WO2016027583A1 - Solution électrolytique de batteries rechargeables non aqueuses, batterie rechargeable non aqueuse, et additif utilisé pour une solution électrolytique de batteries rechargeables non aqueuses - Google Patents

Solution électrolytique de batteries rechargeables non aqueuses, batterie rechargeable non aqueuse, et additif utilisé pour une solution électrolytique de batteries rechargeables non aqueuses Download PDF

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WO2016027583A1
WO2016027583A1 PCT/JP2015/069655 JP2015069655W WO2016027583A1 WO 2016027583 A1 WO2016027583 A1 WO 2016027583A1 JP 2015069655 W JP2015069655 W JP 2015069655W WO 2016027583 A1 WO2016027583 A1 WO 2016027583A1
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group
secondary battery
atom
carbon atoms
electrolyte solution
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PCT/JP2015/069655
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Japanese (ja)
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吉憲 金澤
郁雄 木下
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富士フイルム株式会社
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Priority to JP2016543861A priority Critical patent/JP6376709B2/ja
Publication of WO2016027583A1 publication Critical patent/WO2016027583A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • 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 non-aqueous secondary battery, a non-aqueous secondary battery using the same, and an additive used in these.
  • Lithium ion secondary batteries can achieve a large energy density in charge and discharge compared to lead batteries and nickel cadmium batteries. Utilizing this characteristic, application to portable electronic devices such as mobile phones and notebook personal computers is widespread. Recently, development of a secondary battery that is particularly lightweight and capable of obtaining a high energy density has been underway. Further, there is a demand for miniaturization and long life.
  • Lithium ion secondary batteries have a wide variety of applications and are increasingly expanding. Therefore, further improvement in battery performance is desired, and in particular, improvement in cycle characteristics is desired. In addition, from the diversification of applications, a battery having higher reliability and better battery performance is desired.
  • An object of the present invention is to provide an electrolyte for a non-aqueous secondary battery that can improve cycle characteristics in a non-aqueous secondary battery, and an additive used therefor. Furthermore, an object of the present invention is to provide an electrolyte for a non-aqueous secondary battery that can improve cycle characteristics and improve flame retardancy, and an additive used therefor. It is another object of the present invention to provide a non-aqueous secondary battery using an electrolytic solution having such excellent characteristics.
  • M represents a metal element.
  • R 1 and R 2 each independently represents a substituent. When there are a plurality of R 1 and R 2 , a plurality of R 1 or a plurality of R 2 may be bonded to each other to form an aliphatic or aromatic ring.
  • X and Y each independently represent a hydrogen atom or a substituent.
  • X and Y, or a plurality of Xs or Ys in the case where a plurality exist may be bonded to each other to form a ring.
  • L represents a linking group.
  • a and b each independently represents an integer of 0 to 4.
  • m and n represent integers satisfying 0 ⁇ m + n ⁇ 3.
  • (2) L includes a hydrocarbon group having 1 to 20 carbon atoms, a group containing a halogen atom, a group containing a silicon atom, a group containing a nitrogen atom, a group containing a phosphorus atom, a group containing a titanium atom, or a zirconium atom Electrolyte for non-aqueous secondary batteries as described in (1) which is group.
  • R 1 and R 2 are each independently an alkyl group, alkenyl group, alkynyl group, alkoxy group, alkylthio group, aryloxy group, amino group, group containing an amide bond, group containing an ester bond, cyano group , A carboxyl group, a group containing a carbonyl bond, a group containing a sulfonyl bond, a phosphino group, or a halogen atom, (1) or (2).
  • X and Y are each independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group, alkylamino group, silylamino group, sulfo group, isocyanate group, isothiocyanate group, sulfanyl group,
  • the electrolyte solution for a non-aqueous secondary battery according to any one of (1) to (3), which is a phosphinyl group, a group containing a carbonyl bond, a halogen atom, an aryl group, or a heteroaryl group.
  • R 3 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an alkylamino group, a silylamino group, a sulfo group, an isocyanate group, an isothiocyanate group, It represents a sulfanyl group, a phosphinyl group, a group containing a carbonyl bond, a halogen atom, an aryl group or a heteroaryl group.
  • the plurality of R 3 may be the same even if different from each other.
  • a plurality of R 3 may be bonded to each other to form a ring.
  • Ra 11 to Ra 16 and Ra 21 to Ra 28 each independently represent a monovalent substituent.
  • the adjacent Ra 11 to Ra 16 and Ra 21 to Ra 28 may be bonded to each other to form a ring.
  • (9) The electrolyte solution for a non-aqueous secondary battery according to (8), wherein the compound represented by the formula (A1) is a fluorinated phosphazene compound represented by the following formula (A1-1).
  • Ra 41 represents an alkoxy group or a dialkylamino group.
  • M represents a metal element.
  • R 1 and R 2 each independently represents a substituent. When there are a plurality of R 1 and R 2 , a plurality of R 1 or a plurality of R 2 may be bonded to each other to form an aliphatic or aromatic ring.
  • X and Y each independently represent a hydrogen atom or a substituent.
  • X and Y, or a plurality of Xs or Ys in the case where a plurality exist may be bonded to each other to form a ring.
  • L represents a linking group.
  • a and b each independently represents an integer of 0 to 4.
  • m and n represent integers satisfying 0 ⁇ m + n ⁇ 3.
  • substituents and the like may be the same as or different from each other. Further, when a plurality of substituents and the like are close to each other, they may be bonded to each other to form a ring. In the case of a substituent on the ring, a plurality of substituents are bonded to form a ring, and the original ring And may form a condensed ring. Further, in the present specification, when simply referred to as a substituent, the substituent T is referred to. In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the electrolyte solution for a non-aqueous secondary battery and the additive of the present invention can improve cycle characteristics in the non-aqueous secondary battery. Moreover, cycle characteristics can be improved and flame retardancy can be improved. Thereby, the non-aqueous secondary battery of the present invention exhibits excellent cycle characteristics and reliability as well as good battery performance.
  • the electrolyte solution for non-aqueous secondary batteries of the present invention (also referred to as electrolyte solution) contains an organometallic compound represented by the following formula (I).
  • the additive (also referred to as an electrolyte additive) used in the electrolyte solution for non-aqueous secondary batteries of the present invention is an organometallic compound represented by the following formula (I).
  • M represents a metal element.
  • R 1 and R 2 each independently represents a substituent. When there are a plurality of R 1 and R 2 , a plurality of R 1 or a plurality of R 2 may be bonded to each other to form an aliphatic or aromatic ring.
  • X and Y each independently represent a hydrogen atom or a substituent.
  • X and Y, or a plurality of Xs or Ys in the case where a plurality exist may be bonded to each other to form a ring.
  • L represents a linking group.
  • a and b each independently represents an integer of 0 to 4.
  • m and n represent integers satisfying 0 ⁇ m + n ⁇ 3.
  • M represents a metal element.
  • M is preferably a transition element or a rare earth element, more preferably a transition element of Group 4 to Group 8 or a lanthanoid, still more preferably a transition element of Group 4, 5 or 8, and a group 4 or 8 Group transition elements are particularly preferred, and Group 8 transition elements are most preferred.
  • M is preferably Fe, Ru, Cr, V, Ta, Mo, Ti, Zr, Hf, Y, La, Ce, Sw, Nd, Lu, Er, Yb, Gd, and Ti, Zr, Hf, V, Nb, Fe, and Ru are more preferable, Ti, Zr, Fe, and V are more preferable, Ti, Zr, and Fe are particularly preferable, and Fe is most preferable.
  • R 1 , R 2 R 1 and R 2 represent a substituent.
  • substituents include the substituent T described later.
  • a linear or branched substituent may be an aliphatic or aromatic ring or a group containing such a ring.
  • ring groups include hydrocarbon ring groups such as cycloalkyl groups, cycloalkenyl groups, cycloalkynyl groups, and aryl groups (eg, phenyl, naphthyl), and nitrogen-containing heterocycles.
  • a heterocyclic group or a heteroaryl ring group (preferably a ring-constituting hetero atom is preferably an oxygen atom, a sulfur atom or a nitrogen atom, preferably a 5- or 6-membered ring group, and other ring (preferably a benzene ring or a hetero ring) ) May be condensed.).
  • R 1 and R 2 are preferably an alkyl group (preferably having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), an alkylsilyl group (preferably having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms).
  • An alkenyl group (preferably 2 to 6 carbon atoms, more preferably 2 or 3 carbon atoms), an alkynyl group (preferably 2 to 6 carbon atoms, more preferably 2 or 3 carbon atoms), an alkoxy group (preferably carbon atoms) 1 to 6, more preferably 1 to 3 carbon atoms, an alkylthio group (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), an aryloxy group (preferably 6 to 12 carbon atoms, more preferably Has 6 to 10 carbon atoms), an amino group (including an alkylamino group) (the carbon number is preferably 0 to 6, more preferably 1 to 6, still more preferably 2 to 6, and particularly preferably 2 to 4).
  • Amide A group containing a group (a carbamoyl group, an acylamino group, a ureido group and a urethane group are preferred, a carbamoyl group and an acylamino group are more preferred.
