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WO2018116491A1 - Batterie secondaire à électrolytique non aqueux et son procédé de fabrication - Google Patents

Batterie secondaire à électrolytique non aqueux et son procédé de fabrication Download PDF

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WO2018116491A1
WO2018116491A1 PCT/JP2017/010141 JP2017010141W WO2018116491A1 WO 2018116491 A1 WO2018116491 A1 WO 2018116491A1 JP 2017010141 W JP2017010141 W JP 2017010141W WO 2018116491 A1 WO2018116491 A1 WO 2018116491A1
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aqueous electrolyte
secondary battery
lithium
acid compound
electrolyte secondary
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Japanese (ja)
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曜 山下
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Maxell Ltd
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Maxell Holdings Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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 a non-aqueous electrolyte secondary battery having excellent load characteristics at low temperatures even after being subjected to high-temperature storage and excellent in reliability, and a method for producing the same.
  • Non-aqueous electrolyte secondary batteries are used in various applications by taking advantage of characteristics such as high capacity and high voltage. And with the spread of the application field, various characteristics improvement is calculated
  • Such a system is required to operate reliably in an emergency, although the opportunity to actually operate is limited. For this reason, a battery serving as a power source is required to have a reliability capable of maintaining its characteristics well even when stored for a long period of time.
  • tire pressure monitoring systems [TirePressure Monitoring System ( Vehicles equipped with TPMS)] are becoming widespread.
  • a non-aqueous electrolyte battery (primary battery) is used as a power source for the system.
  • the battery serving as the power source can be used for a long time. Reliability that can maintain the characteristics is required.
  • Patent Documents 1 and 2 propose proposals have been made to add a phosphoric acid ester compound having a specific structure to the non-aqueous electrolyte (Patent Documents 1 and 2).
  • unsaturated sultone is added to the non-aqueous electrolyte to suppress the decomposition reaction of the solvent on the negative electrode, to reduce the battery capacity during high temperature storage, to suppress gas generation, and to deteriorate the load characteristics of the battery.
  • vinylene carbonate and LiPF 6 and lithium bisoxalate borate [LiB (C 2 O 4 ) 2 ] have been proposed (Patent Documents 3 and 4).
  • Patent Document 5 a proposal has been made to suppress the self-discharge of the battery during high-temperature storage by containing lithium monofluorophosphate or lithium difluorophosphate in the non-aqueous electrolyte.
  • lithium anodes such as metallic lithium and Li—Al (lithium-aluminum) alloys are used as the anode active material of the non-aqueous electrolyte primary battery. Since a lithium alloy can be used as an active material, battery characteristics can be stabilized by forming a negative electrode using a clad material of a metal that can occlude and release lithium and a metal that does not occlude and release lithium. Has also been proposed (Patent Documents 6 and 7).
  • the battery when a system such as that described above is mounted on a vehicle, the battery is likely to be placed in a high temperature environment, and the battery is required to have excellent heat resistance. There is a need for a battery that can be used, has little characteristic deterioration even after being placed in a high temperature environment for a long time, and can exhibit good load characteristics in a low temperature environment.
  • the present invention has been made in view of the above circumstances, and its purpose is to provide a non-aqueous electrolyte secondary battery having excellent load characteristics at low temperatures even after being subjected to high-temperature storage, and excellent in reliability. And to provide a method.
  • the nonaqueous electrolyte secondary battery of the present invention has a negative electrode, a positive electrode, and a nonaqueous electrolyte, and the negative electrode has an alloy of Li and an element that can be alloyed with Li as a negative electrode active material,
  • the non-aqueous electrolyte comprises at least one additive selected from sultone compounds, lithium organic borate, lithium monofluorophosphate and lithium difluorophosphate, and a group represented by the following general formula (1) It contains a phosphoric acid compound or boric acid compound contained in the molecule.
  • X is Si, Ge or Sn
  • R 1 , R 2 and R 3 are each independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or Represents an aryl group having 6 to 10 carbon atoms, and part or all of the hydrogen atoms may be substituted with fluorine.
  • the production method of the present invention is a production method of a non-aqueous electrolyte secondary battery having a negative electrode, a positive electrode and a non-aqueous electrolyte, wherein the negative electrode comprises an alloy of Li and an element that can be alloyed with Li. It has as a negative electrode active material, and the non-aqueous electrolyte contains at least one additive selected from sultone compounds, lithium organic borate, lithium monofluorophosphate and lithium difluorophosphate, and the general formula (1 And a phosphoric acid compound or boric acid compound having a group represented by
  • At least one additive selected from sultone compounds, lithium organic borate salts, lithium monofluorophosphate and lithium difluorophosphate, and a group represented by the general formula (1) are contained in the molecule.
  • a non-aqueous electrolyte containing a phosphoric acid compound or a boric acid compound contained in a non-aqueous electrolyte containing a negative electrode containing an alloy of Li and an alloy capable of alloying with Li as a negative electrode active material The secondary battery can have excellent high-temperature storage characteristics, low-temperature load characteristics, and reliability.
  • FIG. 2 is a perspective view of FIG. 1.
  • the phosphoric acid compound having a group represented by the general formula (1) in the molecule is added to the non-aqueous electrolyte in a non-aqueous electrolyte secondary battery using a carbon material as a negative electrode active material, It is known that it has the effect
  • At least one selected from a sultone compound, an organic borate lithium salt, lithium monofluorophosphate (Li 2 PO 3 F) and lithium difluorophosphate (LiPO 2 F 2 ) in the non-aqueous electrolyte It has been clarified that the above problem can be suppressed by adding an additive.
  • the phosphoric acid compound or boric acid compound having the group represented by the general formula (1) in the molecule and the additive such as a sultone compound are allowed to coexist in a nonaqueous electrolytic solution, thereby forming on the surface of the negative electrode. It is presumed that the shape of the coating film becomes better, and the occurrence of problems in the high-temperature storage can be suppressed.
  • the sultone compound can form a film on the positive electrode surface to suppress decomposition of the nonaqueous electrolytic solution and gas generation at the positive electrode, and by coexisting with the phosphoric acid compound or boric acid compound, Swelling of the battery during high-temperature storage can be further suppressed, and the reliability of the nonaqueous electrolyte secondary battery can be further improved.
