WO2014133161A1 - Batterie secondaire à électrolyte non-aqueux - Google Patents

Batterie secondaire à électrolyte non-aqueux Download PDF

Info

Publication number
WO2014133161A1
WO2014133161A1 PCT/JP2014/055169 JP2014055169W WO2014133161A1 WO 2014133161 A1 WO2014133161 A1 WO 2014133161A1 JP 2014055169 W JP2014055169 W JP 2014055169W WO 2014133161 A1 WO2014133161 A1 WO 2014133161A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
secondary battery
formula
positive electrode
lithium ion
Prior art date
Application number
PCT/JP2014/055169
Other languages
English (en)
Japanese (ja)
Inventor
信也 須藤
佐々木　英明
伊紀子 島貫
川崎　大輔
石川　仁志
Original Assignee
日本電気株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本電気株式会社 filed Critical 日本電気株式会社
Priority to JP2015503063A priority Critical patent/JPWO2014133161A1/ja
Publication of WO2014133161A1 publication Critical patent/WO2014133161A1/fr

Links

Images

Classifications

    • 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
    • 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
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to an electrolytic solution for a secondary battery, a secondary battery using the same, and further to a lithium ion secondary battery.
  • a positive electrode active material based on LiMO 2 having a layered structure (M is at least one of Co, Ni and Mn) or LiMn 2 O 4 having a spinel structure is used.
  • a lithium ion secondary battery having such a positive electrode active material mainly uses a charge / discharge region of 4.2 V or less (hereinafter referred to as a positive electrode mainly having an operating potential of 4.2 V or less with respect to lithium metal). It may be described as “4V class positive electrode”). Further, a carbon material such as graphite is used as the negative electrode active material.
  • a material obtained by substituting a part of Mn of LiMn 2 O 4 with Ni or the like shows a high charge / discharge region of 4.5 to 4.8 V with respect to lithium metal.
  • spinel compounds such as LiNi 0.5 Mn 1.5 O 4 are not redox of conventional Mn 3+ and Mn 4+ , but Mn exists in the state of Mn 4+ and redox of Ni 2+ and Ni 4+ Therefore, a high operating voltage of 4.5 V or higher is shown.
  • Such a material is called a 5V class active material and is expected to be a promising positive electrode material because it can improve the energy density by increasing the voltage.
  • lithium ion de-insertion reaction occurs at the interface between the electrode and the electrolytic solution.
  • the electrolytic solution solvent and supporting salt cause a decomposition reaction, resulting in high resistance.
  • a film is formed on the surface of the electrode, so that the lithium ion deinsertion reaction that is supposed to occur is inhibited.
  • an irreversible decrease in discharge capacity is promoted, leading to deterioration of the battery, and various ideas have been made to suppress it.
  • Patent Documents 1 and 2 when a cyclic disulfonic acid ester is used as an additive for an electrolytic solution, a more stable film is formed on the electrode surface than that using a cyclic monosulfonic acid ester as an additive. It is described that improvement can be achieved.
  • Patent Document 3 describes that the battery characteristics can be improved by using an electrolytic solution containing a disulfonic acid ester having a water content of 300 ppm or less.
  • Patent Document 4 describes that the battery characteristics can be improved by using a cyclic disulfonic acid ester having an unsaturated bond.
  • Patent Document 5 in a secondary battery containing a positive electrode material exhibiting a high potential of 4.5 V or higher with respect to lithium, by incorporating a cyclic sulfonate ester in a non-aqueous electrolyte, charge / discharge characteristics, particularly storage characteristics. It is described that improvement can be achieved.
  • Patent Document 6 in a secondary battery containing a positive electrode active material that operates at 4.5 V or higher with respect to lithium, an electrolytic solution containing a fluorinated ether represented by a predetermined formula and a cyclic sulfonate ester is used. It is described that the capacity reduction in the high temperature cycle can be improved.
  • JP 2004-281368 A Japanese Patent Laid-Open No. 2005-2222846 JP 2008-153118 A JP 2004-281325 A JP 2005-149750 A International Publication No. 2012/127717
  • an object of the present invention is to provide a secondary battery in which a decrease in capacity due to self-discharge is suppressed, that is, excellent in capacity retention characteristics.
  • the present invention is a lithium ion secondary battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte, wherein the positive electrode includes a positive electrode active material having an operating potential of 4.5 V or more with respect to lithium metal,
  • the non-aqueous electrolyte includes a cyclic sulfonate ester represented by the formula (1), and relates to a lithium ion secondary battery.
  • R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen group, or an amino group, provided that both R 1 and R 2 are hydrogen atoms.
  • R 3 represents the number of carbon atoms in which an alkylene unit or a fluoroalkylene unit is bonded via an alkylene group having 1 to 5 carbon atoms, a carbonyl group, a sulfonyl group, a fluoroalkylene group having 1 to 6 carbon atoms, and an ether group.