  • the number of carbon atoms is preferably 1 to 6, more preferably 1 to 3, more specifically, A group represented by C ( ⁇ O) —N (Ra) 2 , —N (Ra) —C ( ⁇ O) Ra), a group containing an ester bond (acyloxy group or oxycarbonyl group is preferred, carbon
  • the number is preferably 1 to 6, more preferably 1 to 4, and specifically, a group represented by —OC ( ⁇ O) —Ra, —C ( ⁇ O) —ORa is preferred), a cyano group, Carboxy group, group containing a carbonyl bond (acyl group is preferred, carbon number is preferably 2-7, more preferably 2-4, specifically, a group represented by —C ( ⁇ O) —Ra is preferred.
  • sulfonyl bonds (A sulfonyl group, a sulfonamido group, a sulfamoyl group are preferred, a sulfonyl group is more preferred.
  • the number of carbon atoms is preferably from 1 to 6, more preferably 1 to 3, specifically, the group represented by -SO 2 -Ra ),
  • Ra represents a hydrogen atom or a substituent, and examples of such a substituent include the substituent T described later.
  • a preferable substituent of the “substituent” includes the substituent T described later.
  • R 1 and R 2 are preferably an alkyl group, an alkylsilyl group, a phosphino group, and an amino group, and particularly preferably an alkyl group.
  • Specific preferred groups include a methyl group, an n-butyl group, a t-butyl group, a trimethylsilyl group, a dimethylphosphino group, a diethylphosphino group, a methylamino group, and an ethylamino group. Most preferred.
  • a and b each independently represents an integer of 0 to 4, preferably an integer of 0 to 3, and particularly preferably 0.
  • ⁇ X, Y X and Y each independently represent a hydrogen atom or a substituent.
  • substituent include the substituent T described later.
  • X and Y are an alkyl group (preferably having 1 to 8 carbon atoms, more preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms), an alkynyl group ( Preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms), an alkoxy group (preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms), an aryloxy group (preferably 6 to 12 carbon atoms).
  • an alkylamino group preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms
  • a silylamino group preferably 0 to 10 carbon atoms, more preferably 2 carbon atoms.
  • the number of carbon atoms is preferably 1 to 6, more preferably 1 to 3.
  • — C ( ⁇ O) —Ra, —O—C ( ⁇ O) —Ra is preferred
  • a halogen atom is preferred
  • an aryl group preferably having 6 to 22 carbon atoms, more preferably 6 to 10 carbon atoms
  • hetero Aryl group ring hetero atom is preferably oxygen atom, sulfur atom, nitrogen atom, ring member is preferably 5 or 6 member, and may be condensed with benzene ring or hetero ring. 2-4 are preferred There.
  • Ra represents a hydrogen atom or a substituent.
  • X and Y may be bonded to each other to form a ring.
  • the ring formed when X and Y are bonded to each other is preferably a ring including an M atom.
  • the bond forming the ring may be a single bond or a multiple bond.
  • a plurality of sulfanyl groups may be bonded and coordinated as a cyclic polysulfide.
  • An alkenyl group (butadiene coordination type metallacycle), a cyclic cumulene group in which a ring is formed by a double bond is preferable, an alkoxy group, a phenoxy group, and a cyclic alkenyl group in which X and Y form a ring by a single bond (butadiene coordination type) (Metallacycle), a cyclic cumulene group in which a ring is formed by a double bond is more preferable, a cyclic alkenyl group (butadiene-coordinated metallacycle) in which X and Y form a ring by a single bond, and a ring is formed by a double bond
  • a cyclic cumulene group is particularly preferred.
  • X and Y may further have a substituent, and examples thereof include the following substituent T.
  • R XY1 to R XY4 each independently represents a hydrogen atom or a substituent, and ** represents a bonding point for bonding to M.
  • R XY1 to R XY4 are preferably a hydrogen atom, an alkyl group, or a silyl group.
  • R XY1 and R XY4 are preferably sterically bulky groups, and tertiary alkyl groups (preferably t-butyl groups) and silyl groups (preferably trialkylsilyl groups) are particularly preferable.
  • n m and n are integers satisfying 0 ⁇ m + n ⁇ 3.
  • m + n is preferably 2 or less.
  • the plurality of groups defined therein may be the same as or different from each other.
  • M Fe
  • M is a metal element other than Fe, for example, Zr, V, and Ti
  • ⁇ L L represents a linking group.
  • a divalent hydrocarbon group having 1 to 20 carbon atoms, a group containing a halogen atom, a group containing a silicon atom, a group containing a nitrogen atom, a group containing a phosphorus atom, a group containing a titanium atom, or zirconium Groups containing atoms are preferred.
  • a divalent hydrocarbon group having 1 to 20 carbon atoms, a group containing a silicon atom, a group containing a phosphorus atom, a group containing a titanium atom or a group containing a zirconium atom is more preferred, and a divalent group having 1 to 20 carbon atoms.
  • hydrocarbon group More preferred are a hydrocarbon group, a group containing a silicon atom or a group containing a phosphorus atom, and a divalent hydrocarbon group having 1 to 20 carbon atoms and a group containing a silicon atom are particularly preferred.
  • L is preferably a group represented by any one of the following formulas (i) to (viii), and the formulas (i), (iii), (iv), (v), (vi), (vii), (viii) ) Is more preferred, and groups represented by formulas (i), (iii), (v), (vi), (vii), (viii) are more preferred, and formulas (i), (iii) ), (Vi), groups represented by (vii) are particularly preferred, and groups represented by formulas (i), (vi) are most preferred.
  • the following * indicates the point of attachment to each of the two cyclopentadienyl rings.
  • the bond between Ti or Zr and R 3 may be a single bond, an ionic bond, or a coordination bond via a ⁇ electron, but may be coordinated via a ⁇ electron.
  • a coordinate bond is preferred.
  • R 3 is a hydrogen atom, an alkyl group (preferably having 1 to 8 carbon atoms, more preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms), an alkynyl group (preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms), an alkoxy group (preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms), An aryloxy group (preferably having 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms), an alkylamino group (preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms), a silylamino group (preferably carbon atoms) having 0 to 10, more preferably 2 to 6 carbon atoms), a sulfo group, an isocyanate group (-NCO), isothiocyanate group (-NCS), sulfanyl
  • the ring may be condensed with a benzene ring or a hetero ring, and the number of carbon atoms is preferably 2 to 8, more preferably 2 to 4.
  • the aryl group in R 3 includes an aryl ring, and the heteroaryl group includes a heteroaryl ring. Preferred ranges thereof are also the same as the aryl group and heteroaryl group, respectively.
  • the aryl group herein includes a cyclopentadienyl group.
  • Ra represents a hydrogen atom or a substituent.
  • Each group of R 3 may further have a substituent, and examples of such a substituent include the substituent T described later.
  • R 3 is preferably a hydrogen atom, an alkyl group, an aryl group, an aryl ring, an alkoxy group, an aryloxy group, a heteroaryl group or a heteroaryl ring, and a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a phenyl group, A methoxy group, an ethoxy group, an isopropoxy group, a phenoxy group, a cyclopentadienyl group, or a cyclopentadiene ring is more preferable.
  • a plurality of R 3 present in the linking group may be different from each other or the same.
  • a plurality of R 3 may be bonded to each other to form a ring.
  • TMS is a trimethylsilyl group [—Si (CH 3 ) 3 ]
  • t-Bu is a t-butyl group [—C 4 H 9 -t ]
  • Et is an ethyl group [—C 2 H 5 ].
  • the method for producing the organometallic compound represented by the general formula (I) of the present invention is not particularly limited.
  • the organometallic compound represented by the formula (I) of the present invention may be used alone or in combination of two or more.
  • Content in the electrolyte solution for non-aqueous secondary batteries of the organometallic compound represented by Formula (I) is more than 0 mass% and 1 mass% or less with respect to the whole quantity containing an electrolyte. By making it in such a range, the effect of improving battery characteristics is effectively exhibited. In particular, 1% by mass or less is preferable because battery performance is not impaired.
  • the content of the organometallic compound represented by the formula (I) is preferably 0.001% by mass or more and 1% by mass or less, more preferably 0.005% by mass or more and 1% by mass or less, and still more preferably. Is preferably 0.01% by mass or more and 1% by mass or less, particularly preferably. It is 0.01 mass% or more and 0.5 mass% or less, Most preferably, it is 0.01 mass% or more and 0.2 mass% or less.
  • the organometallic compound represented by the formula (I) of the present invention crosslinks the cyclopentadiene ring of the metallocene, thereby giving distortion and destabilizing the compound itself, thereby oxidatively decomposing the metal compound of the present invention. Is promoted. As a result, even a battery with a low driving voltage could form a film on the positive electrode, and it seems that the cycle characteristics were greatly improved and the resistance was reduced.
  • the electrolyte for a non-aqueous secondary battery of the present invention preferably further contains a phosphazene compound.
  • the phosphazene compound used in the electrolyte solution for a non-aqueous secondary battery of the present invention is preferably a compound represented by the following formula (A1) or the following formula (A2).
  • Ra 11 to Ra 16 and Ra 21 to Ra 28 each independently represent a monovalent substituent.