  • a solution prepared by dissolving a lithium salt in the following non-aqueous solvent can be used as the non-aqueous electrolyte.
  • numerator, and the said additives, such as a sultone compound are contained and used.
  • the phosphoric acid compound has a structure in which at least one of hydrogen atoms of phosphoric acid is substituted with a group represented by the general formula (1).
  • the boric acid compound has a structure in which at least one of hydrogen atoms of boric acid is substituted with a group represented by the general formula (1).
  • X is Si, Ge, or Sn.
  • a phosphoric acid silyl ester in which X is Si is preferably used.
  • X is Si.
  • the boric acid silyl ester is preferably used.
  • R 1 , R 2 and R 3 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. However, a methyl group or an ethyl group is more preferable.
  • R 1 , R 2 and R 3 may have part or all of the hydrogen atoms substituted with fluorine.
  • the group represented by the general formula (1) is particularly preferably a trimethylsilyl group.
  • the phosphoric acid compound only one of the hydrogen atoms of phosphoric acid may be substituted with the group represented by the general formula (1), and two of the hydrogen atoms of phosphoric acid may be substituted.
  • the group represented by the general formula (1) may be substituted, and all three hydrogen atoms of phosphoric acid may be substituted with the group represented by the general formula (1). It is more preferable that all three hydrogen atoms of phosphoric acid are substituted with the group represented by the general formula (1).
  • Examples of the phosphoric acid compound include mono (trimethylsilyl) phosphate, di (trimethylsilyl) phosphate, tris (trimethylsilyl) phosphate, dimethyltrimethylsilyl phosphate, methylbis (trimethylsilyl) phosphate, diethyltrimethylsilyl phosphate, Diphenyl phosphate (trimethylsilyl), Tris phosphate (triethylsilyl), Tris phosphate (vinyldimethylsilyl), Tris phosphate (triisopropylsilyl), Tris phosphate (dimethylethylsilyl), Tris phosphate (methyldiethylsilyl) , Tris (butyldimethylsilyl) phosphate, tris (vinyldimethylsilyl) phosphate, tris (triphenylsilyl) phosphate, mono (trimethylsilyl) phosphate, di (trimethylsilyl) phosphate, Phos
  • boric acid compound only one of the hydrogen atoms possessed by boric acid may be substituted with the group represented by the general formula (1). Two of them may be substituted with the group represented by the general formula (1), and all three hydrogen atoms of boric acid may be substituted with the group represented by the general formula (1). However, it is more preferable that all three hydrogen atoms of boric acid are substituted with the group represented by the general formula (1).
  • boric acid compounds include mono (trimethylsilyl) borate, di (trimethylsilyl) borate, tris (trimethylsilyl) borate, dimethyltrimethylsilylborate, methylbis (trimethylsilyl) borate, diethyltrimethylsilylborate, Diphenyl borate (trimethylsilyl), tris (triethylsilyl) borate, tris (vinyldimethylsilyl) borate, tris (triisopropylsilyl) borate, tris (dimethylethylsilyl) borate, tris (methyldiethylsilyl) borate, Examples thereof include tris (butyldimethylsilyl) borate, tris (vinyldimethylsilyl) borate, tris (triphenylsilyl) borate, mono (trimethylsilyl) borate, di (trimethylsilyl) borate, Tris (trimethylsilyl) borate dimethyl trimethyl trimethyl
  • the addition amount of the phosphoric acid compound or boric acid compound having in the molecule thereof the group represented by the general formula (1) in the non-aqueous electrolyte is from the viewpoint of ensuring better the above-mentioned effects due to its use. It is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, and particularly preferably 0.7% by mass or more. Most preferably, it is 1 mass% or more. In addition, if the content is too large, the thickness of the coating that can be formed on the negative electrode surface increases, which may increase resistance and decrease load characteristics.
  • the amount of the phosphoric acid compound or boric acid compound having the group represented by the formula (1) in the molecule is preferably 10% by mass or less, more preferably 7% by mass or less, and 5% by mass. It is particularly preferable that the amount is 3% by mass or less.
  • the total amount may be adjusted to be in the above range.
  • the sultone compound is classified into a compound having no unsaturated bond in the ring and a compound having an unsaturated bond in the ring, each of which is a 5-membered ring from the viewpoint of solubility in a nonaqueous electrolytic solution.
  • a compound having a 7-membered ring is preferably used, and a compound having a 5-membered ring structure is more preferably used.
  • Examples of the compound having no unsaturated bond in the ring include 1,3-propane sultone and 1,4-butane sultone, and 1,3-propane sultone is preferably used.
  • Examples of the compound having an unsaturated bond in the ring include those having a 5-membered ring structure represented by the following general formula (2).
  • R 4 , R 5 , R 6 and R 7 are each independently hydrogen, fluorine, or a carbon number of 1 to 12, and part or all of the hydrogens are replaced by fluorine. It may be a hydrocarbon group.
  • R 4 , R 5 , R 6 and R 7 each have hydrogen, fluorine, or 1 to 3 carbon atoms, and part or all of the hydrogen is fluorine.
  • the amount of the sultone compound added to the non-aqueous electrolyte may be 0.1% by mass or more, preferably 0.2% by mass or more. It is more preferably 3% by mass or more, and most preferably 0.5% by mass or more.
  • the amount of the sultone compound in the non-aqueous electrolyte is too large, the internal resistance of the battery may increase and the discharge characteristics may deteriorate.
  • the amount of sultone compound added to the non-aqueous electrolyte is preferably 7% by mass or less, more preferably 5% by mass or less, and more preferably 3% by mass or less. Particularly preferred is 2% by mass or less.
  • phosphoric acid compounds and boric acid compounds having a group represented by the general formula (1) in the molecule in a non-aqueous electrolyte and boron The mass ratio of the total amount of the acid compound added to the amount of the sultone compound added is preferably in the range of 20:80 to 80:20.
  • the amount of the sultone compound added in the non-aqueous electrolyte and the group represented by the general formula (1) is preferably 5% by mass or less, more preferably 4% by mass or less, and particularly preferably 3% by mass or less. Most preferably, it is 2.5 mass% or less.