  • a linking group selected from the group consisting of 2 to 6 divalent groups is shown.
  • the present invention it is possible to suppress a decrease in capacity due to self-discharge of a lithium ion secondary battery containing a 5V class active material, that is, to increase a capacity retention rate.
  • the non-aqueous electrolyte of the lithium ion secondary battery in the present embodiment (hereinafter sometimes simply referred to as “electrolyte”) is a cyclic sulfonate ester represented by the general formula (1) ( Hereinafter, it may be simply referred to as “compound of general formula (1)”.
  • R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen group, or an amino group, provided that both R 1 and R 2 are hydrogen atoms.
  • R 3 represents the number of carbon atoms in which an alkylene unit or a fluoroalkylene unit is bonded via an alkylene group having 1 to 5 carbon atoms, a carbonyl group, a sulfonyl group, a fluoroalkylene group having 1 to 6 carbon atoms, and an ether group.
  • a linking group selected from the group consisting of 2 to 6 divalent groups is shown.
  • the cyclic sulfonate ester of the general formula (1) contained in the non-aqueous electrolyte is decomposed by an electrochemical redox reaction during charge / discharge reaction to form a film on the surface of the electrode active material. Decomposition can be suppressed. This is considered to be effective in extending the life of the lithium ion secondary battery.
  • the present inventors have conducted a 5V class activity using an electrolyte containing a compound of the general formula (1). It has been found that in a lithium ion secondary battery containing a substance, capacity retention characteristics at a high temperature of the battery, in particular, maintenance characteristics of remaining capacity due to self-discharge are improved.
  • the present inventors have a substituent at a specific position of the cyclic sulfonate ester.
  • at least one of R 1 and R 2 is a hydrogen atom. It is presumed that, due to the absence, the reactivity between the decomposition product of the supporting salt and the cyclic sulfonic acid ester decreases, and the generation of free acid from the electrolytic solution can be suppressed.
  • the compound of the general formula (1) is preferably a compound in which at least one of R 1 and R 2 is an alkyl group, and in particular, one is an alkyl group and the other is a hydrogen atom, or both are alkyl groups.
  • a certain compound is preferable, and a compound in which one is an alkyl group and the other is a hydrogen atom is most preferable.
  • R 1 and R 2 is a compound other alkyl group is a hydrogen atom is most preferred reason, at least one of R 1 and R 2 is not hydrogen atom (i.e., at least one of substituents of R 1 and R 2 Group), the reactivity of the supporting salt with the decomposition product is lowered.
  • at least one of R 1 and R 2 is not a hydrogen atom (that is, both R 1 and R 2 are substituents)
  • compared to the case where one is an alkyl group and the other is a hydrogen atom This is probably because the film-forming ability on the surface of the electrode active material is lowered, and the effect of extending the life of the lithium ion secondary battery is lowered.
  • Alkyl groups for R 1 and R 2 include methyl, ethyl, propyl, butyl and pentyl, which may be linear or branched. In particular, methyl, ethyl and propyl are preferable, and methyl and ethyl are more preferable.
  • the halogen for R 1 and R 2 include fluorine, chlorine, bromine and iodine. Among them, fluorine is preferable.
  • R 3 is an alkylene group having 1 to 5 carbon atoms, a carbonyl group, a sulfonyl group, a fluoroalkylene group having 1 to 6 carbon atoms, and an alkylene unit or a fluoroalkylene unit having 2 to 6 carbon atoms bonded via an ether group.
  • a linking group selected from the group consisting of divalent groups is shown.
  • the linking group represented by R 3 is asymmetric, either direction may be used.
  • the alkylene group and the fluoroalkylene group may be linear or branched, and are preferably linear.
  • the alkylene group - (CH 2) n - ( n is an integer of 1-5) is represented by, - (CH 2) n - ( n is 1 or 2) represented by A methylene group or an ethylene group is more preferable, and a methylene group represented by —CH 2 — is more preferable.
  • the branched alkylene group at least one hydrogen atom of the alkylene group represented by — (CH 2 ) n — (n is an integer of 1 to 4) is substituted with an alkyl group.
  • the fluoroalkylene group means that at least one of the hydrogen atoms of the alkylene group is substituted with a fluorine atom, and all the hydrogen atoms may be substituted with a fluorine atom, and the fluorine substitution position and the number of substitutions. Is optional.
  • the fluoroalkylene group may be linear or branched, and is preferably linear. In a linear fluoroalkylene group, when all hydrogen atoms are substituted with fluorine atoms, R 3 is represented by — (CF 2 ) n — (n is an integer of 1 to 5).
  • the fluoroalkylene group is preferably a monofluoromethylene group, a difluoromethylene group, a monofluoroethylene group, a difluoroethylene group, a trifluoroethylene group or a tetrafluoroethylene group.