  • the adjacent Ra 11 to Ra 16 and Ra 21 to Ra 28 may be bonded to each other to form a ring.
  • Ra 11 to Ra 16 and Ra 21 to Ra 28 include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, particularly preferably a fluorine atom), an alkyl group (preferably having 1 to 12 carbon atoms, 1 to 6 are more preferable, and 1 to 3 are particularly preferable), an alkoxy group (including an alkoxy group substituted with an aryl group, an alkoxy group substituted with a fluorine atom, preferably having 1 to 12 carbon atoms, and preferably having 1 to 6 carbon atoms) More preferably, 1 to 3 is particularly preferable, an alkylthio group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and particularly preferably 1 to 3), an aryloxy group (preferably having 6 to 22 carbon atoms, 6 To 14 are more preferred), an arylthio group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms), an aral
  • Ra 11 to Ra 16 and Ra 21 to Ra 28 are preferably a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an aralkyl group or an amino group, and a halogen atom, an alkoxy group, an aryloxy group or An amino group is more preferable.
  • an unsubstituted alkoxy group such as a methoxy group, an ethoxy group, or a butoxy group, or a 2,2,2-trifluoroethoxy group, a 1,1,1,3,3,3-hexafluoroisopropoxy group
  • An alkoxy group substituted with a fluorine atom such as a perfluorobutylethyl group is preferred.
  • the aryloxy group is preferably a phenoxy group or a phenoxy group substituted with a fluorine atom.
  • 3 to 6 (preferably 4 or 5, more preferably 5) of Ra 11 to Ra 16 are fluorine atoms, and 0 to 3 (preferably 1 Or two, more preferably one) is preferably an alkoxy group, an aryloxy group or an amino group.
  • 5 to 8 (preferably 6 or 7, more preferably 7) of Ra 21 to Ra 28 are fluorine atoms, and 0 to 3 (preferably 1 Or two, more preferably one) is preferably an alkoxy group, an aryloxy group or an amino group.
  • the amino group in Ra 11 to Ra 16 and Ra 21 to Ra 28 preferably has a structure represented by the following formula (N1).
  • Ra 31 and Ra 32 are each independently a monovalent substituent, an alkyl group (preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, An alkyl group having 1 to 3 carbon atoms, an acyl group (an acyl group having 1 to 12 carbon atoms is preferable, an acyl group having 1 to 6 carbon atoms is more preferable, and an acyl group having 1 to 3 carbon atoms is particularly preferable) Or an aryl group (an aryl group having 6 to 22 carbon atoms is preferable, an aryl group having 6 to 14 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is particularly preferable).
  • an alkyl group preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, An alkyl group having 1 to 3 carbon atoms, an acyl group (an acyl group having
  • Ra 31 and Ra 32 may be bonded to each other or condensed to form a ring.
  • a hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom may be incorporated.
  • the ring formed is preferably a 5-membered ring or a 6-membered ring.
  • the 5-membered ring is preferably a compound containing a nitrogen-containing 5-membered ring, such as pyrrole, imidazole, pyrazole, indazole, indole, benzimidazole, pyrrolidine, imidazolidine, pyrazolidine, indoline, carbazole, or derivatives thereof (all N substitution).
  • Preferred examples of the 6-membered ring include piperidine, morpholine, piperazine, and derivatives thereof (all are N-substituted).
  • the compound represented by the above formula (A1) is preferably a fluorinated phosphazene compound represented by the following formula (A1-1) or the following formula (A1-2).
  • Ra 41 and Ra 42 have the same meaning as Ra 11 and are preferably an alkoxy group, an aryloxy group, a fluorine atom or an amino group. From the viewpoint of imparting flame retardancy to the electrolytic solution, Ra 41 and Ra 42 are preferably an alkoxy group or a dialkylamino group, and more preferably a dialkylamino group. As the dialkylamino group, an amino group represented by the above formula (N1) is preferably applied.
  • the phosphazene compound represented by the above formula (A1) is more preferably a fluorinated phosphazene compound represented by the above formula (A1-1) from the viewpoint of imparting flame retardancy to the electrolytic solution.
  • Me is a methyl group
  • Et is an ethyl group
  • Bu is a butyl group
  • Ph is a phenyl group.
  • the phosphazene compounds used in the present invention may be used singly or in combination of two or more. Further, the concentration of the phosphazene compound in the electrolyte solution for non-aqueous secondary batteries is not particularly limited, but the total amount including the electrolyte is preferably 0.5% by mass or more, and preferably 1% by mass or more. More preferred is 3% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less. By blending the phosphazene compound at the lower limit value or more, sufficient flame retardancy can be imparted, and good charge / discharge performance can be realized in battery performance.
  • phosphazene compound used in the present invention a commercially available compound can be used, or a compound obtained by modifying it can be used.
  • a fluorinated phosphazene compound substituted with an alkoxy group is a fluorinated phosphazene compound represented by (PNF 2 ) na (na represents 3 or 4).
  • R-OM r R is an alkyl group, M r in.
  • the electrolyte used in the electrolytic solution of the present invention is preferably a salt of a metal ion belonging to Group 1 or Group 2 of the periodic table.
  • the metal ion salt to be used is appropriately selected depending on the intended use of the electrolytic solution.
  • lithium salt, potassium salt, sodium salt, calcium salt, magnesium salt and the like can be mentioned.
  • lithium salt is preferable from the viewpoint of output.
  • a lithium salt may be selected as a metal ion salt.
  • the lithium salt normally used for the electrolyte of the nonaqueous electrolyte solution for lithium secondary batteries is preferable, For example, what is described below is preferable.
  • Inorganic lithium salts inorganic fluoride salts such as LiPF 6 , LiBF 4 , LiAsF 6 , LiSbF 6 ; perhalogenates such as LiClO 4 , LiBrO 4 , LiIO 4 ; inorganic chloride salts such as LiAlCl 4 etc
  • Oxalatoborate salt lithium bis (oxalato) borate, lithium difluorooxalatoborate, etc.
  • LiPF 6 , LiBF 4 , LiAsF 6 , LiSbF 6 , LiClO 4 , Li (Rf 1 SO 3 ), LiN (Rf 1 SO 2 ) 2 , LiN (FSO 2 ) 2 , and LiN (Rf 1 SO 2 ) (Rf 2 SO 2 ) are preferred, and lithium imides such as LiPF 6 , LiBF 4 , LiN (Rf 1 SO 2 ) 2 , LiN (FSO 2 ) 2 and LiN (Rf 1 SO 2 ) (Rf 2 SO 2 ) More preferred are salts.
  • Rf 1 and Rf 2 each represent a perfluoroalkyl group.
  • the electrolyte used for electrolyte solution may be used individually by 1 type, or may combine 2 or more types arbitrarily.
  • the electrolyte in the electrolytic solution (preferably a metal ion belonging to Group 1 or Group 2 of the periodic table or a metal salt thereof) is added in such an amount that a preferable salt concentration described below in the method for preparing the electrolytic solution is obtained. It is preferable.
  • the salt concentration is appropriately selected depending on the intended use of the electrolytic solution, but is generally 10% to 50% by mass, more preferably 15% to 30% by mass, based on the total mass of the electrolytic solution.
  • the molar concentration is preferably 0.5M to 1.5M.
  • concentration of ion what is necessary is just to calculate by salt conversion with the metal applied suitably.
  • Non-aqueous solvent As the non-aqueous solvent used in the present invention, an aprotic organic solvent is preferable, and an aprotic organic solvent having 2 to 10 carbon atoms is particularly preferable.
  • Such non-aqueous solvents include carbonate compounds, lactone compounds, chain or cyclic ether compounds, ester compounds, nitrile compounds, amide compounds, oxazolidinone compounds, nitro compounds, chain or cyclic sulfone or sulfoxide compounds, phosphoric acid. Examples include esters.
  • a compound having an ether bond, a carbonyl bond, an ester bond or a carbonate bond is preferable. These compounds may have a substituent, for example, the below-mentioned substituent T is mentioned.
  • non-aqueous solvent examples include ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, ⁇ -butyrolactone, ⁇ -valerolactone, 1,2-dimethoxyethane, tetrahydrofuran, 2 -Methyltetrahydrofuran, tetrahydropyran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,3-dioxane, 1,4-dioxane, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, butyric acid Methyl, methyl isobutyrate, methyl trimethylacetate, ethyl trimethylacetate, acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, 3-
  • ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate, and ⁇ -butyrolactone is preferable.
  • high viscosity high dielectric constant
  • ethylene carbonate or propylene carbonate A combination of a solvent (for example, relative dielectric constant ⁇ ⁇ 30) and a low viscosity solvent (for example, viscosity ⁇ 1 mPa ⁇ s) such as dimethyl carbonate, ethyl methyl carbonate, or diethyl carbonate is more preferable.
  • a mixed solvent of such a combination the dissociation property of the electrolyte salt and the ion mobility are improved.
  • the nonaqueous solvent used in the present invention is not limited to these.
  • the electrolyte solution of the present invention preferably contains various functional additives in order to improve flame retardancy, improve cycle characteristics, improve capacity characteristics, and the like. Examples of functional additives that are preferably applied to the electrolytic solution of the present invention are shown below.