  • lithium organic borate examples include lithium tetrakis (acetate) borate, lithium tetrakis (fluoroacetate) borate, lithium tetrakis (difluoroacetate) borate, lithium tetrakis (trifluoroacetate) borate, lithium bis (oxalate) borate [LiB ( C 2 O 4 ) 2 ] (LiBOB) and the like, and lithium bis (oxalate) borate is more preferably used.
  • the addition amount of the organic borate lithium salt in the non-aqueous electrolyte may be 0.05% by mass or more, and is 0.1% by mass or more. Is preferably 0.2% by mass or more, and most preferably 0.3% by mass or more.
  • the amount of the organic borate lithium salt in the non-aqueous electrolyte is too large, the internal resistance of the battery may increase and the discharge characteristics may deteriorate.
  • the addition amount of the organic borate lithium salt in the nonaqueous electrolytic solution is preferably 5% by mass or less, more preferably 3% by mass or less, and more preferably 2% by mass. More preferably, it is more preferably 1% by mass or less, and most preferably 0.5% by mass or less.
  • a phosphoric acid compound and boric acid having a group represented by the general formula (1) in the molecule in a non-aqueous electrolyte used for a battery In the total amount of the total addition amount of the compound and the addition amount of the organic borate lithium salt, the proportion of the organic borate lithium salt is preferably 3% or more on a mass basis. Furthermore, from the viewpoint of better suppressing the deterioration of the discharge characteristics due to the increase in the internal resistance of the battery, the addition amount of the organic borate salt in the non-aqueous electrolyte and the general formula (1) are used.
  • the total of the addition amount of the phosphoric acid compound and boric acid compound having a group in the molecule is preferably 5% by mass or less, more preferably 4% by mass or less, and preferably 3% by mass or less. Particularly preferred is 2.5% by mass or less.
  • the amount of lithium monofluorophosphate or lithium difluorophosphate in the non-aqueous electrolyte is 0.1% by mass or more. It is preferably 0.3% by mass or more, and more preferably 0.5% by mass or more. However, if the amount of lithium monofluorophosphate or lithium difluorophosphate in the non-aqueous electrolyte is too large, the internal resistance of the battery may increase and the discharge characteristics may deteriorate.
  • the amount of lithium monofluorophosphate or lithium difluorophosphate in the non-aqueous electrolyte is preferably 3% by mass or less, and more preferably 2% by mass or less. It is preferably 1% by mass or less.
  • the total amount may be adjusted to be in the above range.
  • the total amount of lithium monofluorophosphate and lithium difluorophosphate in the non-aqueous electrolyte is represented by the general formula (1). It is preferable that the mass ratio of the phosphoric acid compound and boric acid compound having the same group in the molecule is in the range of 5:95 to 95: 5.
  • the addition amount of lithium monofluorophosphate and lithium difluorophosphate in the non-aqueous electrolyte and the general formula ( The total of the addition amount of the phosphoric acid compound and boric acid compound having the group represented by 1) in the molecule is preferably 6% by mass or less, and more preferably 3% by mass or less.
  • the total amount of lithium phosphate is preferably 4% by mass or less, and more preferably 3.5% by mass or less.
  • solvent for the non-aqueous electrolyte examples include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (MEC), ⁇ -Butyrolactone ( ⁇ -BL), 1,2-dimethoxyethane (DME), tetrahydrofuran (THF), 2-methyltetrahydrofuran, dimethyl sulfoxide (DMSO), 1,3-dioxolane, formamide, dimethylformamide (DMF), Dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphoric acid triester, trimethoxymethane, dioxolane derivatives, sulfolane, 3-methyl-2-oxazolidinone, propylene carbonate derivatives, Aprotic organic solvents such as a trahydrofuran derivative, diethyl ether,
  • the lithium salt according to the non-aqueous electrolyte solution for example, LiClO 4, LiPF 6, LiBF 4, LiAsF 6, LiSbF 6, LiCF 3 SO 3, LiCF 3 CO 2, Li 2 C 2 F 4 (SO 3) 2, At least selected from LiN (CF 3 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , LiC n F 2n + 1 SO 3 (n ⁇ 2), LiN (RfOSO 2 ) 2 [where Rf is a fluoroalkyl group] One type is mentioned.
  • the concentration of these lithium salts in the non-aqueous electrolyte is preferably 0.6 to 1.8 mol / l, and more preferably 0.9 to 1.6 mol / l.
  • the additives such as the sultone compound and additives other than the phosphoric acid compound and the boric acid compound having the group represented by the general formula (1) in the molecule are added as necessary. It can also be contained.
  • additives include acid anhydrides such as maleic anhydride and phthalic anhydride; dinitriles such as succinonitrile, glutaronitrile, and adiponitrile.
  • non-aqueous electrolyte may be in the form of a gel (gel electrolyte) using a known gelling agent such as a polymer.
  • an alloy of Li and an alloyable element (Al, Si, Sn, etc.) and Li is used as the negative electrode active material.
  • an alloy of Li and Al is preferable.
  • a Li—Al alloy as a negative electrode active material
  • a Li foil and an Al foil are bonded together and introduced into a battery, and Li and Al are reacted in the presence of a non-aqueous electrolyte.
  • the negative electrode is made using Al powder as described above, or the negative electrode is made using Al foil, etc. What is necessary is just to charge a battery and to make Al react with Li electrochemically.
  • a metal foil (Cu (copper) foil, Cu alloy foil, etc.) to be a current collector is simply stacked on a laminate of Li foil and Al foil. If the battery is simply inserted into the battery, the internal resistance of the battery may increase after storage (particularly after storage in a high temperature environment), and sufficient characteristics may not be obtained.
  • the volume change occurs when the Li—Al alloy is formed by the laminated body of the Li foil and the Al foil, or the Li—Al alloy is formed and pulverization occurs. This is because the water electrolyte solution is easily absorbed and a volume change occurs, and the adhesion between the Li—Al alloy layer (Al foil) and the current collector cannot be secured.
