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WO2015088051A1 - Électrolyte pour batterie secondaire au lithium et batterie secondaire au lithium le comprenant - Google Patents

Électrolyte pour batterie secondaire au lithium et batterie secondaire au lithium le comprenant Download PDF

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Publication number
WO2015088051A1
WO2015088051A1 PCT/KR2013/011339 KR2013011339W WO2015088051A1 WO 2015088051 A1 WO2015088051 A1 WO 2015088051A1 KR 2013011339 W KR2013011339 W KR 2013011339W WO 2015088051 A1 WO2015088051 A1 WO 2015088051A1
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Prior art keywords
carbonate
secondary battery
lithium secondary
electrolyte
lithium
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English (en)
Korean (ko)
Inventor
김진성
김준희
김휘성
임종호
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SK Innovation Co Ltd
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SK Innovation Co 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
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • 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
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • 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 a high-voltage lithium secondary battery electrolyte and a high-voltage lithium secondary battery containing the same, and more particularly, the electrolyte thickness is not oxidized / decomposed when left at high temperature under high voltage, thereby suppressing gas generation to prevent expansion of the battery.
  • the present invention relates to a high voltage lithium secondary battery electrolyte and a high voltage lithium secondary battery including the same, while reducing the increase rate and having excellent high temperature storage characteristics and excellent discharge characteristics at low temperatures.
  • the battery which is a power source, is also compact, lightweight, and can be charged and discharged for a long time, and have high rate characteristics. Development is strongly demanded.
  • lithium secondary batteries developed in the early 1990s have higher operating voltage and significantly higher energy density than conventional batteries such as Ni-MH, Ni-Cd, and sulfuric acid-lead batteries that use an aqueous electrolyte solution. I am in the spotlight.
  • lithium secondary batteries have safety problems such as ignition and explosion due to the use of nonaqueous electrolyte, and these problems become more serious as the capacity density of the battery increases.
  • the deterioration in safety of the battery generated during continuous charging is a major problem.
  • One of the causes that can affect this is the heat generated by the structural collapse of the anode.
  • the positive electrode active material of the non-aqueous electrolyte battery is composed of lithium-containing metal oxides capable of occluding and releasing lithium and / or lithium ions. Such a positive electrode active material is transformed into a thermally unstable structure as a large amount of lithium is released during overcharging. do.
  • a method of adding an aromatic compound as a redox shuttle additive in an electrolyte is used to control the ignition or explosion caused by the temperature rise inside the battery as described above.
  • Japanese Patent JP2002-260725 discloses a non-aqueous lithium ion battery that can prevent an overcharge current and consequent thermal runaway by using an aromatic compound such as biphenyl.
  • U.S. Patent No. 5,879,834 also adds a small amount of aromatic compounds such as biphenyl and 3-chlorothiophene to electrochemically polymerize at abnormal overvoltage to increase internal resistance to improve battery safety. A method is described.
  • the amount of biphenyl, etc. gradually decreases when the battery is locally discharged at a high temperature for a long time when the relatively high voltage is generated at a normal operating voltage. After 300 cycles of charging and discharging, there are problems in which safety cannot be guaranteed and problems in storage characteristics.
  • high-voltage batteries (4.4V systems) have been continuously researched and developed as a way to increase the electric charge for miniaturization of batteries.
  • increasing the charge voltage generally increases the charge amount.
  • safety problems such as electrolyte decomposition, lack of lithium storage space, and danger caused by the potential rise of the electrode occur. Therefore, in order to make a battery operated at a high voltage, the standard reduction potential difference between the negative electrode active material and the positive electrode active material is easily maintained large, and the overall conditions are managed by the system so that the electrolyte is not decomposed at this voltage.
  • the present invention is to solve the conventional problems, while maintaining the basic performance such as high rate charge and discharge characteristics, life characteristics, etc., the swelling of the battery is significantly improved due to the oxidation / decomposition of the electrolyte in a high voltage state
  • the present invention provides a high voltage lithium secondary battery electrolyte having excellent high temperature storage characteristics and excellent discharge characteristics at low temperature, and a high voltage lithium secondary battery including the same.