  • a divalent group having 2 to 6 carbon atoms in which an alkylene unit or a fluoroalkylene unit is bonded via an ether group includes, for example, —R 4 —O—R 5 — ( R 4 and R 5 each independently represents an alkylene group or a fluoroalkylene group, and the total number of carbon atoms of R 4 and R 5 is 2 to 6), or —R 6 —O—R 7 —O— R 8 — (R 6 , R 7 and R 8 each independently represents an alkylene group or a fluoroalkylene group, and the total number of carbon atoms of R 6 , R 7 and R 8 is 3 to 6).
  • R 4 and R 5 may both be an alkylene group, or both may be a fluoroalkylene group, or one may be an alkylene group and the other may be a fluoroalkylene group.
  • R 6 , R 7 and R 8 may each independently be an alkylene group or a fluoroalkylene group.
  • —CH 2 —O—CH 2 —, —CH 2 —O—C 2 H 4 —, —C 2 H 4 —O—C 2 H 4 —, —CH 2 —O—CH 2 —O—CH 2 —, —CH 2 —O—CHF—, —CH 2 —O—CF 2 —, —CF 2 —O—CF 2 —, —C 2 F 4 —O—C 2 F 4 —, —CF 2 — O—CF 2 —O—CF 2 —, —CH 2 —O—CF 2 —O—CH 2 — and the like can be mentioned.
  • R 3 is preferably an alkylene group, a carbonyl group or a fluoroalkylene group, more preferably an alkylene group or a fluoroalkylene group, and — (CH 2 ) n — (n is 1 or 2 ), —C (CH 3 ) 2 —, —CH (CH 3 ) —, monofluoromethylene group, difluoromethylene group, monofluoroethylene group, difluoroethylene group, trifluoroethylene group or tetrafluoroethylene group. More preferred.
  • R 3 is preferably —CH 2 —, —C (CH 3 ) 2 —, —CH (CH 3 ) —, —CHF— or —CF 2 —, and —CH 2 — or —CF 2 -Is more preferable.
  • the reason for this is not clear, but when the compound represented by the formula (1) is a compound having a 6-membered ring structure, the electrochemical reactivity when forming a film as compared with the compound having a 7-membered ring structure It is presumed that this is because the resistance is lower, and a stronger and better quality film is formed.
  • R 3 is particularly preferably a methylene group represented by —CH 2 —.
  • R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen or an amino group, provided that both R 1 and R 2 are hydrogen atoms.
  • R 3 is a methylene group optionally substituted with fluorine.
  • R represents methyl, ethyl, propyl, butyl or pentyl, and preferably represents methyl or ethyl.
  • R represents methyl, ethyl, propyl, butyl or pentyl, and preferably represents methyl or ethyl.
  • Table 1 specifically illustrates representative examples of the compound represented by the general formula (1), but the present invention is not limited thereto.
  • R 1 is a methyl group or an ethyl group
  • R 2 is hydrogen
  • R 3 can be cited compounds is a methylene group or an ethylene group.
  • a compound in which R 1 is a methyl group or an ethyl group, R 2 is hydrogen, and R 3 is a methylene group is preferable, R 1 is a methyl group, R 2 is hydrogen, and R 3 is a methylene group. Certain compounds are more preferred.
  • the compounds represented by the general formula (1) may be used singly or in combination of two or more.
  • the compound of the general formula (1) is prepared by a production method described in, for example, US Pat. No. 4,950,768, JP-A 61-501089, JP-A 5-44946, JP-A 2005-336155, and the like. Can be obtained.
  • the proportion of the compound represented by the general formula (1) in the electrolytic solution is not particularly limited, but it is preferably contained at 0.005 to 10 wt% of the entire electrolytic solution.
  • concentration of the compound represented by the general formula (1) By setting the concentration of the compound represented by the general formula (1) to 0.005 wt% or more, a sufficient film effect can be obtained. More preferably, 0.01 wt% or more is added. By doing so, the battery characteristics can be further improved.
  • the raise of the viscosity of electrolyte solution and the increase in resistance accompanying it can be suppressed. More preferably, 5 wt% or less is added, and by doing so, the battery characteristics can be further improved.
  • the electrolyte solution can also contain other additives other than the above compounds, if necessary.
  • additives include an overcharge inhibitor and a surfactant.
  • the non-aqueous electrolyte is not particularly limited, and for example, the compound of the general formula (1) can be used as an additive to a solution obtained by dissolving a supporting salt in a non-aqueous solvent.
  • a lithium salt can be used as the supporting salt.
  • the lithium salt include LiPF 6 , lithium imide salt, LiAsF 6 , LiAlCl 4 , LiClO 4 , LiBF 4 , LiSbF 6, and the like.
  • the lithium imide salt include LiN (C k F 2k + 1 SO 2 ) (C m F 2m + 1 SO 2 ) (where k and m are each independently a natural number, preferably 1 or 2). It is done. These may use only 1 type and may use 2 or more types together.
  • the concentration of the lithium salt in the non-aqueous electrolyte is preferably 0.7 mol / L or more and 2.0 mol / L or less.
  • concentration of the lithium salt By setting the concentration of the lithium salt to 0.7 mol / L or more, sufficient ionic conductivity can be obtained.
  • concentration of lithium salt 2.0 mol / L or less a viscosity can be made low and the movement of lithium ion is not prevented.
  • the electrolytic solution preferably contains a cyclic carbonate as a nonaqueous electrolytic solvent.
  • the cyclic carbonate include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and vinylene carbonate (VC). Further, some or all of hydrogen in these compounds may be substituted with fluorine.