  • an Al metal layer (Al foil or the like) for forming a Li—Al alloy, and Li acting as a current collector. It is preferable to use a laminate (laminated metal foil) in which a metal base layer (such as a Cu foil) that is not alloyed with a metal substrate is joined in advance for battery assembly. Further, it is preferable to form a Li—Al alloy by alloying at least the surface side of the Al metal layer with Li, and to form a negative electrode composed of a laminate of the metal base layer and the Li—Al alloy layer. Let it be an aspect.
  • the formation of the Li—Al alloy on at least the surface side of the Al metal layer may be performed in the step of chemical conversion treatment of the battery assembled using the laminate (laminated metal foil).
  • an electrode body is constituted by laminating a laminated metal foil in which an Al metal layer is bonded to the surface of a metal base layer and a positive electrode through a separator.
  • the battery that has it is assembled.
  • the assembled battery has a step of charging (charging step), preferably further through a chemical conversion treatment step that also includes a step of discharging (discharge step), thereby changing the negative electrode precursor to a negative electrode,
  • a sufficient function as a water electrolyte secondary battery can be produced. That is, in the charging step, Al in the Al metal layer electrochemically reacts with Li ions in the non-aqueous electrolyte, and a Li—Al alloy is formed on at least the surface side of the Al metal layer facing the positive electrode. A negative electrode having a laminate of the metal substrate layer and the Li—Al alloy layer is formed.
  • the metal base layer described above as a preferred embodiment for forming the negative electrode is a metal such as Cu, Ni, Ti, Fe, or other elements and other elements.
  • the base material layer may be made of a material having a high tensile strength such as a metal selected from nickel, titanium and iron or an alloy thereof, and a material having a tensile strength at room temperature of 400 N / mm 2 or more. It is preferable to do.
  • a battery having a predetermined characteristic can be formed by resistance welding the base material layer to the sealing plate.
  • the characteristic deterioration due to the expansion of the negative electrode is increased.
  • the base material layer is made of a metal selected from Ni, Ti and Fe, such as Ni (490 N / mm 2 ), Ti (410 N / mm 2 ), SUS304 (600 N / mm 2 ), or an alloy thereof.
  • Ni 490 N / mm 2
  • Ti 410 N / mm 2
  • SUS304 600 N / mm 2
  • an alloy thereof an alloy thereof.
  • the base material layer should be composed of a material having a low volume resistivity at room temperature, and the volume resistivity should be 80 ⁇ 10 ⁇ 6 ⁇ ⁇ cm or less. More preferably, the material has a volume resistivity of 30 ⁇ 10 ⁇ 6 ⁇ ⁇ cm or less, and particularly preferably a material having a volume resistivity of 15 ⁇ 10 ⁇ 6 ⁇ ⁇ cm or less.
  • the volume resistivity of the material is Ni: 6.8 ⁇ 10 ⁇ 6 ⁇ ⁇ cm, Ti: 55 ⁇ 10 ⁇ 6 ⁇ ⁇ cm, and SUS304: 72 ⁇ 10 ⁇ 6 ⁇ ⁇ cm, respectively. From the point of view, it is particularly preferable that the base material layer is made of Ni or an alloy thereof.
  • the base material layer is composed of the metal or alloy foil, a vapor deposition film, a plating film, or the like.
  • the Al metal layer is made of an Al or Al alloy foil, a vapor-deposited film, a plating film, etc., and the laminated metal foil formed by joining the base material layer and the Al metal layer constitutes the base material layer.
  • a clad material of a metal foil and an Al or Al alloy foil, or a laminated film in which an Al metal layer is formed by vapor-depositing Al or an Al alloy on the surface of the metal foil constituting the base layer is preferably used. .
  • the Al metal layer can be provided on one side or both sides of the base material layer, but the Al metal layer is bonded to both sides of the base material layer, and at least on the surface side of each Al metal layer.
  • the deformation (curvature, etc.) of the negative electrode and the accompanying battery are compared with the case where the Al metal layer is bonded to only one surface of the base material layer and the Li—Al alloy is formed. Therefore, it is desirable to assemble a battery using a laminated metal foil in which an Al metal layer is bonded to both surfaces of a base material layer.
  • the base material layer is Cu (Cu foil) and the case where the base material layer is Ni (Ni foil) will be described as an example, but the base material layer is a material other than Cu or Ni. Is the same.
  • the Cu layer related to the laminated metal foil formed by joining the Cu layer and the Al metal layer a layer made of Cu (and inevitable impurities), Zr, Cr, Zn, Ni, Si, P, etc. as alloy components are used. And a layer composed of Cu alloy with the balance being Cu and inevitable impurities (the content of the alloy components is, for example, 10% by mass or less, preferably 1% by mass or less in total).
  • the Ni layer related to the laminated metal foil formed by joining the Ni layer and the Al metal layer includes a layer made of Ni (and inevitable impurities), and Zr, Cr, Zn, Cu, Fe, Si, P as alloy components. And the like, and the balance is Ni and an inevitable impurity Ni alloy (the content of the alloy components is, for example, 20% by mass or less in total).
  • Al As an Al metal layer related to a laminated metal foil formed by joining a Cu layer and an Al metal layer or a laminated metal foil formed by joining an Ni layer and an Al metal layer, Al (and inevitable impurities) is used.
  • the ratio of the Li—Al alloy serving as the negative electrode active material is a certain level or more. Therefore, when the thickness of the Cu layer or Ni layer as the base material layer is 100, the thickness of the Al metal layer (however, the Al metal layer is bonded to both sides of the Cu layer or Ni layer as the base material layer). In this case, the thickness per side.
  • the thickness of the Al metal layer is preferably 180 or less, more preferably 150 or less, when the thickness of the Cu layer or Ni layer as the base material layer is 100. It is particularly preferred that it be less than 100, and most preferred is 100 or less.
  • the thickness of the Cu layer or Ni layer as the base material layer is preferably 10 to 50 ⁇ m, more preferably 40 ⁇ m or less, and particularly preferably 30 ⁇ m or less.
