WO2013018212A1 - Électrolyte de batterie secondaire au lithium-ion et batterie secondaire au lithium-ion qui l'utilise - Google Patents

Électrolyte de batterie secondaire au lithium-ion et batterie secondaire au lithium-ion qui l'utilise Download PDF

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WO2013018212A1
WO2013018212A1 PCT/JP2011/067789 JP2011067789W WO2013018212A1 WO 2013018212 A1 WO2013018212 A1 WO 2013018212A1 JP 2011067789 W JP2011067789 W JP 2011067789W WO 2013018212 A1 WO2013018212 A1 WO 2013018212A1
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ion secondary
lithium ion
electrolyte
secondary battery
group
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PCT/JP2011/067789
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English (en)
Japanese (ja)
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登志雄 阿部
奥村　壮文
井上　亮
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日立ビークルエナジー株式会社
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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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to an electrolyte for a lithium ion secondary battery, a lithium ion secondary battery using the same, and a lithium ion secondary battery module.
  • Lithium ion secondary batteries are often used in mobile phones and notebook computers because they have higher energy density and output density than secondary batteries such as lead batteries and nickel metal hydride batteries.
  • lithium ion secondary batteries have been used not only for small mobile batteries but also for large batteries for hybrid electric vehicles (HEV) and electric vehicles (EV). This is because reduction of carbon dioxide emissions is desired for the purpose of environmental protection and suppression of global warming, and the demand for HEVs and EVs as environment-friendly vehicles is expanding.
  • a large-sized lithium ion secondary battery is expected as a secondary battery for suppressing output fluctuations of electric power generated by natural energy. For applications with large capacity, it is often used as a module in which a plurality of lithium ion secondary batteries are connected in series or in parallel depending on the purpose.
  • the shelf life in a high temperature environment is an issue. Specifically, there is a concern that the lifespan deteriorates due to decomposition or alteration of the constituent materials at high temperatures.
  • a lithium ion secondary battery includes a positive electrode composed of a positive electrode mixture layer containing a lithium-containing transition metal composite oxide such as LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiFeO 2 and a positive electrode current collector such as an aluminum foil, graphite And the like, a negative electrode composed of a negative electrode mixture layer containing copper and a negative electrode current collector such as copper, a separator disposed between the positive electrode and the negative electrode, and an electrolyte containing a solvent, an electrolyte, and an additive.
  • a positive electrode composed of a positive electrode mixture layer containing a lithium-containing transition metal composite oxide such as LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiFeO 2 and a positive electrode current collector such as an aluminum foil, graphite And the like
  • a negative electrode composed of a negative electrode mixture layer containing copper and a negative electrode current collector such as copper
  • LiPF 6 lithium hexafluorophosphate
  • LiPF 6 When LiPF 6 is used, a small amount of moisture present in or entering the battery during the production or use of the secondary battery reacts with LiPF 6 to generate hydrogen fluoride (HF). . Specifically, LiPF 6 is dissociated by heat (LiPF 6 ⁇ LiF + PF 5 ), and PF 5 generated at that time reacts with water to generate HF. In addition to LiPF 6 , fluorine-containing compounds such as polyvinylidene fluoride (PVDF) that are widely used as binders can be decomposed to cause generation of HF. The HF dissolves and corrodes the battery container and the metal mixed as a foreign substance, and dissolves the positive electrode active material to elute the transition metal. Furthermore, an inactive film SEI (Solid Electrolyte Interface) layer containing metal is formed on the surface of the negative electrode active material, which inhibits the movement of Li + ions and causes battery deterioration.
  • PVDF polyvinylidene fluoride
  • the main cause of the internal short circuit of the lithium ion secondary battery is considered to be that the metal foreign matter contained in the raw material or mixed in the manufacturing process exists in the battery. If foreign metal is present in the battery, the foreign metal may break through the separator and penetrate, or the foreign metal may be dissolved and re-deposited in the electrolyte, causing an internal short circuit. As described above, when HF generated from LiPF 6 or the like is present in the electrolytic solution, the amount of dissolved metal increases, and there is a problem that an internal short circuit is likely to occur with a decrease in life and safety is lowered. .