  • a cyclic carbonate can be used individually by 1 type or in mixture of 2 or more types. EC and PC are preferable because they have a high dielectric constant and excellent electrolyte solubility, and EC is more preferable.
  • the content of cyclic carbonate in the total nonaqueous electrolytic solvent is preferably 1 to 50% by volume, more preferably 5 to 40% by volume, and further preferably 10 to 40% by volume. If the content of the cyclic carbonate is too small, the conductivity of the electrolytic solution is lowered, and the cycle characteristics may be deteriorated. If the content of the cyclic carbonate is too large, the cyclic carbonate is likely to be decomposed at a high potential. Therefore, in a lithium ion secondary battery containing a 5V-class positive electrode active material, an increase in gas generation is likely to occur.
  • the nonaqueous electrolytic solvent is a fluorinated ether represented by the formula (2) (hereinafter sometimes simply referred to as “fluorinated ether”), the formula (3), in addition to the cyclic carbonate.
  • fluorinated ether represented by the formula (2)
  • fluorinated phosphoric acid esters hereinafter sometimes simply referred to as “fluorinated phosphoric acid esters”.
  • the nonaqueous electrolytic solvent can contain a fluorinated ether represented by the following formula (2).
  • R 101 and R 102 each independently represents an alkyl group or a fluorinated alkyl group, and at least one of R 101 and R 102 is a fluorinated alkyl group.
  • the total number of carbon atoms of R 101 and R 102 is preferably 10 or less.
  • the fluorinated alkyl group is an alkyl group having at least one fluorine atom.
  • the fluorine atom content in the fluorinated alkyl group is preferably 50% or more, more preferably 60% or more, based on the total of fluorine atoms and hydrogen atoms.
  • the withstand voltage is further improved, and even when a positive electrode active material that operates at a potential of 4.5 V or higher with respect to lithium is used, deterioration of battery capacity after cycling is more effectively reduced. Is possible.
  • fluorinated ether examples include CF 3 OCH 3 , CF 3 OC 2 H 5 , F (CF 2 ) 2 OCH 3 , F (CF 2 ) 2 OC 2 H 5 , and CF 3 (CF 2 ).
  • the content of the fluorinated ether compound represented by the formula (2) is preferably 0% by volume or more and 90% by volume or less in the nonaqueous electrolytic solvent, and preferably 15% by volume or more and 80% by volume or less, More preferably, it is 30 volume% or more and 70 volume% or less.
  • the content of the fluorinated ether is too large, the dielectric constant of the electrolytic solution is lowered, the supporting salt cannot be dissociated, and the capacity is similarly reduced.
  • the fluorinated ether has high oxidation resistance, the oxidative decomposition of the solvent can be suppressed in a lithium ion secondary battery containing a 5V class active material. As a result, it is possible to improve the capacity maintenance rate of the charge / discharge cycle and reduce gas generation.
  • the nonaqueous electrolytic solvent can contain a fluorinated phosphate ester represented by the following formula (3).
  • R 1 , R 2 and R 3 each independently represents an alkyl group or a fluorinated alkyl group, and at least one of them is a fluorinated alkyl group.
  • the fluorinated alkyl group is an alkyl group having at least one fluorine atom.
  • R 1 , R 2 and R 3 each independently have 1 to 3 carbon atoms.
  • At least one of R 1 , R 2 and R 3 is preferably a fluorinated alkyl group in which 50% or more of the hydrogen atoms of the corresponding unsubstituted alkyl group are substituted with fluorine atoms.
  • all of R 1 , R 2 and R 3 are fluorinated alkyl groups, and 50% or more of the hydrogen atoms of the unsubstituted alkyl group to which R 1 , R 2 and R 3 correspond are substituted with fluorine atoms.
  • a fluorinated alkyl group More preferred is a fluorinated alkyl group.
  • the content of fluorine atoms is large, the voltage resistance is further improved, and even when a positive electrode active material that operates at a potential of 4.5 V or higher with respect to lithium is used, the deterioration of battery capacity after cycling is further reduced. Because it can.
  • the ratio of fluorine atoms in the substituent containing a hydrogen atom in the fluorinated alkyl group is more preferably 55% or more.
  • fluorinated phosphate ester examples include, but are not limited to, for example, tris (trifluoromethyl) phosphate, tris (pentafluoroethyl) phosphate, tris phosphate.
  • (2,2,2-trifluoroethyl) Tris (2,2,2-trifluoroethyl) phosphate (TTFP)] tris (2,2,3,3-tetrafluoropropyl) phosphate (Tris (2,2 , 3,3-tetrafluoropropyl) phosphate), tris (3,3,3-trifluoropropyl) phosphate (Tris (3,3,3-trifluorofluoro) phosphate), Phosphate tris (2,2,3,3,3-pentafluoro-propyl) (Tris (2,2,3,3,3-pentafluoropropyl) phosphate) fluorinated alkyl phosphoric acid ester compounds and the like.
  • the content of the fluorinated phosphate ester contained in the nonaqueous electrolytic solvent is not particularly limited, but is preferably 0% by volume to 95% by volume in the nonaqueous electrolytic solvent, and is preferably 10% by volume to 95% by volume. Is more preferable, and 20 volume% or more and 70 volume% or less are further more preferable.