  • the thickness of the Al metal layer (however, when the Al metal layer is bonded to both surfaces of the Cu layer and Ni layer as the base material layer), the thickness per side is preferably 5 ⁇ m or more. More preferably, it is 15 ⁇ m or more, more preferably 100 ⁇ m or less, more preferably 70 ⁇ m or less, particularly preferably 50 ⁇ m or less, and 30 ⁇ m or less. Is most preferred.
  • the thickness of the laminated metal foil formed by joining the Cu layer and the Al metal layer and the thickness of the laminated metal foil formed by joining the Ni layer and the Al metal layer are 50 ⁇ m or more in order to make the capacity of the negative electrode constant or more.
  • it is preferably 200 ⁇ m or less, and more preferably 150 ⁇ m or less. It is especially preferable that it is 120 micrometers or less.
  • a laminated metal foil in which a Li foil is previously laminated on the surface of the Al metal layer and the Li foil is further laminated. It is also possible to assemble a battery using, and charge the assembled battery to form a Li—Al alloy layer having a desired composition.
  • a negative electrode lead body can be provided on the Cu layer or Ni layer in the laminate used as the negative electrode precursor for forming the negative electrode according to a conventional method before the battery is assembled.
  • the positive electrode related to the non-aqueous electrolyte secondary battery for example, one having a structure in which a positive electrode mixture layer containing a positive electrode active material, a conductive additive, a binder and the like is provided on one side or both sides of a current collector can be used.
  • a positive electrode active material lithium-containing composite oxides (lithium-containing composite oxides capable of inserting and extracting Li ions) and positive electrode active materials other than lithium-containing composite oxides can be used.
  • the lithium-containing composite oxide used as the positive electrode active material is represented by Li 1 + x M 1 O 2 ( ⁇ 0.1 ⁇ x ⁇ 0.1, M 1 : Co, Ni, Mn, Al, Mg, etc.).
  • the olivine type compound etc. which are represented by this.
  • Examples of the lithium-containing composite oxide having a layered structure include lithium cobalt oxide such as LiCoO 2 and LiNi 1-a Co ab Al b O 2 (0.1 ⁇ a ⁇ 0.3, 0.01 ⁇ b ⁇ 0).
  • examples of the positive electrode active material other than the lithium-containing composite oxide include metal oxides such as manganese dioxide, vanadium pentoxide, and chromium oxide, and metal sulfides such as titanium disulfide and molybdenum disulfide. .
  • the positive electrode active material only one of the above-exemplified compounds may be used, or two or more of them may be used in combination.
  • the lithium-containing composite has a high capacity and excellent storage stability. It is preferable to use an oxide, and it is more preferable to use lithium cobaltate.
  • Examples of the conductive auxiliary agent related to the positive electrode mixture layer include acetylene black; ketjen black; carbon blacks such as channel black, furnace black, lamp black, and thermal black; carbon materials such as carbon fibers; and metal fibers.
  • Conductive fibers such as carbon fluoride, metal powders such as copper and nickel, organic conductive materials such as polyphenylene derivatives, and the like can be used.
  • binder related to the positive electrode mixture layer examples include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), styrene butadiene rubber (SBR), carboxymethyl cellulose (CMC), polyvinyl pyrrolidone (PVP), and the like.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • SBR styrene butadiene rubber
  • CMC carboxymethyl cellulose
  • PVP polyvinyl pyrrolidone
  • a positive electrode mixture containing a positive electrode active material, a conductive additive and a binder is dispersed in a solvent (an organic solvent such as NMP or water) to form a positive electrode mixture-containing composition (paste, slurry, etc.).
  • a solvent an organic solvent such as NMP or water
  • the positive electrode mixture-containing composition can be prepared, applied to one side or both sides of the current collector, dried, and subjected to a press treatment as necessary.
  • a molded body may be formed using the positive electrode mixture, and a part or all of one side of the molded body may be bonded to a positive electrode current collector to form a positive electrode. Bonding of the positive electrode mixture molded body and the positive electrode current collector can be performed by press treatment or the like.
  • metal foil such as Al or Al alloy, punching metal, net, expanded metal, or the like can be used, but Al foil is usually preferably used.
  • the thickness of the positive electrode current collector is preferably 10 to 30 ⁇ m.
  • the composition of the positive electrode mixture layer is, for example, 80.0 to 99.8% by mass of the positive electrode active material, 0.1 to 10% by mass of the conductive auxiliary agent, and 0.1 to 10% by mass of the binder. It is preferable.
  • the thickness of the positive electrode mixture layer is preferably 30 to 300 ⁇ m per side of the current collector.
  • the positive electrode current collector can be provided with a positive electrode lead body according to a conventional method.
  • the positive electrode and the negative electrode are, for example, an electrode body formed by overlapping with a separator, and a winding formed by further winding the electrode body in a spiral shape. It is used in the form of a rotating electrode body or a laminated electrode body in which a plurality of positive electrodes and a plurality of negative electrodes are alternately stacked.
  • the separator preferably has a property of blocking its pores (that is, a shutdown function) at 80 ° C. or higher (more preferably 100 ° C. or higher) and 170 ° C. or lower (more preferably 150 ° C. or lower).
  • a separator used in a water electrolyte secondary battery for example, a microporous membrane made of polyolefin such as polyethylene (PE) or polypropylene (PP) can be used.
  • the microporous film constituting the separator may be, for example, one using only PE or one using PP, or a laminate of a PE microporous film and a PP microporous film. There may be.
  • a porous membrane formed by binding inorganic particles such as alumina, boehmite, kaolin, Mg (OH) 2 with a binder, or an aramid porous membrane is formed on the surface of the microporous membrane made of polyolefin. You may use the laminated body for a separator.
  • the thickness of the separator is preferably 10 to 30 ⁇ m, for example.
  • the non-aqueous electrolyte secondary battery is formed by, for example, loading an electrode body into the exterior body, injecting the non-aqueous electrolyte into the exterior body and immersing the electrode body in the non-aqueous electrolyte, and then opening the exterior body. It is manufactured by sealing the part.
  • an exterior body made of steel, aluminum, aluminum alloy, an exterior body composed of a laminated film on which a metal is deposited, or the like can be used.