  • Patent Document 1 proposes a method for improving high-temperature storage characteristics by adding dimethallyl carbonate to an electrolytic solution.
  • Patent Document 2 includes a crosslinked polymer electrolyte composition composed of a polyether multi-polymer, an aprotic organic solvent, an additive composed of a phosphorus-containing compound, and an electrolyte compound composed of a lithium salt compound. A method for improving high-temperature storage characteristics using a lithium ion secondary battery has been proposed.
  • Non-Patent Document 1 examines the relationship between the composition of the electrolyte and the storage characteristics. It is shown that by adding 2% by weight of vinylene carbonate (VC) to an electrolyte composed of LiPF 6 , ethylene carbonate (EC) and dimethyl carbonate (DMC), deterioration under a high temperature environment at 60 ° C. can be suppressed. ing.
  • VC vinylene carbonate
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • At least one of a positive electrode plate, a negative electrode plate, a separator, and a nonaqueous electrolytic solution is an organic and / or inorganic Cu corrosion inhibitor, or an organic and / or inorganic Cu trapping agent.
  • Inhibitors include 1,2,3-benzotriazole, or derivatives and analogs thereof such as 4 or 5-methyl-1H-benzotriazole, toltriazole, benzimidazole, 2-benzimidazole, and 2-mercaptobenzimidazole. 2-benzoxazole, 2-methylbenzothiazole, indole, 2-mercaptothiazoline, 2-mercaptobenzothiazole and the like.
  • Patent Document 4 proposes a method in which a non-aqueous electrolyte contains a leveling agent that suppresses the concentrated precipitation of metal ions on the electrode plate.
  • leveling agents include 1,5-naphthalene-sodium disulfonate, 1,3,6-naphthalene-trisulfonate sodium, saccharin, aldehyde, gelatin, 2-butyne-1,4-diol, quinaldine, pyridium.
  • Compounds, ethylene cyanohydrin, azo dyes, potassium thiocyanate, potassium pyrophosphate and the like are mentioned.
  • Patent Document 5 proposes a method of containing a chelating agent that does not react with lithium ions or form a coordination bond but forms a complex with a transition metal ion in the battery.
  • the chelating agent include EDTA, NTA, DCTA, DTPA, EGTA and the like.
  • the present invention has been made in view of such a problem, and an object of the present invention is to provide an electrolytic solution for a lithium ion secondary battery that can improve a storage life in a high temperature environment while suppressing a short circuit of the lithium ion secondary battery. And a lithium ion secondary battery using the same.
  • the inventors of the present invention each contain a specific compound as a substance that suppresses the generation of hydrofluoric acid and a substance that suppresses the precipitation of transition metal in the electrolyte. As a result, it has been found that the improvement of the storage life under high temperature environment and the suppression of short circuit can be achieved at the same time, and the present invention has been completed.
  • the electrolyte for a lithium ion secondary battery of the present invention and the lithium ion secondary battery using the same can suppress a short circuit while suppressing deterioration of the battery due to HF.
  • the lithium ion secondary battery Can improve the service life and safety.
  • the electrolytic solution for a lithium ion secondary battery of the present invention uses a substance that suppresses the generation of HF in the electrolytic solution in order to suppress deterioration of the battery due to HF generation during high-temperature storage, and at the same time, transition in the electrolytic solution.
  • the main feature is to use a substance that suppresses metal deposition. When transition metal foreign matter is present inside the battery and the amount of HF generated increases, dissolution of the transition metal is promoted. Therefore, in a state where the HF concentration in the electrolytic solution is high, short-circuiting due to precipitation of dissolved transition metal ions at the negative electrode is likely to occur.
  • the lithium ion secondary battery of the present invention may be any of a cylindrical type, a laminated type, a coin type, a card type, and the like, and is not particularly limited. As an example, the structure of a wound type lithium ion secondary battery will be described below. .
  • FIG. 1 is a partial cross-sectional view of a wound lithium ion secondary battery.
  • a wound type lithium ion secondary battery has a positive electrode and a negative electrode laminated via a separator, the laminated electrode is wound in a spiral shape to produce an electrode body, the electrode body is loaded into a battery container, and an electrolyte solution Obtained by sealing the battery container.