  • the content of the fluorinated phosphate ester in the nonaqueous electrolytic solvent is 10% by volume or more, the effect of increasing the voltage resistance is further improved.
  • the ion conductivity of electrolyte solution improves that the content rate in the nonaqueous electrolytic solvent of fluorinated phosphate ester is 95 volume% or less, and the charge / discharge rate of a battery becomes more favorable.
  • the fluorinated phosphate ester also has high oxidation resistance, oxidative decomposition of the solvent when a 5V class active material is used can be suppressed. As a result, it is possible to improve the capacity maintenance rate of the charge / discharge cycle and reduce gas generation.
  • the nonaqueous electrolytic solvent includes at least one selected from fluorinated ethers and fluorinated phosphates, and may include two or more.
  • the higher the concentration of these solvents the better the decomposition of the electrolytic solution is suppressed.
  • the nonaqueous electrolytic solvent may further contain a chain carbonate. Since the cyclic carbonate has a high viscosity, the viscosity can be reduced by mixing the chain carbonate.
  • the chain carbonate include dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), dipropyl carbonate (DPC), and derivatives thereof (including fluorinated products).
  • the nonaqueous electrolytic solvent may contain an aliphatic carboxylic acid ester, ⁇ -lactone, a cyclic ether, a chain ether other than the above formula (2), and the like.
  • the aliphatic carboxylic acid ester include methyl formate, methyl acetate, ethyl propionate, and derivatives thereof (including fluorinated products).
  • ⁇ -lactone include ⁇ -butyrolactone and its derivatives (including fluorinated products).
  • the cyclic ether include tetrahydrofuran, 2-methyltetrahydrofuran and derivatives thereof (including fluorinated products).
  • chain ether examples include 1,2-ethoxyethane (DEE), ethoxymethoxyethane (EME), diethyl ether, and derivatives thereof (including fluorinated compounds). These can be used individually by 1 type or in mixture of 2 or more types.
  • non-aqueous electrolytic solvents for example, dimethyl sulfoxide, formamide, acetamide, dimethylformamide, dioxolane (for example, 1,3-dioxolane), acetonitrile, propionitrile, nitromethane, ethyl monoglyme, phosphate triester , Trimethoxymethane, dioxolane derivatives, 1,3-dimethyl-2-imidazolidinone, 3-methyl-2-oxazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, anisole, N-methylpyrrolidone, and derivatives thereof (fluorinated compounds) Can also be used.
  • dimethyl sulfoxide formamide
  • acetamide dimethylformamide
  • dioxolane for example, 1,3-dioxolane
  • acetonitrile for example, 1,3-dioxolane
  • propionitrile for example, 1,3-dioxo
  • the positive electrode in the present embodiment includes a positive electrode active material (5 V class active material) having an operating potential of 4.5 V or higher with respect to lithium metal. That is, the positive electrode active material used in the present embodiment has a charge / discharge region at 4.5 V or higher with respect to lithium metal.
  • the 5V class active material is preferably a lithium-containing composite oxide.
  • Examples of the 5V class active material of the lithium-containing composite oxide include spinel-type lithium manganese composite oxide, olivine-type lithium manganese-containing composite oxide, reverse spinel-type lithium manganese-containing composite oxide, Li 2 MnO 3 -based solid solution, and the like. Can be mentioned.
  • the positive electrode active material it is preferable to use a lithium manganese composite oxide represented by the following formula (4).
  • M includes only Ni or one or more of Co and Fe containing Ni as a main component.
  • A is more preferably one or more of B, Mg, Al, and Ti.
  • Z is more preferably F. Such a substitution element serves to stabilize the crystal structure and suppress the deterioration of the active material.
  • the average particle diameter (D 50 ) of the positive electrode active material is preferably 1 to 50 ⁇ m, and more preferably 5 to 25 ⁇ m.
  • the average particle diameter (D 50 ) of the positive electrode active material can be measured by a laser diffraction scattering method (microtrack method).
  • the 5V class active material is a positive electrode active material other than the above formula (4) as long as it is a positive electrode active material having a charge / discharge region of 4.5 V (vs. Li / Li + ) or more with respect to lithium metal. It doesn't matter. It is considered that the quality and stability of the film formed on the surface of the positive electrode active material are dominated by the potential and are not directly influenced by the composition of the active material.
  • Li x MPO 4 F y (0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 1, M is at least one of Co and Ni).
  • Si-containing composite oxide represented by Li x MSiO 4 (0 ⁇ x ⁇ 2, M: at least one of Mn, Fe and Co); Li x [Li a M b Mn 1-ab ] O 2 (0 ⁇ x ⁇ 1, 0.02 ⁇ a ⁇ 0.3, 0.1 ⁇ b ⁇ 0.7, M is at least Ni, Co, Fe and Cr
  • One type of positive electrode active material may be used alone, or two or more types may be used in combination.
  • a 4V class active material may be included.