  • the non-aqueous electrolyte secondary battery of the present invention in the case where the negative electrode precursor is used, in order to form an alloy of Li with an element that can be alloyed with Li, at least one battery is assembled. It is preferable to perform the chemical conversion treatment which has a charge process which has a discharge process in addition to the charge process of a charge.
  • an element that can be alloyed with Li contained in the negative electrode precursor electrochemically reacts with Li ions in the nonaqueous electrolytic solution to form an alloy of Li and an element that can be alloyed with Li.
  • the negative electrode precursor changes to a negative electrode.
  • the Al metal layer undergoes a large volume expansion, so that a large number of cracks are generated in the Li—Al alloy layer, compared with the case where the chemical conversion treatment is not performed.
  • the load characteristics after high temperature storage can be further improved.
  • Conditions for chemical conversion treatment such as charging conditions can be appropriately set according to required characteristics.
  • Example 1 ⁇ Preparation of positive electrode> LiNi 0.8 Co 0.15 Al 0.05 O 2 as a positive electrode active material: 97 parts by mass, acetylene black as a conductive auxiliary agent: 1.5 parts by mass, PVDF as a binder: 1.5 parts by mass Is applied to both surfaces of a 12 ⁇ m-thick Al foil, dried, and subjected to a press treatment, whereby approximately 12.7 mg / ml is applied to one surface of the Al foil current collector. A positive electrode mixture layer having a mass of cm 2 was formed. Furthermore, the positive electrode mixture layer was pressed and an aluminum lead body was attached to produce a strip-like positive electrode having a length of 974 mm and a width of 43 mm.
  • a clad material (laminated metal foil) having a size of 988 mm ⁇ 44.5 mm, in which an Al foil having a thickness of 20 ⁇ m was laminated on both surfaces of a 35 ⁇ m-thick Cu foil, was used for the production of the negative electrode.
  • a nickel lead body for conductive connection with the outside of the battery was attached to the clad material to form a negative electrode (negative electrode precursor).
  • a separator made of a laminate in which a porous film having a thickness of 4 ⁇ m formed by binding boehmite with acrylic resin on the surface of a microporous film made of PE having a thickness of 12 ⁇ m is connected to the positive electrode and the negative electrode. After being laminated and wound in a spiral shape, they were crushed to form a flat electrode body. In the production of the electrode body, the surface side to which the boehmite of the separator was bound was made to face the positive electrode.
  • LiBF 4 was dissolved at a concentration of 1.2 mol / l in a mixed solvent of propylene carbonate (PC), ethyl methyl carbonate (EMC) and dimethyl carbonate (DEC) at a volume ratio of 17:63:20, and adiponitrile was further added. : 5% by mass, tris (trimethylsilyl) phosphate (TMSP): 0.3% by mass, 1,3-propene sultone (PRS): 0.5% by mass Prepared.
  • PC propylene carbonate
  • EMC ethyl methyl carbonate
  • DEC dimethyl carbonate
  • the electrode body is inserted into a rectangular battery container made of aluminum alloy having a thickness of 0.8 mm, and after the nonaqueous electrolyte is injected, the battery container is sealed, so that the standard capacity is 1200 mAh.
  • a 103450-size square nonaqueous electrolyte secondary battery having the structure shown in FIG. 2 was assembled.
  • FIG. 1 is a partial sectional view of the battery, and the positive electrode 1 and the negative electrode 2 are spirally wound via a separator 3 and then flattened.
  • the flat wound electrode body 6 is pressurized and accommodated in a rectangular (rectangular tube) battery container 4 together with a non-aqueous electrolyte.
  • the layers of the positive electrode 1 and the negative electrode 2, the nonaqueous electrolytic solution, and the like are not shown in order to avoid complication.
  • the battery container 4 is made of an aluminum alloy and constitutes an outer package of the battery, and the battery container 4 also serves as a positive electrode terminal.
  • the insulator 5 which consists of PE sheets is arrange
  • the positive electrode lead body 7 and the negative electrode lead body 8 thus drawn are drawn out.
  • a stainless steel terminal 11 is attached to a sealing lid plate 9 made of aluminum alloy for sealing the opening of the battery container 4 via an insulating packing 10 made of polypropylene, and an insulator 12 is attached to the terminal 11.
  • a stainless steel lead plate 13 is attached.
  • this cover plate 9 is inserted into the opening of the battery container 4, and the opening of the battery container 4 is sealed and the inside of the battery is sealed by welding the joint of both.
  • a non-aqueous electrolyte inlet 14 is provided in the cover plate 9, and a sealing member is inserted into the non-aqueous electrolyte inlet 14, for example, laser welding or the like.
  • the lid plate 9 is provided with a cleavage vent 15 as a mechanism for discharging the internal gas to the outside when the temperature of the battery rises.
  • the positive electrode lead body 7 is directly welded to the lid plate 9 so that the battery container 4 and the lid plate 9 function as a positive electrode terminal, and the negative electrode lead body 8 is welded to the lead plate 13.
  • the terminal 11 functions as a negative electrode terminal by connecting the negative electrode lead body 8 and the terminal 11 through the lead plate 13.
  • the sign may be reversed. There is also.
  • FIG. 2 is a perspective view schematically showing the external appearance of the battery shown in FIG. 1.
  • FIG. 2 is shown for the purpose of showing that the battery is a square battery.
  • FIG. 1 schematically shows a battery, and only specific members of the battery are shown. Also in FIG. 1, the inner peripheral portion of the electrode body is not cross-sectional.
  • Example 2 A square nonaqueous electrolyte secondary battery was assembled in the same manner as in Example 1 except that the amount of tris (trimethylsilyl) phosphate added to the nonaqueous electrolyte was changed to 2% by mass.
  • Example 3 A rectangular nonaqueous electrolyte secondary battery was assembled in the same manner as in Example 1 except that the amount of tris (trimethylsilyl) phosphate added to the nonaqueous electrolyte was changed to 3% by mass.
  • Example 4 A square nonaqueous electrolyte secondary battery was assembled in the same manner as in Example 1 except that the amount of tris (trimethylsilyl) phosphate added to the nonaqueous electrolyte was changed to 7% by mass.