  • Aromatic compounds include biphenyl compounds and alkyl-substituted benzene compounds.
  • the biphenyl compound has a partial structure in which two benzene rings are bonded by a single bond, and the benzene ring may have a substituent.
  • Preferred substituents are alkyl groups having 1 to 4 carbon atoms (for example, Methyl, ethyl, propyl, t-butyl, etc.) and aryl groups having 6 to 10 carbon atoms (eg, phenyl, naphthyl, etc.).
  • the biphenyl compound examples include biphenyl, o-terphenyl, m-terphenyl, p-terphenyl, 4-methylbiphenyl, 4-ethylbiphenyl, and 4-tert-butylbiphenyl.
  • the alkyl-substituted benzene compound is preferably a benzene compound substituted with an alkyl group having 1 to 10 carbon atoms, and specifically includes ethylbenzene, isopropylbenzene, cyclohexylbenzene, t-amylbenzene, t-butylbenzene, and tetrahydrohydronaphthalene. Can be mentioned.
  • the halogen atom contained in the compound having a halogen atom is preferably a fluorine atom, a chlorine atom or a bromine atom, and more preferably a fluorine atom.
  • the number of halogen atoms is preferably 1 to 6, more preferably 1 to 3.
  • the compound having a halogen atom is preferably a carbonate compound substituted with a fluorine atom, a polyether compound having a fluorine atom, or a fluorine-substituted aromatic compound.
  • the carbonate compound substituted with halogen may be either linear or cyclic.
  • a cyclic carbonate compound having a high coordination property of an electrolyte salt for example, lithium ion
  • a 5-membered cyclic carbonate compound is particularly preferable.
  • Preferred specific examples of the carbonate compound substituted with a halogen atom are shown below. Among these, compounds of Bex1 to Bex4 are particularly preferable, and Bex1 is most preferable.
  • a compound having a carbon-carbon double bond is preferable.
  • a carbonate compound having a double bond such as vinylene carbonate or vinyl ethylene carbonate, an acryloyloxy group, a methacryloyloxy group, a cyanoacryloyloxy group, ⁇ -CF 3
  • a compound having a group selected from an acryloyloxy group and a compound having a styryl group are preferred, and a carbonate compound having a double bond or a compound having two or more polymerizable groups in the molecule is more preferred.
  • the compound having a sulfur atom is preferably a compound containing a sulfur atom and having a —SO 2 —, —SO 3 —, —OS ( ⁇ O) O— bond, such as propane sultone, propene sultone, and ethylene sulfite. Cyclic sulfur-containing compounds and sulfonic acid esters are preferred.
  • sulfur-containing cyclic compound a compound represented by the following formula (E1) or (E2) is preferable.
  • X 1 and X 2 each independently represent —O— or —C (Ra1) (Rb1) —.
  • Ra1 and Rb1 each independently represent a hydrogen atom or a substituent.
  • the substituent is preferably an alkyl group having 1 to 8 carbon atoms, a fluorine atom, or an aryl group having 6 to 12 carbon atoms.
  • ⁇ represents an atomic group necessary for forming a 5- to 6-membered ring.
  • the skeleton of ⁇ may contain a sulfur atom, an oxygen atom, etc. in addition to a carbon atom.
  • ⁇ may be substituted, and examples of the substituent include a substituent T, preferably an alkyl group, a fluorine atom, and an aryl group.
  • R F1 represents an alkyl group, an alkenyl group, an acyl group, an acyloxy group, or an alkoxycarbonyl group.
  • R F2 represents an alkyl group, an alkenyl group, an alkynyl group or an alkoxy group.
  • a plurality of R F1 and R F2 in one formula may be different from each other or the same.
  • nitrile compound a compound represented by the following formula (G) is preferable.
  • R G1 to R G3 each independently represent a hydrogen atom, an alkyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a carbamoyl group, a sulfonyl group, a halogen atom or a phosphonyl group.
  • Preferred examples of each substituent can refer to the examples described in the corresponding group of the substituent T described later.
  • a nitrile compound in which any one of R G1 to R G3 contains a cyano group can be used. preferable.
  • Ng represents an integer from 1 to 8.
  • Specific examples of the compound represented by the formula (G) include acetonitrile, propionitrile, isobutyronitrile, succinonitrile, malononitrile, glutaronitrile, adiponitrile, 2-methylglutanonitrile, hexanetricarbonitrile, Propanetetracarbonitrile and the like are preferable. Particularly preferred are succinonitrile, malononitrile, glutaronitrile, adiponitrile, 2-methylglutanonitrile, hexanetricarbonitrile, and propanetetracarbonitrile.
  • the compound having a boron atom is preferably a compound represented by the following formulas (H1) to (H3).
  • R H1 and R H4 to R H11 are each independently an alkyl group, an alkoxy group, an alkylcarbonyloxy group, an aryl group, an aryloxy group, an arylcarbonyloxy group, a heteroaryl group, A heteroaryloxy group, a heteroarylcarbonyloxy group, an alkylamino group, an arylamino group, a cyano group, a carbamoyl group or a halogen atom;
  • a plurality of groups may be bonded to each other to form a ring.
  • R H2 and R H3 each independently represents an alkyl group, an alkylcarbonyl group, an aryl group, an arylcarbonyl group, a heteroaryl group, a heteroarylcarbonyl group, or a boron atom.
  • Z + represents an inorganic or organic cation, and is preferably an ammonium cation, Li + , Na + , or K + .
  • Specific examples of the compound having a boron atom include the following structures, more preferably Hex1, Hex2 or Hex10, and further preferably Hex10.
  • ⁇ Metal complex compound> In this invention, you may contain the metal complex compound different from the organometallic compound represented by Formula (I) with the organometallic compound represented by Formula (I) of this invention.
  • a metal complex compound a transition metal complex or a rare earth complex is preferable.
  • complexes represented by any of the following formulas (H-1) to (H-3) are preferred.
  • X H and Y H each independently represent a methyl group, an n-butyl group, a bis (trimethylsilyl) amino group or a thioisocyanate group.
  • X H and Y H are bonded to one another, with M H, it may form a cyclic alkenyl group (butadiene coordinated metallacycle).
  • MH represents a transition element or a rare earth element. Specifically, MH is preferably Fe, Ru, Cr, V, Ta, Mo, Ti, Zr, Hf, Y, La, Ce, Sw, Nd, Lu, Er, Yb, and Gd.
  • n H and n H are integers satisfying 0 ⁇ m H + n H ⁇ 3.
  • n H + m H is preferably 1 or more.
  • the 2 or more groups defined therein may be different from each other.
  • the metal complex compound is also preferably a compound having a partial structure represented by the following formula (H-4).
  • MH represents a transition element or a rare earth element, and is synonymous with the formulas (H-1) to (H-3), and the preferred range is also the same.
  • R 1H and R 2H are each a hydrogen atom, an alkyl group (preferably having 1 to 6 carbon atoms), an alkenyl group (preferably having 2 to 6 carbon atoms), an alkynyl group (preferably having 2 to 6 carbon atoms), an aryl group (preferably carbon atoms). The number represents 6 to 14), a heteroaryl group (preferably 3 to 6 carbon atoms), an alkylsilyl group (preferably 1 to 6 carbon atoms) or a halogen atom.
  • R 1H and R 2H may be bonded to each other to form a ring.
  • Such a ring is preferably a 5- to 6-membered ring, and examples thereof include a pyrrolidine ring, a piperidine ring, a piperazine ring, a morpholine ring, and a thiomorpholine ring.
  • R 1H and R 2H include examples of the substituent T described later. Of these, a methyl group, an ethyl group, and a trimethylsilyl group are preferable.
  • q H represents an integer of 1 to 4, preferably an integer of 2 to 4. More preferably, it is 2 or 4. When q H is 2 or more, where a plurality of groups as defined may be the same or different from each other.
  • the metal complex compound is also preferably a compound represented by any of the following formulas.
  • the central metal M h is, Ti, Zr, ZrO, Hf , V, Cr, Fe, Ce is particularly preferred, Ti, Zr, Hf, V , Cr is the most preferred.
  • R 3h , R 5h and R 7h to R 10h R 3h , R 5h and R 7h to R 10h represent a substituent.
  • an alkyl group, an alkoxy group, an aryl group, an alkenyl group, and a halogen atom are preferable.
  • alkenyl groups of 6 to 6 and methyl, ethyl, propyl, isopropyl, isobutyl, t-butyl, perfluoromethyl, methoxy, phenyl and ethenyl are further preferred.
  • R 33h and R 55h represent a hydrogen atom or a substituent of R 3h .
  • Examples of the substituent for R 3h include the substituent T described later.
  • Y h is preferably an alkyl group having 1 to 6 carbon atoms or a bis (trialkylsilyl) amino group, and more preferably a methyl group or a bis (trimethylsilyl) amino group.
  • ⁇ L h, m h and o h l h, m h and o h represents an integer of 0-3, an integer of 0 to 2 is preferred.
  • l h , m h and o h are 2 or more, the plurality of structural portions defined therein may be the same as or different from each other.