  • the present invention to achieve the above object
  • R is an alkyl group of C1-C5
  • n is an integer of 1 to 10.
  • R is methyl, ethyl, propyl, butyl or pentyl
  • n may be an integer of 1, 2 or 3.
  • the nitrile ester compound may be selected from nitrile ester compounds of the following structure:
  • the nitrile ester compound may be included in 1 to 20% by weight based on the total weight of the electrolyte.
  • the electrolyte is one selected from the group consisting of an oxalatoborate compound, a carbonate compound substituted with fluorine, a vinylidene carbonate compound and a sulfinyl group-containing compound or It may further comprise two or more additives.
  • the electrolyte is lithium difluoro oxalatoborate (LiFOB), lithium bisoxalatoborate (LiB (C 2 O 4 ) 2 , LiBOB), fluoroethylene Carbonate (FEC), vinylene carbonate (VC), vinylethylene carbonate (VEC), divinyl sulfone, ethylene sulfite, propylene sulfite, diallyl sulfonate ), Ethane sultone, propane sultone (PS), butane sulton, butene sultone, ethene sultone, butene sultone and propene sultone (PRS) may further include an additive selected from the group.
  • LiFOB lithium difluoro oxalatoborate
  • LiB (C 2 O 4 ) 2 LiBOB
  • FEC fluoroethylene Carbonate
  • VC vinylene carbonate
  • VEC vinylethylene carbonate
  • divinyl sulfone
  • the additive may be included in 0.1 to 5% by weight based on the total weight of the electrolyte.
  • the non-aqueous organic solvent may be selected from a cyclic carbonate solvent, a linear carbonate solvent and a mixed solvent thereof
  • the cyclic carbonate is ethylene carbonate, propylene carbonate , Butylene carbonate, vinylene carbonate, vinyl ethylene carbonate, fluoroethylene carbonate and mixtures thereof
  • the linear carbonate is dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, methyl Propyl carbonate, methyl isopropyl carbonate, ethyl propyl carbonate and mixtures thereof.
  • the non-aqueous organic solvent may have a mixing volume ratio of 9: 1 to 5: 5 of a linear carbonate solvent: cyclic carbonate solvent.
  • the lithium salt is LiPF 6 , LiBF 4 , LiClO 4 , LiSbF 6 , LiAsF 6 , LiN (SO 2 C 2 F 5 ) 2 , LiN (CF 3 SO 2 ) 2 , LiN (SO 3 C 2 F 5 ) 2 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiC 6 H 5 SO 3 , LiSCN, LiAlO 2 , LiAlCl 4 , LiN (C x F 2x + 1 SO 2 ) (C y F 2y + 1 SO 2 ), where x and y are natural numbers, LiCl, LiI, and LiB (C 2 O 4 ) 2 .
  • the lithium salt may be present in a concentration of 0.1 to 2.0 M.
  • the present invention provides a high-voltage lithium secondary battery comprising the high-voltage lithium secondary battery electrolyte.
  • the electrolyte solution for a high voltage lithium secondary battery according to the present invention includes a nitrile ester compound having a specific structure in which the number of carbon atoms of an alkylene group existing between nitrile and carbonyl is changed to 2 or more, so that the electrolyte is oxidized / decomposed under high voltage. Swelling is remarkably improved to show excellent high temperature storage characteristics as well as excellent discharge characteristics even at low temperatures.
  • the high-voltage lithium secondary battery including the high-voltage lithium secondary battery electrolyte according to the present invention is a phenomenon that the battery swells due to oxidation and decomposition of the electrolyte in a high voltage state while maintaining the basic performance such as high efficiency charge and discharge characteristics, life characteristics, etc.
  • the swelling is remarkably improved to show excellent high temperature storage characteristics as well as excellent discharge characteristics even at low temperatures.
  • the present invention relates to a high voltage lithium secondary battery electrolyte for providing a battery having excellent high temperature storage characteristics and lifespan while ensuring stability of the battery in a high voltage state.