  • 9 is a negative electrode lead
  • 10 is a positive electrode lead
  • 11 is a positive electrode insulator
  • 12 is a negative electrode insulator
  • 13 is a negative electrode battery can
  • 14 is a gasket
  • 15 is a positive electrode battery lid.
  • the following materials can be used for the lithium ion secondary battery according to the present invention.
  • the electrolytic solution is composed of a solvent, an additive, and an electrolyte salt.
  • an organic solvent-based nonaqueous electrolytic solution in which a lithium salt is dissolved as an electrolyte salt in an organic solvent is used.
  • Examples of the solvent include cyclic carbonates represented by (Formula 6).
  • R 13 , R 14 , R 15 and R 16 are independently hydrogen, fluorine, chlorine, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 1 to 3 carbon atoms, or one or more hydrogen atoms.
  • a C 1-3 alkyl group substituted with fluorine Chain carbonate represented by (Formula 7)
  • R 17 and R 18 are independently hydrogen, fluorine, chlorine, an alkyl group having 1 to 3 carbon atoms, or an alkyl group in which one or more hydrogens are substituted with fluorine). be able to.
  • Examples of the cyclic carbonate represented by (Formula 6) include ethylene carbonate (EC), trifluoropropylene carbonate (TFPC), chloroethylene carbonate (ClEC), fluoroethylene carbonate (FEC), trifluoroethylene carbonate (TFEC), and difluoro.
  • Ethylene carbonate (DFEC), vinyl ethylene carbonate (VEC), or the like can be used. In particular, it is preferable to use EC from the viewpoint of film formation on the negative electrode.
  • DMC dimethyl carbonate
  • EMC ethyl methyl carbonate
  • DEC diethyl carbonate
  • MPC methyl propyl carbonate
  • EPC ethyl propyl carbonate
  • TFEMC trifluoromethyl Ethyl carbonate
  • TFEMC 1,1,1-trifluoroethyl methyl carbonate
  • DMC is a highly compatible solvent and is suitable for use in a mixture with EC or the like.
  • DEC has a lower melting point than DMC and is excellent in low temperature ( ⁇ 30 ° C.) characteristics.
  • EMC is excellent in low temperature characteristics because of its asymmetric molecular structure and low melting point.
  • EPC and TFMEC have propylene side chains and an asymmetric molecular structure, they are suitable as adjusting solvents for low temperature characteristics.
  • TFEMC is suitable for maintaining the dissociation property of lithium salt at a low temperature because it fluorinates a part of the molecule and has a large dipole moment, and has excellent low temperature characteristics.
  • the ratio (capacity ratio) of the cyclic carbonate represented by (Formula 6) and the chain carbonate represented by (Formula 7) in the electrolytic solution is preferably 1: 4 to 1: 2. .
  • the electrolytic solution of the present invention includes a compound represented by (formula 1) as a substance that suppresses the generation of hydrofluoric acid in the electrolytic solution and prevents deterioration during high-temperature storage.
  • R 1 , R 2 and R 3 are each independently fluorine or an alkyl group having 1 to 3 carbon atoms in which one or more hydrogens are substituted with fluorine
  • a compound represented by (formula 2) (Wherein R 4 , R 5 and R 6 are independently hydrogen, fluorine, chlorine, an alkyl group having 1 to 3 carbon atoms, or an alkyl group in which one or more hydrogens are substituted with fluorine) At least one selected from is added.
  • the compound represented by (Formula 4) (Wherein R 9 and R 10 are independently hydrogen, fluorine, chlorine, an alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms)
  • a compound represented by (formula 5) (Wherein R 11 and R 12 are each independently an allyl group, a methallyl group, an etharyl group, a vinyl group, an acrylic group, or a methacryl group)
  • At least one selected from the above can be added.
  • Examples of the compound represented by the formula (1) include tris (2,2,2-trifluoroethyl) phosphite, tris (2,2,2-difluoroethyl) phosphite, tris (2,2,2-fluoro Ethyl) phosphite, tris (2-fluoroethyl-2-difluoroethyl-2-trifluoroethyl) phosphite and the like can be used.