  • L h is preferably an alkylene group, a cycloalkylene group or an arylene group, more preferably a cycloalkylene group having 3 to 6 carbon atoms or an arylene group having 6 to 14 carbon atoms, and further preferably cyclohexylene or phenylene.
  • an imide compound in which all of the hydrogen atoms on the carbon atom are fluorinated is preferable, and a perfluorinated sulfonimide compound is preferable, specifically, perfluorinated.
  • a sulfoimide lithium compound is mentioned.
  • Specific examples of the imide compound include the following structures, and Cex1 and Cex2 are more preferable.
  • the electrolytic solution of the present invention may contain at least one selected from the above, a negative electrode film forming agent, a flame retardant, an overcharge preventing agent and the like.
  • the content ratio of these functional additives in the nonaqueous electrolytic solution is not particularly limited, and is preferably 0.001% by mass to 10% by mass with respect to the entire nonaqueous electrolytic solution (including the electrolyte).
  • a substituent that does not specify substitution / non-substitution means that the group may have an arbitrary substituent. This is also synonymous for compounds that do not specify substitution / non-substitution.
  • Preferred substituents include the following substituent T.
  • substituent T examples include the following.
  • An alkyl group preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.
  • alkenyl A group preferably an alkenyl group having 2 to 20 carbon atoms such as vinyl, allyl, oleyl and the like
  • an alkynyl group preferably an alkynyl group having 2 to 20 carbon atoms such as ethynyl, butynediynyl, phenylethynyl and the like
  • a cycloalkyl group preferably a cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclo
  • each group may be further substituted with the above-described substituent T.
  • substituent T For example, an aralkyl group in which an aryl group is substituted for an alkyl group.
  • a compound or a substituent / linking group includes an alkyl group / alkylene group, an alkenyl group / alkenylene group, an alkynyl group / alkynylene group, etc., these may be cyclic or linear, and may be linear or branched These may be substituted as described above or may be unsubstituted.
  • the nonaqueous electrolytic solution of the present invention is prepared by a conventional method by dissolving each of the above components in the nonaqueous electrolytic solution solvent, including an example in which a lithium salt is used as a metal ion salt.
  • non-water means that water is not substantially contained, and a trace amount of water may be contained as long as the effect of the invention is not hindered.
  • substantially not containing means that the concentration of water is 200 ppm (mass basis) or less, preferably 100 ppm or less, more preferably 20 ppm or less. Actually, it is difficult to make it completely anhydrous, and 1 ppm or more is included.
  • the viscosity of the electrolytic solution of the present invention is not particularly limited. At 25 ° C., 10 to 0.1 mPa ⁇ s is preferable, and 5 to 0.5 mPa ⁇ s is more preferable.
  • the viscosity of the electrolytic solution is measured using 1 mL of a sample in a rheometer (for example, CLS 500 manufactured by TA Instruments) and using Steel Cone (for example, manufactured by TA Instruments) having a diameter of 4 cm / 2 °.
  • the sample is kept warm in advance until the temperature becomes constant at the measurement start temperature, and the measurement starts thereafter.
  • the measurement temperature is 25 ° C.
  • the nonaqueous secondary battery of the present invention uses the above-described nonaqueous electrolyte of the present invention.
  • a lithium ion secondary battery will be described with reference to FIG.
  • the lithium ion secondary battery 10 of the present embodiment includes the electrolyte solution 5 for a non-aqueous secondary battery of the present invention and a positive electrode C capable of inserting and releasing lithium ions (a positive electrode current collector 1 and a positive electrode active material layer 2). And a negative electrode A (negative electrode current collector 3, negative electrode active material layer 4) capable of inserting and releasing lithium ions or dissolving and depositing lithium ions.
  • the separator 9 disposed between the positive electrode and the negative electrode, a current collecting terminal (not shown), an outer case, etc. ).
  • a protective element may be attached to at least one of the inside of the battery and the outside of the battery.
  • the battery shape to which the lithium secondary battery of the present embodiment is applied is not particularly limited, and examples thereof include a bottomed cylindrical shape, a bottomed square shape, a thin shape, a sheet shape, and a paper shape. Any of these may be used. Further, it may be of a different shape such as a horseshoe shape or a comb shape considering the shape of the system or device to be incorporated. Among them, from the viewpoint of efficiently releasing the heat inside the battery to the outside, a square shape such as a bottomed square shape or a thin shape having at least one surface that is relatively flat and has a large area is preferable.
  • FIG. 2 is an example of a bottomed cylindrical lithium secondary battery 100.
  • This battery is a bottomed cylindrical lithium secondary battery 100 in which a positive electrode sheet 14 and a negative electrode sheet 16 overlapped with a separator 12 are wound and accommodated in an outer can 18.
  • the 2S / T value is preferably 100 or more, and more preferably 200 or more.
  • the lithium secondary battery according to the present embodiment is configured to include the electrolytic solution 5, the positive electrode and negative electrode electrode mixture C and A, and the separator basic member 9, based on FIG. 1. Hereinafter, each of these members will be described.
  • Electrode mixture The electrode mixture is obtained by applying a dispersion of an active material and a conductive agent, a binder, a filler, etc. on a current collector (electrode substrate).
  • the active material is a positive electrode active material. It is preferable to use a negative electrode mixture in which the positive electrode mixture and the active material are negative electrode active materials.
  • each component in the dispersion (electrode composition) constituting the electrode mixture will be described.
  • a transition metal oxide for the positive electrode active material, and in particular, it has a transition element M a (one or more elements selected from Co, Ni, Fe, Mn, Cu, V). Is preferred. Further, mixed element M b (elements of the first (Ia) group of the metal periodic table other than lithium, elements of the second (IIa) group, Al, Ga, In, Ge, Sn, Pb, Sb, Bi, Si , P, B, etc.) may be mixed. Examples of such transition metal oxides include specific transition metal oxides including those represented by any of the following formulas (MA) to (MC), or other transition metal oxides such as V 2 O 5 , MnO 2. Etc.
  • a particulate positive electrode active material may be used. Specifically, a transition metal oxide capable of reversibly inserting and releasing lithium ions can be used, but the above-described specific transition metal oxide is preferably used.
  • the transition metal oxides, oxides containing the above transition element M a is preferably exemplified.
  • a mixed element M b (preferably Al) or the like may be mixed.
  • the mixing amount is preferably 0 to 30 mol% with respect to the amount of the transition metal. Further, it is more preferable that the molar ratio of Li / M a was synthesized were mixed so that 0.3 to 2.2.
  • M 1 are as defined above M a, and the preferred range is also the same.
  • aa represents 0 to 1.2, preferably 0.1 to 1.15, more preferably 0.6 to 1.1.
  • bb represents 1 to 3 and is preferably 2.
  • a part of M 1 may be substituted with the mixed element M b .
  • the transition metal oxide represented by the formula (MA) typically has a layered rock salt structure.
  • the transition metal oxide is more preferably represented by the following formulas.
  • g has the same meaning as the above aa, and the preferred range is also the same.
  • j represents 0.1 to 0.9.
  • i represents 0 to 1; However, 1-ji is 0 or more.
  • k has the same meaning as the above bb, and the preferred range is also the same.
  • transition metal compounds represented by the formulas (MA-1) to (MA-7) include LiCoO 2 (lithium cobaltate [LCO]), LiNi 2 O 2 (lithium nickelate) LiNi 0.85 Co 0.1 Al 0.05 O 2 (nickel cobalt lithium aluminum oxide [NCA]), LiNi 0.33 Co 0.33 Mn 0.33 O 2 (nickel manganese lithium cobalt oxide [NMC]), LiNi 0.5 Mn 0.5 O 2 (lithium manganese nickelate).
  • transition metal oxide represented by the formula (MA) partially overlaps, but when expressed in different notations, the following are also preferable examples.
  • M 2 are as defined above M a, and their preferable ranges are also the same.
  • c represents 0 to 2, preferably 0.1 to 1.15, and more preferably 0.6 to 1.5.
  • d represents 3 to 5 and is preferably 4.
  • the transition metal oxide represented by the formula (MB) is more preferably represented by the following formulas.
  • mm is synonymous with c, and the preferred range is also the same.
  • nn has the same meaning as d, and the preferred range is also the same.
  • p represents 0-2.
  • Specific examples of the transition metal compound include LiMn 2 O 4 and LiMn 1.5 Ni 0.5 O 4 .
  • transition metal oxide represented by the formula (MB) those represented by the following are also preferable examples.
  • an electrode containing Ni is more preferable from the viewpoint of high capacity and high output.
  • Transition metal oxide represented by formula (MC) As the lithium-containing transition metal oxide, it is also preferable to use a lithium-containing transition metal phosphor oxide, and among them, one represented by the following formula (MC) is also preferable.
  • e 0 to 2, preferably 0.1 to 1.15, and more preferably 0.5 to 1.5.
  • f represents 1 to 5, preferably 0.5 to 2.
  • M 3 represents one or more elements selected from V, Ti, Cr, Mn, Fe, Co, Ni, and Cu.
  • M 3 represents, in addition to the mixing element M b above, Ti, Cr, Zn, Zr, may be substituted by other metals such as Nb.