  • these active materials are mixed with a conductive material such as carbon black granular graphite, flake graphite, carbon fiber, a binder such as polyvinylidene fluoride (PVDF), an acrylic polymer, and N-methyl-2- It can be obtained by dispersing and kneading in a solvent such as pyrrolidone (NMP) and applying this to a positive electrode current collector such as an aluminum foil.
  • a conductive material such as carbon black granular graphite, flake graphite, carbon fiber, a binder such as polyvinylidene fluoride (PVDF), an acrylic polymer, and N-methyl-2- It can be obtained by dispersing and kneading in a solvent such as pyrrolidone (NMP) and applying this to a positive electrode current collector such as an aluminum foil.
  • PVDF polyvinylidene fluoride
  • NMP pyrrolidone
  • the positive electrode current collector aluminum, nickel, silver, and alloys thereof are preferable.
  • the shape include foil, flat plate, and 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.
  • the negative electrode active material used for the layer 2 containing the negative electrode active material is selected from the group consisting of, for example, lithium metal, a lithium alloy, and a material capable of inserting and extracting lithium.
  • One or more substances can be used. Examples of materials that occlude and release lithium ions include carbon materials and oxides.
  • the carbon material examples include graphite that absorbs lithium, amorphous carbon, diamond-like carbon, carbon nanotubes, and composite oxides thereof. Of these, graphite material or amorphous carbon is preferable.
  • the graphite material has high electron conductivity, excellent adhesion to a current collector made of a metal such as copper, and voltage flatness, and is formed at a high processing temperature, so it contains few impurities and has negative electrode performance. It is advantageous for improvement and is preferable.
  • the oxide examples include silicon oxide, tin oxide, indium oxide, zinc oxide, lithium oxide, phosphorus oxide (phosphoric acid), boric oxide, and a composite thereof.
  • silicon oxide is preferably included.
  • the structure is preferably in an amorphous state. This is because silicon oxide is stable and does not cause a reaction with other compounds, and the amorphous structure does not lead to deterioration due to nonuniformity such as crystal grain boundaries and defects.
  • a film forming method a vapor deposition method, a CVD method, a sputtering method, or the like can be used.
  • the lithium alloy is composed of lithium and a metal capable of forming an alloy with lithium.
  • the lithium alloy is, for example, a binary or ternary alloy of a metal such as Al, Si, Pb, Sn, In, Bi, Ag, Ba, Ca, Hg, Pd, Pt, Te, Zn, La, and lithium. Consists of.
  • As the lithium metal or lithium alloy an amorphous one is particularly preferable. This is because the amorphous structure hardly causes deterioration due to non-uniformity such as crystal grain boundaries and defects.
  • Lithium metal or lithium alloy is formed by an appropriate method such as a melt cooling method, a liquid quenching method, an atomizing method, a vacuum deposition method, a sputtering method, a plasma CVD method, a photo CVD method, a thermal CVD method, a sol-gel method, etc. can do.
  • binder for the negative electrode examples include polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, styrene-butadiene copolymer rubber, polytetrafluoroethylene, polypropylene, polyethylene, Polyimide, polyamideimide, or the like can be used.
  • the amount of the binder for the negative electrode used is 0.5 to 25 parts by mass with respect to 100 parts by mass of the negative electrode active material from the viewpoints of “sufficient binding force” and “high energy” which are in a trade-off relationship. Is preferred.
  • the negative electrode current collector aluminum, nickel, copper, silver, and alloys thereof are preferable in view of electrochemical stability.
  • Examples of the shape include foil, flat plate, and mesh.
  • 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 by a method such as vapor deposition or sputtering to form a negative electrode current collector.
  • FIG. 1 is an example of a schematic configuration diagram of a secondary battery using the nonaqueous electrolytic solution of the present invention.
  • the battery according to the present invention has a structure as shown in FIG.
  • the layer 1 containing the positive electrode active material was formed on the positive electrode current collector 3
  • the layer 2 containing the negative electrode active material was formed on the negative electrode current collector 4. Is.
  • These positive electrode and negative electrode are arranged to face each other with a porous separator 5 interposed therebetween.
  • the porous separator 5 is disposed substantially parallel to the layer 2 containing the negative electrode active material.
  • the electrode element in which the positive electrode and the negative electrode are arranged to face each other, and the electrolytic solution are included in the exterior bodies 6 and 7.
  • a positive electrode tab 9 is connected to the positive electrode current collector 3
  • a negative electrode tab 8 is connected to the negative electrode current collector 4, and these tabs are drawn out of the container.
  • the shape of the non-aqueous electrolyte secondary battery according to the present embodiment is not particularly limited, and examples thereof include a laminate exterior type, a cylindrical type, a square type, and a coin type.