  • Example 5 A square nonaqueous electrolyte secondary battery was assembled in the same manner as in Example 2 except that the addition amount of 1,3-propene sultone in the nonaqueous electrolyte was changed to 1% by mass.
  • Example 6 A square nonaqueous electrolyte secondary battery was assembled in the same manner as in Example 2 except that the addition amount of 1,3-propene sultone in the nonaqueous electrolyte was changed to 2 mass%.
  • Example 7 A square nonaqueous electrolyte secondary battery was assembled in the same manner as in Example 2 except that the amount of 1,3-propene sultone added in the nonaqueous electrolyte was changed to 3% by mass.
  • Example 8 A square nonaqueous electrolyte secondary battery was assembled in the same manner as in Example 2 except that the addition amount of 1,3-propene sultone in the nonaqueous electrolyte was changed to 5% by mass.
  • Example 1 A square nonaqueous electrolyte secondary battery was assembled in the same manner as in Example 1 except that tris (trimethylsilyl) phosphate and 1,3-propene sultone were not added to the nonaqueous electrolyte.
  • Example 2 A prismatic nonaqueous electrolyte secondary battery was assembled in the same manner as in Example 1 except that tris (trimethylsilyl) phosphate was not added to the nonaqueous electrolyte.
  • Each battery after chemical conversion treatment is charged to 3.8 V at a constant current of 0.2 C (240 mA), and then charged until the current value decreases to 0.01 C (12 mA) at a constant voltage of 3.8 V.
  • Continuous constant current-constant voltage charging was performed, and each battery in a charged state was placed in a thermostat at 100 ° C. and held for 7 days.
  • each battery After taking out each battery after holding and allowing it to cool to room temperature, it performs a supplementary charge for self-discharge under the above charging conditions, and further holds for 7 days in a constant temperature bath at 100 ° C.
  • the supplementary charging performed at room temperature after taking out was repeated, and high temperature storage was performed for 56 days in a constant temperature bath at 100 ° C.
  • the thickness of the battery was measured immediately after removal from the thermostat, and the difference from the thickness before high temperature storage was determined as “battery swelling” ( ⁇ t).
  • the battery is allowed to cool to room temperature, further cooled to ⁇ 20 ° C., then 5 W constant power discharge is performed in an environment of ⁇ 20 ° C., and the discharge time until the battery voltage drops to 1.4 V is measured. did. Moreover, the minimum value of the discharge voltage was calculated
  • Table 1 shows each measurement result together with the content of the additive in the non-aqueous electrolyte.
  • the non-aqueous solutions of Examples 1 to 8 using non-aqueous electrolytes containing a phosphoric acid compound having a group represented by the general formula (1) in the molecule and an unsaturated cyclic sultone compound Compared to the battery of Comparative Example 1 that does not contain any of these and the battery of Comparative Example 2 that uses a non-aqueous electrolyte containing only a sultone compound, the electrolyte secondary battery discharges in a low-temperature environment after high-temperature storage. The transient voltage at the time can be increased, whereby a battery having a long discharge time and excellent load characteristics can be obtained.
  • Example 9 A square nonaqueous electrolyte secondary battery was assembled in the same manner as in Example 2 except that 0.5% by mass of lithium difluorophosphate was added to the nonaqueous electrolyte instead of 1,3-propene sultone (PRS). It was.
  • 0.5% by mass of lithium difluorophosphate was added to the nonaqueous electrolyte instead of 1,3-propene sultone (PRS). It was.
  • Example 10 A square nonaqueous electrolyte secondary battery was assembled in the same manner as in Example 9 except that the amount of lithium difluorophosphate added in the nonaqueous electrolyte was changed to 0.1% by mass.
  • Example 11 A prismatic nonaqueous electrolyte secondary battery was assembled in the same manner as in Example 9 except that the amount of lithium difluorophosphate added in the nonaqueous electrolyte was changed to 1% by mass.
  • Example 12 A prismatic nonaqueous electrolyte secondary battery was assembled in the same manner as in Example 9 except that the amount of lithium difluorophosphate added in the nonaqueous electrolyte was changed to 2% by mass.
  • Example 13 A square nonaqueous electrolyte secondary battery was assembled in the same manner as in Example 9 except that the amount of tris (trimethylsilyl) phosphate added to the nonaqueous electrolyte was changed to 0.5% by mass.
  • Example 14 A prismatic nonaqueous electrolyte secondary battery was assembled in the same manner as in Example 9 except that the amount of tris (trimethylsilyl) phosphate added in the nonaqueous electrolyte was changed to 5% by mass.
  • Example 15 A square nonaqueous electrolyte secondary battery was assembled in the same manner as in Example 9 except that lithium monofluorophosphate was added to the nonaqueous electrolyte instead of lithium difluorophosphate.
  • Each battery after chemical conversion treatment is charged to 3.8 V at a constant current of 0.2 C (240 mA), and then charged until the current value decreases to 0.01 C (12 mA) at a constant voltage of 3.8 V.
  • Continuous constant current-constant voltage charging was performed, and each battery in a charged state was placed in a thermostat at 100 ° C. and held for 7 days.
  • each battery After taking out each battery after holding and allowing it to cool to room temperature, it performs a supplementary charge for self-discharge under the above charging conditions, and further holds for 7 days in a constant temperature bath at 100 ° C.
  • the battery was repeatedly taken out and supplemented at room temperature, and stored in a constant temperature bath at 100 ° C. for a total of 28 days.
  • Table 2 shows each measurement result together with the content of the additive in the non-aqueous electrolyte.
  • Examples using a nonaqueous electrolytic solution containing a phosphoric acid compound having a group represented by the general formula (1) in the molecule and lithium monofluorophosphate or lithium difluorophosphate are higher in temperature than the battery of Comparative Example 1 that does not contain any of these and the battery of Comparative Example 3 that uses a non-aqueous electrolyte containing only lithium difluorophosphate.
  • the transient voltage during discharge in a low-temperature environment after storage could be increased, whereby a battery having a long discharge time and excellent load characteristics could be obtained.