  • the present invention is a lithium salt; Non-aqueous organic solvents; And a nitrile ester compound represented by Formula 1; provides a high voltage lithium secondary battery electrolyte comprising:
  • R is an alkyl group of C1-C5
  • n is an integer of 1 to 10.
  • the electrolyte solution for a high voltage lithium secondary battery according to the present invention contains a nitrile ester compound having a specific structure in which the carbon number of the alkylene group existing between the nitrile group and carbonyl is changed to two or more, and thus, between the nitrile group and the carbonyl Since the hydrogen atoms of the alkylene present are stably bonded, the side reactions in the battery are suppressed.
  • the electrolyte is oxidized / decomposed under high voltage, thereby significantly improving the swelling of the battery and thus exhibiting excellent high temperature storage characteristics. It also exhibits excellent discharge characteristics even at low temperatures.
  • R may be selected from methyl, ethyl, propyl, butyl or pentyl, and most preferably from a nitrile ester compound having the following structure: Can:
  • the nitrile ester compound of Formula 1 may be included in 1 to 20% by weight based on the total weight of the secondary battery electrolyte, more preferably 1 to 15% by weight Included in%.
  • the content of the nitrile ester compound of Formula 1 is less than 1% by weight, the effect of suppressing the swelling of the battery during high temperature storage or the improvement of capacity retention is insignificant, and there is no added effect, and the discharge capacity of the lithium secondary battery Or if the improvement effect, such as output is insignificant and it contains more than 20 weight%, the sudden deterioration of lifetime will generate
  • the electrolyte is a life improvement additive for improving battery life, oxalatoborate-based compound, carbonate-based compound substituted with fluorine, vinylidene carbonate-based compound and sulfide It may further include one or two or more additives selected from the group consisting of a silyl group-containing compound.
  • the oxalatoborate-based compound may be a compound represented by Formula 2 or lithium bisoxalatoborate (LiB (C 2 O 4 ) 2 , LiBOB):
  • R 11 and R 12 are each independently a halogen element or a halogenated C1 to C10 alkyl group.
  • oxalatoborate-based additives include LiB (C 2 O 4 ) F 2 (lithium difluoro oxalatoborate, LiFOB) or LiB (C 2 O 4 ) 2 (lithium bisoxalatoborate, LiBOB). Can be mentioned.
  • the carbonate compound substituted with fluorine may be fluoroethylene carbonate (FEC), difluoroethylene carbonate (DFEC), fluorodimethyl carbonate (FDMC), fluoroethyl methyl carbonate (FEMC), or a combination thereof.
  • FEC fluoroethylene carbonate
  • DFEC difluoroethylene carbonate
  • FDMC fluorodimethyl carbonate
  • FEMC fluoroethyl methyl carbonate
  • the vinylidene carbonate-based compound may be vinylene carbonate (VC), vinyl ethylene carbonate (VEC), or a mixture thereof.
  • the sulfinyl group (S ⁇ O) -containing compound may be sulfone, sulfite, sulfonate and sulfone (cyclic sulfonate), which may be used alone or in combination.
  • the sulfone may be represented by the following Chemical Formula 3, and may be divinyl sulfone.
  • the sulfite may be represented by the following Chemical Formula 4, and may be ethylene sulfite or propylene sulfite.
  • the sulfonate may be represented by Formula 5, and may be diallyl sulfonate.
  • sultone include ethane sultone, propane sulton, butane sulton, ethene sultone, butene sultone, propene sultone, and the like.
  • R 13 and R 14 are each independently hydrogen, a halogen atom, an alkyl group of C1-C10, an alkenyl group of C2-C10, an alkyl group or halogen of C1-C10 substituted with halogen. A substituted C2-C10 alkenyl group.