  • the content of the compound represented by (formula 1) in the electrolytic solution is not particularly limited, but is 0.01% by weight to 5% with respect to the total weight of the cyclic carbonate, the chain carbonate, and the electrolyte salt. It is preferable to set it as weight%. More desirably, the content is 0.1% by weight to 2% by weight.
  • Examples of the compound represented by (Formula 2) include formamide, acetamide, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, N-methylacetamide, N, N-dimethylacetamide (DMA), N-methylpropionamide and the like can be used.
  • the content of the compound represented by (Formula 2) in the electrolytic solution is not particularly limited, but is 0.1% by weight to 2% with respect to the total weight of the cyclic carbonate, the chain carbonate, and the electrolyte salt. It is preferable to set it to 0.0% by weight. When the content is higher than 2.0% by weight, the internal resistance of the battery is increased, and the output of the battery is decreased.
  • VC vinylene carbonate
  • MVC methyl vinylene carbonate
  • DMVC dimethyl vinylene carbonate
  • EVC ethyl vinylene carbonate
  • DEVC diethyl vinylene carbonate
  • VC has a low molecular weight and is considered to form a dense electrode film.
  • MVC, DMVC, EVC, DEVC, etc., in which the hydrogen atom of VC is substituted with an alkyl group, is considered to form a lower density electrode coating according to the size of the alkyl chain, and effectively acts to improve low temperature characteristics it is conceivable that.
  • the content of the compound represented by (Formula 4) in the electrolytic solution is not particularly limited, but is 0.1% by weight to 2% with respect to the total weight of the cyclic carbonate, the chain carbonate, and the electrolyte salt. It is preferably 0.0% by weight. When the content is higher than 2.0% by weight, the internal resistance of the battery is increased, and the output of the battery is decreased.
  • diallyl carbonate, dimethallyl carbonate (DMAC), dietalyl carbonate, allyl methallyl carbonate, allyl etalyl carbonate and the like can be used.
  • the content of the compound represented by (Formula 5) in the electrolytic solution is not particularly limited, but is 0.1% by weight to 2% with respect to the total weight of the cyclic carbonate, the chain carbonate, and the electrolyte salt. It is preferably 0.0% by weight. When the content is higher than 2.0% by weight, the internal resistance of the battery is increased, and the output of the battery is decreased.
  • the electrolytic solution of the present invention includes a nitrogen-containing cyclic compound represented by (Formula 3) as a substance for suppressing transition metal precipitation and preventing internal short circuit.
  • R 7 and R 8 are independently hydrogen, fluorine, chlorine, bromine, an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms in which one or more hydrogen atoms are substituted with fluorine, At least one selected from a compound having a sulfonyl group, polyethylene glycol (PEG), polyethylene oxide, polypropylene glycol and polypropylene oxide (which is a hydroxyl group, a nitro group or an amino group).
  • PEG polyethylene glycol
  • PEG polyethylene oxide
  • polypropylene glycol polypropylene oxide
  • Examples of the nitrogen-containing cyclic compound represented by (Formula 3) include triazole and triazole derivatives. Specifically, 1,2,3-benzotriazole (BTA), 1,2,4-triazole, 5- Methyl-1H-benzotriazole (TTA), 3-amino-1,2,4-triazole, pyrazole, imidazole and the like can be used.
  • the content of the nitrogen-containing cyclic compound is not particularly limited, but is 0.01% by weight to 5% by weight, preferably 0.05% by weight with respect to the total weight of the cyclic carbonate, the chain carbonate and the electrolyte salt. % To 1% by weight.
  • the compound having a sulfonyl group sulfolane, 1,3-propane sultone (PS), 1,4-butane sultone, hydroxypropane sultone, or the like can be used.
  • the content of the compound having a sulfonyl group is not particularly limited, but is preferably 0.01% by weight to 10% by weight with respect to the total weight of the cyclic carbonate, the chain carbonate, and the electrolyte salt. If it is less than 0.01% by weight, the effect is small, and if it is more than 10% by weight, not only does not dissolve, but the viscosity of the electrolyte may increase, which is not preferable. More desirably, it is in the range of 0.1 wt% to 5 wt%.