  • the non-aqueous electrolyte secondary battery of FIG. 1 has a negative electrode and a positive electrode laminated via a porous separator 5 in a dry air or inert gas atmosphere. It accommodates in exterior bodies, such as a flexible film which consists of a laminated body of resin and metal foil, and is impregnated with the nonaqueous electrolyte solution containing the cyclic sulfonate ester represented by the said General formula (1) as an additive. And a favorable membrane
  • coat can be formed on a negative electrode by charging a non-aqueous-electrolyte secondary battery before sealing an exterior body or after sealing.
  • porous separator 5 porous films, such as polyolefin, such as a polypropylene and polyethylene, a fluororesin, are used.
  • the exterior body can be appropriately selected as long as it is stable to the electrolytic solution and has a sufficient water vapor barrier property.
  • a laminate film made of aluminum, silica-coated polypropylene, polyethylene, or the like can be used as the outer package.
  • Example 1 (Production of battery) The production of the battery of this example will be described.
  • An aluminum foil having a thickness of 20 ⁇ m was used as the positive electrode current collector, and LiNi 0.5 Mn 1.5 O 4 (hereinafter referred to as positive electrode active material A) was used as the positive electrode active material.
  • a 15 ⁇ m thick copper foil was used as the negative electrode current collector, and graphite was used as the negative electrode active material.
  • the negative electrode and the positive electrode were laminated
  • electrolyte solution A a solvent for the nonaqueous electrolyte solution to form a nonaqueous solvent
  • LiPF 6 was dissolved in the non-aqueous electrolyte so as to be 0.8 mol / L as a supporting electrolyte salt.
  • the compound No. described in Table 1 above is used as an additive. 1 was added so that 0.05 mol / L was contained in the non-aqueous electrolyte. The secondary battery was produced using this non-aqueous electrolyte.
  • Example 2 In Example 1, compound no. In place of compound 1, compound no. A secondary battery was fabricated in the same manner as in Example 1 except that 5 was used.
  • Example 3 In Example 1, compound no. In place of compound 1, compound no. A secondary battery was fabricated in the same manner as in Example 1 except that 7.
  • Example 4 In Example 1, compound no. In place of compound 1, compound no. A secondary battery was fabricated in the same manner as in Example 1 except that 8 was used.
  • Example 5 In Example 1, compound no. In place of compound 1, compound no. A secondary battery was fabricated in the same manner as in Example 1 except that 9 was used.
  • Example 1 compound no. A secondary battery was fabricated in the same manner as in Example 1 except that methylenemethane disulfonate (hereinafter referred to as “Compound A”) was used instead of 1.
  • Compound A methylenemethane disulfonate
  • Example 6 In Example 5, except that the positive electrode active material is changed to the positive electrode active material A and LiNi 0.5 Mn 1.3 Ti 0.2 O 4 (hereinafter referred to as positive electrode active material B), Similarly, a secondary battery was produced.
  • electrolyte solution B a non-aqueous solvent
  • a secondary battery was produced in the same manner as in Example 5 except that the above was prepared using
  • Example 8 a secondary battery was fabricated in the same manner as in Example 6 except that the electrolytic solution was changed to the electrolytic solution A and the electrolytic solution B was used. The results are shown in Table 4.
  • Examples of use of the present invention include driving devices such as electric vehicles, 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 generation. Examples include storage batteries such as systems.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne une batterie secondaire à ion lithium comprenant une électrode positive, une électrode négative et une solution d'électrolyte non-aqueux. L'invention est caractérisée en ce que l'électrode positive contient un matériau actif d'électrode positive ayant un potentiel opérationnel de 4,5 V ou plus par rapport au métal lithium ; et en ce que la solution d'électrolyte non-aqueux contient un ester d'acide sulfonique cyclique représenté par la formule (1). La présente invention concerne une batterie secondaire à ion lithium contenant un matériau actif de catégorie 5V, ladite batterie secondaire ayant d'excellentes caractéristiques de rétention de capacité. (Dans la formule (1), R1 et R2 représentent chacun indépendamment un atome d'hydrogène, un groupe alkyle ayant 1-5 atomes de carbone, un groupe halogène ou un groupe amino, à condition que R1 et R2 ne soient pas des atomes d'hydrogène en même temps ; et R3 représente un groupe de liaison choisi dans le groupe constitué d'un groupe alcylène ayant 1-5 atomes de carbone, d'un groupe carbonyle, d'un groupe sulfonyle, d'un groupe fluoroalcylène ayant 1-6 atomes de carbone, et d'un groupe divalent ayant 2-6 atomes de carbone, auquel une unité alcylène ou une unité fluoroalcylène est liée par un groupe éther.)
PCT/JP2014/055169 2013-03-01 2014-02-28 Batterie secondaire à électrolyte non-aqueux WO2014133161A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2015503063A JPWO2014133161A1 (ja) 2013-03-01 2014-02-28 非水電解液二次電池

