foil made of aluminum, it was rolled to obtain a positive electrode plate. The thickness of the mixture layer was 100 ⁇ m on one side and the porosity was about 30%.
  • Natural graphite, sodium carboxymethyl methylcellulose as a thickener, and styrene butadiene rubber as a binder are mixed in an aqueous solution at a weight ratio of 98: 1: 1 to prepare a slurry, which is applied to a copper current collector foil. And dried to form a negative electrode active material layer. Similarly, after forming an active material layer on the back surface of the current collector foil made of copper, a negative electrode plate was obtained by rolling. The thickness of the mixture layer was 100 ⁇ m on one side and the porosity was about 30%.
  • Separator A microporous polypropylene sheet having a thickness of 25 ⁇ m was used as a separator. The porosity of this separator was about 40%.
  • the positive electrode plate was cut to 200 mm ⁇ 200 mm as a dimension excluding the current extraction part, and the negative electrode plate was cut to 204 mm ⁇ 204 mm as a dimension excluding the current extraction part, and laminated via a separator.
  • the laminate was fixed on four sides with a tape having a width of 10 mm and placed in a bag made of an aluminum laminate film. Thereafter, 120 cc of each pregel electrolyte prepared above was poured and vacuum-sealed.
  • the measurement of ultrasonic transmission was performed as follows using an aerial ultrasonic system (NAUT: Japan Probe).
  • NAUT aerial ultrasonic system
  • the battery was placed horizontally between the transmission probe and the reception probe, and the ultrasonic wave transmittance distribution of the battery was scanned.
  • the transmission intensity is extremely lowered because the ultrasonic waves are reflected and scattered.
  • the projected area was measured assuming that the part where the ultrasonic wave did not pass was a part where bubbles were present, and the ratio of the projected area of the part where bubbles were present to the projected area of the battery was used as an index indicating the impregnation property of the electrolyte. It can be said that the smaller the ratio, the higher the impregnation property.
  • the ratio of the bubbles in the layered body part (the ratio of the projected area of the part where the bubbles are present to the projected area of the battery) is less than 1% in the measurement one day after vacuum sealing, and ⁇
  • the ratio of air bubbles in the laminate part is less than 1% in the measurement after 2 days after vacuum sealing out of 1% or more in the measurement after 1 day after vacuum sealing. Items were evaluated as ⁇ and those with 5% or more as x. The results are shown in Tables 1 to 3.
  • the electrolyte viscosity before gelation affects the impregnation property of the battery.
  • the higher the viscosity of the electrolyte solution the longer the time required for impregnation.
  • the distance between the center and the end of the wound and laminated electrode group becomes longer, requiring a longer time.
  • air pockets are formed and impregnation to the center is impossible.
  • the viscosity of the pregel electrolyte was measured at 20 ° C. to 25 ° C. using a tuning fork viscometer (A & D, SV-1A). The measurement results are shown in Tables 1 to 3.
  • the impregnation property in the battery is consistent with the tendency of the viscosity of the pregel electrolyte, and if the pregel viscosity is 10 mPa ⁇ s or less, the impregnation property is ⁇ if it exceeds 10 mPa ⁇ s and 25 mPa ⁇ s or less. , If it exceeds 25 mPa ⁇ s and not more than 40 mPa ⁇ s, it is determined to be X if it exceeds 40 mPa ⁇ s.
  • the pregel electrolyte solution was stored in a constant temperature bath at 50 ° C. for 2 days while being put in a test tube, thereby carrying out a crosslinking reaction of the functional group (epoxy group and / or oxetane group) of the compound. Subsequently, the test tube was allowed to cool to room temperature and then gelation was determined. When the test tube was turned upside down, the electrolyte did not fall from the bottom of the test tube due to gelation; ⁇ , some of the liquid separated or some dropped from the bottom of the test tube; Those that maintained fluidity were evaluated as x. The results are shown in Tables 1 to 3.
  • Examples of applications of the present invention include driving devices such as electric vehicles, plug-in hybrid vehicles, electric motorcycles, and electric assist bicycles, tools such as electric tools, electronic devices such as portable terminals and laptop computers, household power storage systems, and solar power. Examples include storage batteries such as photovoltaic power generation systems.