  • Polyethylene glycol, polyethylene oxide, polypropylene glycol, and polypropylene oxide have a mean molecular weight of 2,000 to 2,000,000 because the effect is small when the molecular weight is small, and the molecular weight is too small to dissolve in the solvent.
  • the content of these compounds is not particularly limited, but is preferably 0.1% by weight to 2.0% by weight with respect to the total weight of the cyclic carbonate, the chain carbonate, and the electrolyte salt.
  • the electrolyte salt is not particularly limited, inorganic lithium salt, LiPF 6, LiBF 4, LiClO 4, LiI, LiCl, LiBr , etc., and as organic lithium salt, LiB [OCOCF 3] 4, LiB [OCOCF 2 CF 3] 4, LiPF 4 (CF 3) 2, LiN (SO 2 CF 3) 2, LiN (SO 2 CF 2 CF 3) may be used 2 or the like.
  • LiPF 6 is preferable because of its excellent quality stability and high ion conductivity in a carbonate solvent.
  • the concentration of the electrolyte salt is preferably 0.5 mol / l to 2 mol / l with respect to the total amount of cyclic carbonate and chain carbonate.
  • the positive electrode is formed by applying a positive electrode mixture containing a positive electrode active material, a binder, and a conductive agent on a current collector such as an aluminum foil.
  • a lithium composite oxide can be used as the positive electrode active material.
  • M1 is Ni or Co and M2 is Co or Ni.
  • LiM x PO 4 Fe or Mn, 0.01 ⁇ x ⁇ 0.4
  • LiMn 1-x M x PO 4 M: divalent cation other than Mn, 0.01 ⁇ x
  • An orthorhombic phosphate compound having symmetry of the space group Pmnb represented by ⁇ 0.4 may be used.
  • binder used for producing the positive electrode examples include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyacrylic acid, polyimide resin, and styrene butadiene rubber (SBR).
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • SBR styrene butadiene rubber
  • Examples of the conductive agent include graphite, acetylene black, carbon black, ketjen black, carbon nanotubes and derivatives thereof, carbon fibers, metal powder, and metal fibers.
  • the negative electrode is formed by applying a negative electrode mixture containing a negative electrode active material, a binder, and a conductive agent on a current collector such as a copper foil.
  • a carbonaceous material As the negative electrode active material, a carbonaceous material, a compound alloyed with lithium, lithium metal, or the like is applicable.
  • Carbonaceous materials include natural graphite, composite carbonaceous materials in which a film is formed on natural graphite by a dry CVD method or a wet spray method, resin materials such as epoxy and phenol, or pitch materials obtained from petroleum or coal. And artificial graphite obtained by firing, amorphous carbon materials, and the like.
  • Examples of the compound that forms an alloy with lithium include oxides or nitrides of Group 4 elements such as silicon, germanium, and tin.
  • binder used for producing the negative electrode examples include PVDF, PTFE, polyacrylic acid, polyimide resin, SBR, and the like.
  • Examples of the conductive agent include graphite, acetylene black, carbon black, ketjen black, carbon nanotubes and derivatives thereof, carbon fibers, metal powder, and metal fibers.
  • the well-known separator currently used for the conventional lithium ion secondary battery can be used.
  • examples thereof include microporous films made of polyolefin such as polyethylene and polypropylene, and nonwoven fabrics.
  • the thickness of the separator is preferably thin, and is preferably 20 ⁇ m or less.
  • the lower limit of the thickness is preferably 10 ⁇ m.
  • Battery container those used in conventional lithium ion secondary batteries can be appropriately used.
  • an aluminum or stainless steel container having a battery lid that is laser-welded to the battery container or sealed with a crimp seal through a packing can be used.
  • the positive electrode and the negative electrode are isolated from the container by a glass or resin insulator in the battery container.
  • Method for producing lithium ion secondary battery As an example, a method for manufacturing a wound lithium ion secondary battery will be described below.
  • a conductive material such as graphite, acetylene black, or carbon black was added to and mixed with the lithium composite oxide particles as the positive electrode active material, and then further dissolved in a solvent such as N-methyl-2-pyrrolidinone (NMP).