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013041323 2013-03-01
JP2013-041323 2013-03-01

Publications (1)

Publication Number Publication Date
WO2014133161A1 true WO2014133161A1 (fr) 2014-09-04

Family

ID=51428419

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/055169 WO2014133161A1 (fr) 2013-03-01 2014-02-28 Batterie secondaire à électrolyte non-aqueux

Country Status (2)

Country Link
JP (1) JPWO2014133161A1 (fr)
WO (1) WO2014133161A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11450888B2 (en) 2017-08-10 2022-09-20 Gs Yuasa International Ltd. Nonaqueous electrolyte and nonaqueous electrolyte energy storage device

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004281368A (ja) * 2002-08-29 2004-10-07 Nec Corp 二次電池用電解液およびそれを用いた二次電池
JP2004281325A (ja) * 2003-03-18 2004-10-07 Nec Corp 二次電池用電解液およびそれを用いた二次電池
JP2008153118A (ja) * 2006-12-19 2008-07-03 Nec Tokin Corp 非水電解液およびそれを用いた非水電解液二次電池
WO2011096572A1 (fr) * 2010-02-08 2011-08-11 Ｎｅｃエナジーデバイス株式会社 Batterie secondaire à électrolyte non aqueux

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004281368A (ja) * 2002-08-29 2004-10-07 Nec Corp 二次電池用電解液およびそれを用いた二次電池
JP2004281325A (ja) * 2003-03-18 2004-10-07 Nec Corp 二次電池用電解液およびそれを用いた二次電池
JP2008153118A (ja) * 2006-12-19 2008-07-03 Nec Tokin Corp 非水電解液およびそれを用いた非水電解液二次電池
WO2011096572A1 (fr) * 2010-02-08 2011-08-11 Ｎｅｃエナジーデバイス株式会社 Batterie secondaire à électrolyte non aqueux

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11450888B2 (en) 2017-08-10 2022-09-20 Gs Yuasa International Ltd. Nonaqueous electrolyte and nonaqueous electrolyte energy storage device

Also Published As

Publication number Publication date
JPWO2014133161A1 (ja) 2017-02-09

Similar Documents

Publication Publication Date Title
JP6380376B2 (ja) 非水電解液二次電池
US20180108935A1 (en) Electrolyte solution for secondary batteries, and secondary battery
CN110720156B (zh) 锂离子二次电池
WO2013005521A1 (fr) Batterie secondaire
WO2015037451A1 (fr) Batterie secondaire au lithium-ion
US10749215B2 (en) Electrolyte solution for secondary battery and secondary battery
JP6380377B2 (ja) リチウムイオン二次電池
JP7062171B2 (ja) 電解質及びこれを含むリチウム二次電池
JP6341195B2 (ja) 二次電池用電解液およびそれを用いた二次電池
WO2016021596A1 (fr) Batterie rechargeable au lithium et son procédé de fabrication
JP2015115268A (ja) 非水電解質二次電池
JP4304570B2 (ja) 非水電解液およびそれを用いた二次電池
WO2013042503A1 (fr) Batterie secondaire non aqueuse
JP6500775B2 (ja) リチウムイオン二次電池
JP6319092B2 (ja) 二次電池
JP4265169B2 (ja) 二次電池用電解液およびそれを用いた二次電池
CN111052486B (zh) 非水电解质二次电池
JP4525018B2 (ja) リチウム二次電池用電解液およびそれを用いたリチウム二次電池
WO2014133161A1 (fr) Batterie secondaire à électrolyte non-aqueux
JP6086116B2 (ja) リチウム二次電池用電解液およびこれを含むリチウム二次電池
JP6179511B2 (ja) リチウム二次電池
JP5369017B2 (ja) リチウムイオン二次電池用電解液及びリチウムイオン二次電池
CN115720687A (zh) 非水电解液用添加剂、非水电解液及蓄电器件
CN116941088A (zh) 锂二次电池用非水电解液及包含其的锂二次电池
JP2023525314A (ja) リチウム二次電池用非水電解液及びこれを含むリチウム二次電池

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14756902

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2015503063

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14756902

Country of ref document: EP

Kind code of ref document: A1