  • Example 16 instead of 1,3-propene sultone (PRS), a rectangular non-aqueous solution was obtained in the same manner as in Example 2 except that 0.3% by mass of LiB (C 2 O 4 ) 2 [LiBOB] was added to the non-aqueous electrolyte. An electrolyte secondary battery was assembled.
  • PRS 1,3-propene sultone
  • Example 17 A square nonaqueous electrolyte secondary battery was assembled in the same manner as in Example 16 except that the amount of LiB (C 2 O 4 ) 2 added in the nonaqueous electrolyte was changed to 0.5% by mass.
  • Example 18 A prismatic non-aqueous electrolyte secondary battery was assembled in the same manner as in Example 16 except that the amount of LiB (C 2 O 4 ) 2 added in the non-aqueous electrolyte was changed to 0.75% by mass.
  • Example 19 A square nonaqueous electrolyte secondary battery was assembled in the same manner as in Example 17 except that the amount of tris (trimethylsilyl) phosphate added to the nonaqueous electrolyte was changed to 3% by mass.
  • Each battery after chemical conversion treatment is charged to 3.8 V at a constant current of 0.2 C (240 mA), and then charged until the current value decreases to 0.01 C (12 mA) at a constant voltage of 3.8 V.
  • Continuous constant current-constant voltage charging was performed, and each battery in a charged state was placed in a thermostat at 100 ° C. and held for 7 days.
  • Each battery after holding is taken out, allowed to cool to room temperature, then subjected to a supplementary charge for self-discharge under the above charging conditions, and further held in a 100 ° C. constant temperature bath for 7 days, in a 100 ° C. constant temperature bath And stored for 14 days at high temperature.
  • the thickness of the battery was measured immediately after removal from the thermostat, and the difference from the thickness before high temperature storage was determined as “battery swelling” ( ⁇ t).
  • the battery is allowed to cool to room temperature, further cooled to ⁇ 20 ° C., then 5 W constant power discharge is performed in an environment of ⁇ 20 ° C., and the discharge time until the battery voltage drops to 2.0 V is measured. did.
  • Table 3 shows each measurement result together with the content of the additive in the non-aqueous electrolyte.
  • the non-aqueous solutions of Examples 16 to 19 using a non-aqueous electrolyte containing a phosphoric acid compound having a group represented by the general formula (1) in the molecule and an organic borate lithium salt Compared with the battery of Comparative Example 1 that does not contain any of these, the electrolyte secondary battery had a long discharge time in a low-temperature environment after high-temperature storage and had excellent load characteristics.
  • the batteries of Examples 16 and 17 used a non-aqueous electrolyte solution containing only a phosphoric acid compound having a group represented by the general formula (1) in the molecule for swelling of the battery after high-temperature storage. Compared with the battery of Reference Example 1, it could be suppressed.
  • the non-aqueous electrolyte secondary battery of the present invention can exhibit excellent load characteristics even at low temperatures even after being stored in a high temperature environment, and also has excellent reliability. Taking advantage of this, it can be preferably applied to applications that require good discharge even at low temperatures after being placed in a high temperature environment, such as power supply applications for vehicle emergency notification systems.

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Abstract

La batterie secondaire à électrolyte non aqueux selon la présente invention est caractérisée en ce qu'elle comprend une électrode négative, une électrode positive et un électrolyte non aqueux, l'électrode négative contenant, en tant que matériau actif d'électrode négative, un alliage de Li et un élément pouvant être allié à Li, et l'électrolyte non aqueux contient au moins un additif choisi parmi un composé sultone, un sel de lithium d'acide borique organique, du monofluorophosphate de lithium et du difluorophosphate de lithium et un composé d'acide phosphorique ou un composé d'acide borique contenant chacun un groupe représenté par la formule générale (1) dans sa molécule. [Dans la formule générale (1), X représente le silicium (Si), le germanium (Ge) ou l'étain (Sn) et R1, R2 et R3 représentent indépendamment un groupe alkyle ayant de 1 à 10 atomes de carbone, un groupe alcényle ayant de 2 à 10 atomes de carbone ou un groupe aryle ayant de 6 à 10 atomes de carbone, chacune d'une partie ou de la totalité des atomes d'hydrogène pouvant être substitués par un atome de fluor.]
PCT/JP2017/010141 2016-12-22 2017-03-14 Batterie secondaire à électrolytique non aqueux et son procédé de fabrication Ceased WO2018116491A1 (fr)

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JP2020004596A (ja) * 2018-06-27 2020-01-09 マクセルホールディングス株式会社 非水電解液二次電池およびその製造方法
JP2020155253A (ja) * 2019-03-19 2020-09-24 三菱ケミカル株式会社 非水系電解液二次電池

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JP2007080680A (ja) * 2005-09-14 2007-03-29 Sanyo Electric Co Ltd 耐熱性リチウム二次電池
JP2011049152A (ja) * 2009-07-30 2011-03-10 Mitsubishi Chemicals Corp 非水系電解液及びそれを用いた非水系電解液二次電池
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JP2001319685A (ja) * 1999-03-16 2001-11-16 Sumitomo Chem Co Ltd 非水電解液およびこれを用いたリチウム二次電池
JP2007080680A (ja) * 2005-09-14 2007-03-29 Sanyo Electric Co Ltd 耐熱性リチウム二次電池
JP2011049152A (ja) * 2009-07-30 2011-03-10 Mitsubishi Chemicals Corp 非水系電解液及びそれを用いた非水系電解液二次電池
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JP2020004596A (ja) * 2018-06-27 2020-01-09 マクセルホールディングス株式会社 非水電解液二次電池およびその製造方法
JP7112265B2 (ja) 2018-06-27 2022-08-03 マクセル株式会社 非水電解液二次電池およびその製造方法
JP2020155253A (ja) * 2019-03-19 2020-09-24 三菱ケミカル株式会社 非水系電解液二次電池
JP7246981B2 (ja) 2019-03-19 2023-03-28 三菱ケミカル株式会社 非水系電解液二次電池
JP2023063490A (ja) * 2019-03-19 2023-05-09 三菱ケミカル株式会社 非水系電解液二次電池
JP7494346B2 (ja) 2019-03-19 2024-06-03 三菱ケミカル株式会社 非水系電解液二次電池

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