  • NMP N-methyl-2-pyrrolidinone
  • a binder such as PVDF is added and kneaded to obtain a slurry-like positive electrode mixture. Next, after apply
  • Conductive material such as carbon black, acetylene black and carbon fiber is added to graphite carbon or soft carbon, which is the negative electrode active material, and mixed.
  • PVDF dissolved in NMP as a binder or SBR that is a rubber-based binder is added and then kneaded to obtain a slurry-like negative electrode mixture.
  • coating this slurry on copper foil it dries and produces a negative electrode.
  • the positive electrode and the negative electrode are dried after the mixture is applied to both sides of the current collector. Further, it is densified by rolling and cut into a desired shape to produce an electrode. Next, lead pieces for passing a current through these electrodes are formed. And the separator which consists of a porous insulating material is inserted
  • a battery container battery can
  • Lithium ion secondary battery module As a form using the said lithium ion secondary battery, the lithium ion secondary battery module which connected the some lithium ion secondary battery in series or in parallel is mentioned.
  • This positive electrode mixture is applied onto an aluminum foil as the positive electrode current collector 1, dried at 80 ° C., then pressed with a pressure roller and dried at 120 ° C., whereby the positive electrode mixture layer 2 is collected into the positive electrode collector. It was formed on the electric body 1.
  • the ratio of the pore volume of the positive electrode mixture layer to the total volume of the positive electrode mixture layer was 30 vol%.
  • pseudo-anisotropic carbon which is amorphous carbon
  • carbon black (CB1) as the conductive material
  • PVDF as the binder
  • This negative electrode mixture is applied onto a copper foil as the negative electrode current collector 3 and dried at 80 ° C., and then pressed with a pressure roller and dried at 120 ° C. to thereby form the negative electrode mixture layer 4 in the negative electrode collector. It was formed on the electric body 3.
  • the ratio of the pore volume in the negative electrode mixture layer to the total volume of the negative electrode mixture layer was 35 vol%.
  • a separator 7 was sandwiched between the produced electrodes to form a wound body. Thereafter, this wound body was inserted into the negative electrode battery can 13 and an electrolytic solution was injected.
  • Example 2 The wound lithium ion secondary is the same as Example 1 except that 1.5 wt% VC, 1.5 wt% DMA, and 1.0 wt% TTA are used as additives. A battery was produced.
  • Example 3 The wound lithium ion secondary is the same as in Example 1 except that 2.5 wt% VC, 1.0 wt% DMA, and 2.0 wt% PS are used as additives. A battery was produced.
  • Example 4 The wound lithium ion secondary is the same as Example 1 except that 1.0 wt% VC, 1.0 wt% DMA, and 1.5 wt% PEG2000 were used as additives. A battery was produced.
  • Example 5 The wound lithium ion secondary is the same as Example 1 except that 1.0 wt% VC, 1.0 wt% TTFP, and 1.0 wt% BTA are used as additives. A battery was produced.
  • Example 6 The wound lithium ion secondary is the same as Example 1 except that 1.0 wt% DMAC, 2.0 wt% TTFP, and 0.5 wt% TTA are used as additives. A battery was produced.
  • Example 7 The wound lithium ion secondary is the same as Example 1 except that 1.0 wt% VC, 1.0 wt% DMA, and 0.01 wt% BTA are used as additives. A battery was produced.
  • Example 8 The wound lithium ion secondary is the same as Example 1 except that 1.0 wt% VC, 1.0 wt% DMA, and 5.0 wt% BTA are used as additives. A battery was produced.
  • Example 9 The wound lithium ion secondary is the same as Example 1 except that 1.5 wt% VC, 1.5 wt% DMA, and 0.01 wt% TTA are used as additives. A battery was produced.
  • Example 10 The wound lithium ion secondary is the same as in Example 1 except that 1.5 wt% VC, 1.5 wt% DMA, and 5.0 wt% TTA are used as additives. A battery was produced.
  • Example 11 A wound lithium ion secondary battery was fabricated in the same manner as in Example 1 except that 1.5% by weight of DMA and 1.0% by weight of BTA were used as additives.