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Abstract

L'invention concerne une solution électrolytique pour batterie secondaire au lithium-ion qui contient 0,5 à 3% en masse d'une résine (méth)acrylique possédant au moins un groupe fonctionnel choisi parmi un groupe oxétane et un groupe époxy, 1 à 6% en masse d'un monomère polyfonctionnel possédant deux groupes fonctionnels ou plus d'au moins une sorte choisie parmi un groupe oxétane et un groupe époxy.
PCT/JP2017/006087 2017-02-20 2017-02-20 Solution électrolytique pour batterie secondaire au lithium-ion, et batterie secondaire au lithium-ion mettant en œuvre celle-ci WO2018150567A1 (fr)

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JP2019500148A JP6750723B2 (ja) 2017-02-20 2017-02-20 リチウムイオン二次電池用電解液およびこれを用いたリチウムイオン二次電池
PCT/JP2017/006087 WO2018150567A1 (fr) 2017-02-20 2017-02-20 Solution électrolytique pour batterie secondaire au lithium-ion, et batterie secondaire au lithium-ion mettant en œuvre celle-ci

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023112787A1 (fr) * 2021-12-15 2023-06-22 第一工業製薬株式会社 Solution électrolytique non aqueuse et batterie secondaire au lithium-ion
JP7440697B1 (ja) 2023-11-13 2024-02-28 第一工業製薬株式会社 非水電解液用添加剤、非水電解液、及びリチウムイオン二次電池
JP7514725B2 (ja) 2020-10-15 2024-07-11 日本特殊陶業株式会社 二次電池の取扱方法及び二次電池の取扱システム

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JP2002150836A (ja) * 2000-11-14 2002-05-24 Ube Ind Ltd 高分子固体電解質及びその製造方法
JP2005149822A (ja) * 2003-11-13 2005-06-09 Hitachi Maxell Ltd ゲル状電解質
JP2007122902A (ja) * 2005-10-25 2007-05-17 Nitto Denko Corp リチウムイオン電池の製造方法
WO2011004483A1 (fr) * 2009-07-09 2011-01-13 Ｎｅｃエナジーデバイス株式会社 Électrolyte gel polymère et batterie secondaire à polymère l'utilisant
JP2016072119A (ja) * 2014-09-30 2016-05-09 日立マクセル株式会社 リチウム二次電池

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Publication number Priority date Publication date Assignee Title
JP2001250584A (ja) * 1999-12-28 2001-09-14 Toshiba Corp ゲル電解質前駆体及び化学電池
JP2002150836A (ja) * 2000-11-14 2002-05-24 Ube Ind Ltd 高分子固体電解質及びその製造方法
JP2005149822A (ja) * 2003-11-13 2005-06-09 Hitachi Maxell Ltd ゲル状電解質
JP2007122902A (ja) * 2005-10-25 2007-05-17 Nitto Denko Corp リチウムイオン電池の製造方法
WO2011004483A1 (fr) * 2009-07-09 2011-01-13 Ｎｅｃエナジーデバイス株式会社 Électrolyte gel polymère et batterie secondaire à polymère l'utilisant
JP2016072119A (ja) * 2014-09-30 2016-05-09 日立マクセル株式会社 リチウム二次電池

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7514725B2 (ja) 2020-10-15 2024-07-11 日本特殊陶業株式会社 二次電池の取扱方法及び二次電池の取扱システム
WO2023112787A1 (fr) * 2021-12-15 2023-06-22 第一工業製薬株式会社 Solution électrolytique non aqueuse et batterie secondaire au lithium-ion
JP7440697B1 (ja) 2023-11-13 2024-02-28 第一工業製薬株式会社 非水電解液用添加剤、非水電解液、及びリチウムイオン二次電池

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