  • Specific examples include, for example, olivine-type iron phosphates such as LiFePO 4 and Li 3 Fe 2 (PO 4 ) 3 , iron pyrophosphates such as LiFeP 2 O 7 , cobalt phosphates such as LiCoPO 4 , and Li 3.
  • Monoclinic Nasicon type vanadium phosphate salts such as V 2 (PO 4 ) 3 (lithium vanadium phosphate) can be mentioned.
  • said aa, c, g, mm, and e value showing the composition of Li are the values which change by charging / discharging, and are typically evaluated by the value of the stable state when Li is contained.
  • the composition of Li is shown as a specific value, but this also varies depending on the operation of the battery.
  • a positive electrode active material containing Ni and / or Mn atoms is preferably used, and a positive electrode active material containing both Ni and Mn atoms is more preferably used.
  • particularly preferable positive electrode active materials include the following.
  • LiNi 0.33 Co 0.33 Mn 0.33 O 2 LiNi 0.6 Co 0.2 Mn 0.2 O 2 LiNi 0.5 Co 0.3 Mn 0.2 O 2 LiNi 0.5 Mn 0.5 O 2 LiNi 0.5 Mn 1.5 O 4
  • the battery capacity can be increased, and even when used at a high potential, the capacity retention rate is high, which is particularly preferable.
  • a positive electrode active material having a charging region capable of oxidizing the organometallic compound represented by the formula (I) of the present invention.
  • the positive potential is more preferably 3.8 V or more, further preferably 3.9 V or more, and particularly preferably 4 V or more.
  • the positive potential is preferably 4.1 V or higher, and most preferably 4.2 V or higher.
  • the upper limit is not particularly limited. However, 5V or less is practical. By setting it as such a range, cycling characteristics and high-rate discharge characteristics can be improved.
  • the positive electrode potential (Li / Li + reference) at the time of charging / discharging is represented by the following formula.
  • the negative electrode potential is 1.55V.
  • the negative electrode potential is 0.1V. The battery voltage is observed during charging and the positive electrode potential is calculated.
  • the non-aqueous electrolyte of the present invention is particularly preferably used in combination with a high potential positive electrode.
  • a positive electrode with a high potential When a positive electrode with a high potential is used, the cycle characteristics tend to be greatly reduced.
  • the nonaqueous electrolyte can maintain good performance with this decrease suppressed. .
  • the average particle diameter of the positive electrode active material used is not particularly limited, but is preferably 0.1 ⁇ m to 50 ⁇ m.
  • the specific surface area is not particularly limited, but is preferably 0.01 m 2 / g to 50 m 2 / g by the BET method.
  • the pH of the supernatant when 5 g of the positive electrode active material is dissolved in 100 ml of distilled water is preferably 7 or more and 12 or less.
  • a well-known grinder or classifier is used.
  • a mortar, a ball mill, a vibration ball mill, a vibration mill, a satellite ball mill, a planetary ball mill, a swirling air flow type jet mill, a sieve, or the like is used.
  • the blending amount of the positive electrode active material is not particularly limited, but is preferably 60 to 98% by mass, more preferably 70 to 95% by mass in 100% by mass of the solid component in the dispersion (mixture) for constituting the active material layer. preferable.
  • -Negative electrode active material As a negative electrode active material, what can insert and discharge
  • a carbonaceous material or a lithium composite oxide is preferable from the viewpoint of reliability.
  • the metal composite oxide is preferably one that can occlude and release lithium, and preferably contains titanium and / or lithium as a constituent component from the viewpoint of high current density charge / discharge characteristics.
  • the carbonaceous material used as the negative electrode active material is a material substantially made of carbon.
  • Examples thereof include carbonaceous materials obtained by firing artificial graphite such as petroleum pitch, natural graphite, and vapor-grown graphite, and various synthetic resins such as PAN-based resins and furfuryl alcohol resins.
  • various carbon fibers such as PAN-based carbon fiber, cellulose-based carbon fiber, pitch-based carbon fiber, vapor-grown carbon fiber, dehydrated PVA-based carbon fiber, lignin carbon fiber, glassy carbon fiber, activated carbon fiber, mesophase micro
  • Examples thereof include spheres, graphite whiskers, and flat graphite.
  • carbonaceous materials can be divided into non-graphitizable carbon materials and graphite-based carbon materials depending on the degree of graphitization. Further, the carbonaceous material may have an interplanar spacing, density, and crystallite size as described in JP-A-62-222066, JP-A-2-6856, and 3-45473. preferable.
  • the carbonaceous material does not need to be a single material, and a mixture of natural graphite and artificial graphite described in JP-A-5-90844, graphite having a coating layer described in JP-A-6-4516, and the like. It can also be used.
  • the metal oxide and metal composite oxide which are negative electrode active materials used in the nonaqueous secondary battery of the present invention, preferably contain at least one of these.
  • amorphous oxides are preferable, and chalcogenite, which is a reaction product of a metal element and an element of Group 16 of the periodic table, is also preferably used.
  • chalcogenite which is a reaction product of a metal element and an element of Group 16 of the periodic table.
  • amorphous as used herein means an X-ray diffraction method using CuK ⁇ rays, which has a broad scattering band having a peak in the region of 20 ° to 40 ° in terms of 2 ⁇ , and is a crystalline diffraction line. You may have.
  • the strongest intensity of the crystalline diffraction lines seen from 2 ° to 40 ° to 70 ° is 100 times the diffraction line intensity at the peak of the broad scattering band seen from 2 ° to 20 °. Is preferably 5 times or less, and particularly preferably has no crystalline diffraction line.
  • the amorphous oxide and chalcogenide of the semimetal element are more preferable, and the elements of Groups 13 (IIIB) to 15 (VB) of the periodic table, Al , Ga, Si, Sn, Ge, Pb, Sb, Bi alone or in combination of two or more thereof, and chalcogenide are particularly preferable.
  • preferable amorphous oxides and chalcogenides include, for example, Ga 2 O 3 , SiO, GeO, SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 2 O 4 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , Bi 2 O 3 , Bi 2 O 4 , SnSiO 3 , GeS, SnS, SnS 2 , PbS, PbS 2 , Sb 2 S 3 , Sb 2 S 5 , such as SnSiS 3 may preferably be mentioned. Moreover, these may be a complex oxide with lithium oxide, for example, Li 2 SnO 2 .
  • the average particle diameter of the negative electrode active material is preferably 0.1 ⁇ m to 60 ⁇ m.
  • a well-known pulverizer or classifier is used.
  • a mortar, a ball mill, a sand mill, a vibrating ball mill, a satellite ball mill, a planetary ball mill, a swirling air flow type jet mill or a sieve is preferably used.
  • wet pulverization in the presence of water or an organic solvent such as methanol can be performed as necessary.
  • classification is preferably performed.
  • the classification method is not particularly limited, and a sieve, an air classifier, or the like can be used as necessary. Classification can be used both dry and wet.
  • the chemical formula of the compound obtained by the above firing method can be calculated from an inductively coupled plasma (ICP) emission spectroscopic analysis method as a measurement method, and from a mass difference between powders before and after firing as a simple method.
  • ICP inductively coupled plasma
  • the negative electrode active material that can be used in combination with the amorphous oxide negative electrode active material centering on Sn, Si, and Ge includes carbon materials that can occlude and release lithium ions or lithium metal, lithium, lithium alloy, lithium, and the like.
  • An alloyable metal is preferable.
  • the electrolytic solution of the present invention is preferably combined with a high potential negative electrode (preferably lithium / titanium oxide, a potential of 1.55 V vs. Li metal) and a low potential negative electrode (preferably a carbon material, a silicon-containing material, Excellent characteristics are exhibited in any combination with a potential of about 0.1 V vs. Li metal.
  • metal or metal oxide negative electrodes preferably Si, Si oxide, Si / Si oxide, Sn, Sn oxide, SnB x P y O z , Cu, which can be alloyed with lithium, which are being developed for higher capacity
  • a battery using a composite of these metals or metal oxides and a carbon material as a negative electrode it is particularly preferable to use a negative electrode active material containing at least one selected from carbon, silicon (Si), titanium, and tin.
  • the non-aqueous electrolyte of the present invention is particularly preferably used in combination with a high potential negative electrode.
  • the high potential negative electrode is often used in combination with the above high potential positive electrode, and can suitably cope with large capacity charge / discharge.
  • the conductive material is preferably an electron conductive material that does not cause a chemical change in the configured secondary battery, and a known conductive material can be arbitrarily used.
  • natural graphite scale-like graphite, scale-like graphite, earth-like graphite, etc.
  • artificial graphite carbon black, acetylene black, ketjen black, carbon fiber and metal powder (copper, nickel, aluminum, silver (Japanese Patent Laid-Open No. Sho 63-63)) , Etc.), etc.
  • metal fibers or polyphenylene derivatives (described in JP-A-59-20971) can be contained as one kind or a mixture thereof.
  • the addition amount of the conductive agent is preferably 11 to 50% by mass, and more preferably 2 to 30% by mass. In the case of carbon black or graphite, 2 to 15% by mass is particularly preferable.