  • Example 1 A wound lithium ion secondary battery was fabricated in the same manner as in Example 1 except that only 1.0 wt% VC was used as the additive.
  • Example 2 A wound lithium ion secondary battery was produced in the same manner as in Example 1 except that only 1.5% by weight of DMA was used as an additive.
  • Example 3 A wound lithium ion secondary battery was produced in the same manner as in Example 1 except that only 1.0% by weight of BTA was used as an additive.
  • Example 4 A wound lithium ion secondary battery was produced in the same manner as in Example 1 except that only 0.5 wt% TTA was used as an additive.
  • Example 5 A wound lithium ion secondary battery was produced in the same manner as in Example 1 except that 1.0 wt% VC and 1.5 wt% DMA were used as additives.
  • Example 6 A wound lithium ion secondary battery was produced in the same manner as in Example 1 except that 1.0 wt% VC and 1.0 wt% BTA were used as additives.
  • ⁇ Evaluation method> (Voltage drop rate) Changes in the battery voltage at 25 ° C. of the wound lithium ion secondary batteries produced in each Example and Comparative Example were evaluated. Each battery was charged at 0.3 C with an upper limit voltage of 4.2 V and a constant current and constant voltage charge for 5 hours, and then initialized by repeating charging and discharging up to the lower limit voltage of 2.7 V three times. After the initialization, the battery was left to stand, and the voltage drop rate from the second to third weeks was divided by 7 to obtain the voltage drop rate per day.
  • Capacity maintenance rate Changes in the discharge capacity at 25 ° C. of the wound lithium ion secondary batteries produced in each Example and Comparative Example were evaluated.
  • the capacity retention rate was evaluated by evaluating the rate of change in capacity after storage at 70 ° C. for 30 days, assuming that the discharge capacity after initialization was 100%.
  • the discharge capacity of the battery was measured by charging the battery at 0.3 C to an upper limit voltage of 4.2 V and then discharging to a lower limit voltage of 2.7 V.
  • Table 1 shows the measurement results of the voltage drop rate and the capacity retention rate.
  • the lithium ion secondary battery of the present invention does not impair the capacity even when used in a high temperature environment and has a lower voltage drop than the conventional lithium ion secondary battery. Therefore, the lithium ion secondary battery of the present invention can be widely used as a power source for a hybrid vehicle, a power source for an electric control system of a vehicle, and a backup power source, a power source for industrial equipment such as an electric tool and a forklift, and a power source for a portable device. Also suitable.
  • the present invention is not limited to the above-described embodiment, and includes various modifications.
  • a part of the configuration of one embodiment can be replaced with the configuration of another embodiment, and the configuration of another embodiment can be added to the configuration of one embodiment.
  • Negative electrode battery can 14 Gasket 15 Positive electrode battery cover It quoted by this specification All publications, patents and patent applications are incorporated herein by reference in their entirety.

Abstract

L'invention a pour objet de fournir un électrolyte de batterie secondaire au lithium-ion et une batterie secondaire lithium-ion qui l'utilise qui minimise le court-circuitage d'une batterie secondaire au lithium-ion tout en améliorant la durée de conservation dans un environnement à haute température. Pour ce faire, un électrolyte est utilisé qui comprend en tant qu'agents additifs un matériau permettant de minimiser l'apparition d'acide fluorhydrique dans l'électrolyte et un matériau permettant de minimiser le dépôt d'ions de métal de transition dans l'électrolyte.
PCT/JP2011/067789 2011-08-03 2011-08-03 Électrolyte de batterie secondaire au lithium-ion et batterie secondaire au lithium-ion qui l'utilise WO2013018212A1 (fr)

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CN111048831A (zh) * 2018-10-11 2020-04-21 Sk新技术株式会社 用于二次电池的电解液以及包含电解液的锂二次电池
CN113471534A (zh) * 2021-05-28 2021-10-01 合肥国轩高科动力能源有限公司 一种低温锂离子电池电解液及使用该电解液的锂离子电池
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CN113471534A (zh) * 2021-05-28 2021-10-01 合肥国轩高科动力能源有限公司 一种低温锂离子电池电解液及使用该电解液的锂离子电池

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