  • the binder (hereinafter also referred to as a binder) includes polysaccharides, thermoplastic resins, and polymers having rubber elasticity. Among them, for example, starch, carboxymethylcellulose, cellulose, diacetylcellulose, Methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, sodium alginate, polyacrylic acid, sodium polyacrylate, polyvinylphenol, polyvinylmethylether, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylonitrile, polyacrylamide, polyhydroxy (meth) acrylate, styrene-maleine Water-soluble polymers such as acid copolymers, polyvinyl chloride, polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hex Safluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, polyethylene
  • Binders can be used alone or in combination of two or more.
  • the amount of the binder added is small, the holding power and cohesive force of the electrode mixture are weakened. If the amount is too large, the electrode volume increases and the capacity per electrode unit volume or unit mass decreases. For this reason, the addition amount of the binder is preferably 1 to 30% by mass, and more preferably 2 to 10% by mass.
  • the electrode compound material may contain the filler.
  • the material forming the filler is preferably a fibrous material that does not cause a chemical change in the non-aqueous secondary battery of the present invention.
  • fibrous fillers made of materials such as olefin polymers such as polypropylene and polyethylene, glass, and carbon are used.
  • the addition amount of the filler is not particularly limited, but is preferably 0 to 30% by mass in the dispersion.
  • the positive / negative current collector an electron conductor that does not cause a chemical change is preferably used.
  • the current collector of the positive electrode in addition to aluminum, stainless steel, nickel, titanium, etc., the surface of aluminum or stainless steel is preferably treated with carbon, nickel, titanium, or silver. Among them, aluminum and aluminum alloys are preferable. More preferred.
  • the negative electrode current collector aluminum, copper, stainless steel, nickel and titanium are preferable, and aluminum, copper and copper alloy are more preferable.
  • a film sheet is usually used, but a net, a punched one, a lath body, a porous body, a foamed body, a molded body of a fiber group, and the like can also be used.
  • the thickness of the current collector is not particularly limited. 1 ⁇ m to 500 ⁇ m is preferable.
  • the current collector surface is roughened by surface treatment.
  • An electrode mixture of the lithium secondary battery is formed by a member appropriately selected from these materials.
  • the separator used in the non-aqueous secondary battery of the present invention is made of a material that mechanically insulates the positive electrode and the negative electrode, has ion permeability, and has oxidation / reduction resistance at the contact surface between the positive electrode and the negative electrode.
  • a material a porous polymer material, an inorganic material, an organic-inorganic hybrid material, glass fiber, or the like is used.
  • These separators preferably have a shut-down function for ensuring reliability, that is, a function of closing a gap at 80 ° C. or higher to increase resistance and interrupting current, and the plugging temperature is preferably 90 ° C. or higher and 180 ° C. or lower. .
  • the shape of the separator holes is usually circular or elliptical, and the size is preferably 0.05 ⁇ m to 30 ⁇ m, more preferably 0.1 ⁇ m to 20 ⁇ m. Furthermore, it may be a rod-like or irregular-shaped hole as in the case of making by a stretching method or a phase separation method.
  • the ratio of these gaps, that is, the porosity, is preferably 20% to 90%, and more preferably 35% to 80%.
  • the polymer material may be a single material such as a cellulose nonwoven fabric, polyethylene, or polypropylene, or may be a material using two or more composite materials. What laminated
  • oxides such as alumina and silicon dioxide, nitrides such as aluminum nitride and silicon nitride, and sulfates such as barium sulfate and calcium sulfate are used, and those having a particle shape or fiber shape are used.
  • a thin film shape such as a non-woven fabric, a woven fabric, or a microporous film is used.
  • the thin film shape those having a pore diameter of 0.01 ⁇ m to 1 ⁇ m and a thickness of 5 ⁇ m to 50 ⁇ m are preferably used.
  • a separator formed by forming a composite porous layer containing inorganic particles on the surface layer of the positive electrode and / or the negative electrode using a resin binder can be used.
  • alumina particles having a 90% particle diameter of less than 1 ⁇ m are formed on both surfaces of the positive electrode as a porous layer using a fluororesin binder.
  • the shape of the nonaqueous secondary battery of the present invention can be applied to any shape such as a sheet shape, a square shape, and a cylinder shape.
  • a positive electrode active material or a mixture of negative electrode active materials is mainly used after being applied (coated), dried and compressed on a current collector.
  • FIG. 2 shows an example of a bottomed cylindrical lithium secondary battery 100.
  • This battery is a bottomed cylindrical lithium secondary battery 100 in which a positive electrode sheet 14 and a negative electrode sheet 16 overlapped with a separator 12 are wound and accommodated in an outer can 18.
  • 20 is an insulating plate
  • 22 is a sealing plate
  • 24 is a positive electrode current collector
  • 26 is a gasket
  • 28 is a pressure sensitive valve body
  • 30 is a current interruption element.
  • each member corresponds to the whole drawing by reference numerals.
  • a negative electrode active material is mixed with a binder or filler used as desired in an organic solvent to prepare a slurry or paste negative electrode mixture.
  • the obtained negative electrode mixture is uniformly applied over the entire surface of both surfaces of the metal core as a current collector, and then the organic solvent is removed to form a negative electrode mixture layer.
  • the laminate of the current collector and the negative electrode composite material layer is rolled with a roll press or the like to prepare a predetermined thickness to obtain a negative electrode sheet (electrode sheet).
  • the coating method of each agent, the drying of the coated material, and the method of forming the positive and negative electrodes may be in accordance with conventional methods.
  • a cylindrical battery is taken as an example, but the present invention is not limited to this.
  • the positive and negative electrode sheets produced by the above method are overlapped with a separator and then processed into a sheet battery as it is, or after being folded and inserted into a rectangular can, the can and the sheet After the electrical connection, the electrolyte may be injected, and the opening may be sealed using a sealing plate to produce a square battery.
  • the safety valve can be used as a sealing plate for sealing the opening.
  • the sealing member may be provided with various conventionally known safety elements.
  • a fuse, bimetal, PTC element, or the like is preferably used as the overcurrent prevention element.
  • a method of cutting the battery can a method of cracking the gasket, a method of cracking the sealing plate, or a method of cutting the lead plate can be used.
  • the charger may be provided with a protection circuit incorporating measures against overcharge and overdischarge, or may be connected independently.
  • a metal or alloy having electrical conductivity can be used.
  • metals such as iron, nickel, titanium, chromium, molybdenum, copper, and aluminum, or alloys thereof are preferably used.
  • a known method for example, direct current or alternating current electric welding, laser welding, or ultrasonic welding
  • the cap, can, sheet, and lead plate can be used as the cap, can, sheet, and lead plate.
  • the sealing agent for sealing a conventionally known compound or mixture such as asphalt can be used.
  • lithium batteries are secondary batteries that use the insertion and extraction of lithium for charge / discharge reactions (lithium ion secondary batteries), and secondary batteries that use precipitation and dissolution of lithium (lithium metal secondary batteries). ). In the present invention, application as a lithium ion secondary battery is preferable.
  • the non-aqueous secondary battery of the present invention can be applied to various uses.
  • the application mode for example, when installed in an electronic device, a notebook computer, a pen input personal computer, a mobile personal computer, an electronic book player, a mobile phone, a cordless phone, a pager, a handy terminal, a mobile fax machine, a mobile phone Copy, portable printer, headphone stereo, video movie, LCD TV, handy cleaner, portable CD, minidisc, electric shaver, transceiver, electronic notebook, calculator, memory card, portable tape recorder, radio, backup power supply, memory card, etc. It is done.
  • Other consumer products include automobiles, electric vehicles, motors, lighting equipment, toys, game equipment, road conditioners, watches, strobes, cameras, medical equipment (such as pacemakers, hearing aids, and shoulder grinders). Furthermore, it can be used for various military purposes and space. Moreover, it can also combine with a solar cell.
  • Organometallic compound I (2) was synthesized by the following synthesis scheme.
  • the reaction solution was concentrated, 40 ml of toluene was added, and the mixture was stirred for 5 minutes.
  • the obtained suspension was filtered through Celite, and then toluene was distilled off again with an evaporator.
  • the obtained crude product is dissolved in 200 ml of hexane, cooled to ⁇ 70 ° C. or lower with a dry ice-methanol bath, the precipitated recrystallized product is filtered off, and the organometallic compound I (2) of the present invention: 9.1 g was obtained.
  • Organometallic compound I (4) was synthesized by the following synthesis scheme.
  • Compound X (1) 10.45 g and dehydrated toluene: 100 ml were added to a 200 ml three-necked flask. Next, after cooling to ⁇ 70 ° C. or less with a dry ice-methanol bath, 37.5 ml of n-butyllithium (1.6M: manufactured by Kanto Chemical Co., Inc.) was added dropwise over 30 minutes. Stir. 2,2,7,7-Tetramethylocta-3,5-diyne: 4.87 g (manufactured by ALDRICH) was added, and the reaction solution was warmed to room temperature and further reacted for 3 hours.
  • n-butyllithium 1.5M: manufactured by Kanto Chemical Co., Inc.
  • Organometallic compound I (7) was synthesized according to the following synthesis scheme.
  • Organometallic compound I (8) was synthesized by the following synthesis scheme.
  • Organometallic compounds I (1), (9) to (12) and (14) were synthesized by the same synthesis method as the organometallic compound of the present invention synthesized above.
  • 1M LiPF 6 ethylene carbonate / ethyl methyl carbonate (volume ratio 1 to 2) electrolyte solution an organometallic compound shown in Table 1 below was added in the amount shown in Table 1, and a test electrolyte solution was added.
  • the positive electrode is composed of 85% by mass of active material: lithium manganate (LiMn 2 O 4 ), conductive auxiliary agent: 7% by mass of carbon black, binder: 8% by mass of PVDF (polyvinylidene fluoride). It was made with.
  • a negative electrode was produced with a composition of 92% by mass of active material: Gr (natural graphite) and 8% by mass of binder: PVDF.
  • As the separator a polypropylene separator having a thickness of 25 ⁇ m was prepared. Using the positive and negative electrodes and separators described above, each test electrolyte solution prepared was used to produce a 2032 type coin battery.
  • Discharge capacity maintenance rate (%) (Discharge capacity at the 300th cycle / discharge capacity at the first cycle) ⁇ 100
  • the 2032 type coin battery (101 to 114) of the present invention has a discharge capacity maintenance rate of 76 to 95%.
  • the comparison without using the organometallic compound is performed.
  • the discharge capacity retention rate is improved by 11% or more.
  • the 2032 type coin battery (c02) using the ferrocene of the comparative example it is presumed that the self-discharge progresses due to the redox shuttle and the capacity maintenance rate is lowered. It seems that ferrocene cannot form a film on the positive electrode in a battery having a low driving voltage, and the capacity retention rate is lowered. As a result, it can be seen that the present invention can achieve high cycle characteristics in the lithium ion secondary battery.
  • Example 2 and Comparative Example 2 Preparation of electrolyte solution 1.1M LiPF 6 ethylene carbonate / ethyl methyl carbonate (volume ratio 1 to 2) To the electrolyte solution, an organometallic compound and a phosphazene compound were added in amounts shown in Table 2, and further vinylene was added. An electrolytic solution for each test was prepared by adding 1% by mass of carbonate to the total electrolytic solution and 1% by mass of lithium bisoxalate borate with respect to the total electrolytic solution. All the prepared electrolyte solutions had a viscosity at 25 ° C. of 5 mPa ⁇ s or less, and the water content measured by the Karl Fischer method (JIS K0113) was 20 ppm or less.
  • the flame retardancy of the prepared electrolyte was evaluated as follows at 25 ° C. in the atmosphere. The evaluation was carried out under the following test conditions with reference to the UL-94HB horizontal combustion test. A glass filter paper (ADVANTEC GA-100) having a width of 13 mm and a length of 110 mm was cut out, and 1.5 ml of the prepared electrolyte was evenly dropped onto the glass filter paper. After the electrolyte solution was sufficiently infiltrated into the glass filter paper, the excess electrolyte solution was wiped off and suspended so that the minor axis was vertical.
  • a glass filter paper ADVANTEC GA-100 having a width of 13 mm and a length of 110 mm was cut out, and 1.5 ml of the prepared electrolyte was evenly dropped onto the glass filter paper. After the electrolyte solution was sufficiently infiltrated into the glass filter paper, the excess electrolyte solution was wiped off and suspended so that the minor axis was vertical.
  • the butane gas burner adjusted to 2 cm in total flame length ignites for 3 seconds at the position where it touches the tip of the glass filter paper, and the behavior after releasing the flame (ignition / non-ignition, extinguishing after ignition, flame from ignition point to the other end) was evaluated as follows. Test No. with no additive added. In the glass filter paper using the electrolytic solution of C201, the time for the flame to reach from the ignition point to the other end was less than 5 seconds.
  • the positive electrode is made of active material: lithium nickel manganese cobaltate (LiNi 1/3 Mn 1/3 Co 1/3 O 2 ) 95% by mass, conductive auxiliary agent: carbon black 2% by mass, binder: PVDF (polyvinylidene fluoride) was prepared with a composition of 3% by mass.
  • a negative electrode was prepared with a composition of 97% by mass of active material: graphite, 2% by mass of binder: styrene butadiene rubber (SBR), and 1% by mass of thickener: sodium carboxymethylcellulose (CMC).
  • SBR styrene butadiene rubber
  • CMC sodium carboxymethylcellulose
  • As the separator a polypropylene separator having a thickness of 25 ⁇ m was prepared. Using the positive and negative electrodes and separators described above, each test electrolyte solution prepared was used to produce a 2032 type coin battery.
  • discharge capacity after cycle test The battery after the cycle test was charged and discharged under the same conditions as those for the initial discharge capacity (W 1 ), and the discharge capacity after the cycle test (W 300 ) was measured.
  • Discharge capacity maintenance rate after cycle test Discharge capacity after cycle test (W 300 ) / initial discharge capacity (W 1 )
  • the obtained discharge capacity maintenance rate was evaluated as follows. The larger the value, the higher the capacity is maintained even under severe test conditions.
  • the organometallic compound and the phosphazene compound are specific examples of the organometallic compound represented by the formula (I) and the phosphazene compound described in the specification. Further, the discharge capacity maintenance rate after the cycle test is abbreviated as “discharge capacity maintenance rate”.
  • Example 4 and Comparative Example 4 The electrolyte solution was changed to 1.1M LiPF 6 ethylene carbonate / dimethyl carbonate (volume ratio 1 to 2), and the organometallic compounds and phosphazene compounds shown in Table 4 below were added in the amounts shown in Table 4. The same operations as in Example 2 and Comparative Example 2 were performed. The results are shown in Table 4.
  • Example 5 and Comparative Example 5 The electrolyte is 0.9M LiBF 4 ethylene carbonate / diethyl carbonate (volume ratio 1: 1), the positive electrode active material is nickel cobalt lithium aluminumate (LiNi 0.8 Co 0.15 Al 0.05 O 2 ), vinylene carbonate Was changed to fluoroethylene carbonate, and the same operations as in Example 2 and Comparative Example 2 were carried out except that the organometallic compounds and phosphazene compounds shown in Table 5 below were added in the amounts shown in Table 5. The results are shown in Table 5.
  • the lithium ion secondary battery using the organometallic compound of the present invention shows a good discharge capacity retention rate. It can also be seen that by using the phosphazene compound represented by the formula (A1) or (A2) in combination, a high discharge capacity retention rate can be achieved even under severe use conditions while realizing high flame retardancy.

Abstract

L'invention concerne une solution électrolytique destinée à des batteries rechargeables non aqueuses, qui contient une quantité supérieure à 0 % en masse mais inférieure ou égale à 1 % en masse d'un composé métallique organique représenté par la formule (I) ; un additif pour solutions électrolytiques ; et une batterie rechargeable non aqueuse. Dans la formule (I), M représente un élément métallique ; R1 et R2 représentent chacun un substituant ; si il y a une pluralité de fractions R1 et une pluralité de fractions R2, la pluralité de fragments R1 ou la pluralité de fractions R2 peuvent se combiner ensemble pour former un cycle aliphatique ou aromatique ; X et Y représentent chacun un atome d'hydrogène ou un substituant ; si il y a une pluralité de fractions X et une pluralité de fractions Y, la pluralité de fractions X ou la pluralité de fractions Y peuvent se combiner ensemble pour former un cycle ; L représente un groupe de liaison ; a et b représentent chacun un nombre entier de 0 à 4 ; et m et n représentent des nombres entiers satisfaisant à 0 ≤ m + n ≤ 3.
PCT/JP2015/069655 2014-08-22 2015-07-08 Solution électrolytique de batteries rechargeables non aqueuses, batterie rechargeable non aqueuse, et additif utilisé pour une solution électrolytique de batteries rechargeables non aqueuses WO2016027583A1 (fr)

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US11404692B1 (en) 2021-07-23 2022-08-02 Lyten, Inc. Lithium-sulfur battery cathode formed from multiple carbonaceous regions
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KR20180005105A (ko) * 2016-07-05 2018-01-15 광동 광산 뉴 머터리얼즈 씨오., 엘티디. 난연성의 엔지니어링 플라스틱 및 이의 제조방법
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WO2018016519A1 (fr) * 2016-07-20 2018-01-25 富士フイルム株式会社 Solution électrolytique destinée à une batterie rechargeable non aqueuse et batterie rechargeable non aqueuse
JPWO2018016519A1 (ja) * 2016-07-20 2019-04-04 富士フイルム株式会社 非水二次電池用電解液および非水二次電池
US10923769B2 (en) 2016-07-20 2021-02-16 Fujifilm Corporation Electrolytic solution for non-aqueous secondary battery and non-aqueous secondary battery
US11367895B1 (en) 2021-07-23 2022-06-21 Lyten, Inc. Solid-state electrolyte for lithium-sulfur batteries
US11404692B1 (en) 2021-07-23 2022-08-02 Lyten, Inc. Lithium-sulfur battery cathode formed from multiple carbonaceous regions
US11600876B2 (en) 2021-07-23 2023-03-07 Lyten, Inc. Wound cylindrical lithium-sulfur battery including electrically-conductive carbonaceous materials
US11670826B2 (en) 2021-07-23 2023-06-06 Lyten, Inc. Length-wise welded electrodes incorporated in cylindrical cell format lithium-sulfur batteries

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