  • the electrolyte is lithium difluoro oxalatoborate (LiFOB), lithium bisoxalatoborate (LiB (C 2 O 4 ) 2 , LiBOB), Fluoroethylene carbonate (FEC), vinylene carbonate (VC), vinyl ethylene carbonate (VEC), divinyl sulfone, ethylene sulfite, propylene sulfite, diallyl sulfonate (diallyl sulfonate), ethane sultone, propane sulton (PS), butane sulton, ethene sultone, butene sultone, and propene sultone (PRS).
  • LiFOB lithium difluoro oxalatoborate
  • LiB (C 2 O 4 ) 2 LiBOB
  • FEC fluoroethylene carbonate
  • VC vinylene carbonate
  • VEC vinyl ethylene carbonate
  • divinyl sulfone
  • the content of the additive is not significantly limited, to 0.1 to 5% by weight relative to the total weight of the electrolyte to improve the battery life in the secondary battery electrolyte, Preferably it may be included in 0.1 to 3% by weight.
  • the non-aqueous organic solvent may include carbonate, ester, ether or ketone alone or a mixed solvent thereof, a cyclic carbonate solvent, a linear carbonate solvent And it is preferable to select from these mixed solvents, It is most preferable to mix and use a cyclic carbonate solvent and a linear carbonate solvent.
  • the cyclic carbonate solvent is large in polarity to sufficiently dissociate lithium ions, but has a disadvantage in that a large viscosity causes a small ion conductivity. Therefore, by using a linear carbonate solvent having a small polarity but a low viscosity in the cyclic carbonate solvent, it is possible to optimize the characteristics of the lithium secondary battery.
  • the cyclic carbonate solvent may be selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, vinyl ethylene carbonate, fluoroethylene carbonate, and mixtures thereof, wherein the linear carbonate solvent is dimethyl carbonate, Diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, ethyl propyl carbonate and mixtures thereof.
  • the non-aqueous organic solvent is a mixed solvent of a cyclic carbonate solvent and a linear carbonate solvent
  • the mixing volume ratio of linear carbonate solvent: cyclic carbonate solvent is 1: 1 to 1 It may be 9: 1, preferably used by mixing in a volume ratio of 1.5: 1 to 4: 1.
  • the lithium salt is not limited, LiPF 6 , LiBF 4 , LiClO 4 , LiSbF 6 , LiAsF 6 , LiN (SO 2 C 2 F 5 ) 2 , LiN (CF 3 SO 2 ) 2 , LiN (SO 3 C 2 F 5 ) 2 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiC 6 H 5 SO 3 , LiSCN, LiAlO 2 , LiAlCl 4 , LiN (C one or two selected from the group consisting of x F 2x + 1 SO 2 ) (C y F 2y + 1 SO 2 ), where x and y are natural numbers, LiCl, LiI, and LiB (C 2 O 4 ) 2 It may be abnormal.
  • the concentration of the lithium salt is preferably used in the range of 0.1 to 2.0 M, more preferably in the range of 0.7 to 1.6 M. If the concentration of the lithium salt is less than 0.1 M, the conductivity of the electrolyte is lowered, the performance of the electrolyte is lowered, and if it exceeds 2.0 M, the viscosity of the electrolyte is increased, thereby reducing the mobility of lithium ions.
  • the lithium salt acts as a source of lithium ions in the battery to enable operation of the basic lithium secondary battery.
  • the electrolyte solution for high voltage lithium secondary batteries of the present invention is generally stable at a temperature range of -20 ° C to 60 ° C, and maintains electrochemically stable characteristics even at a voltage of 4.4 V region, so that all lithium secondary batteries such as lithium ion batteries and lithium polymer batteries may be used. Can be applied.
  • the present invention provides a high-voltage lithium secondary battery comprising the high-voltage lithium secondary battery electrolyte.
  • Non-limiting examples of the secondary battery includes a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery or a lithium ion polymer secondary battery.
  • the high-voltage lithium secondary battery prepared from the high-voltage lithium secondary battery electrolyte according to the present invention exhibits low temperature discharge efficiency of 70% or more and high temperature storage efficiency of 75% or more, and increases the thickness of the battery when it is left at a high temperature for 4 to 14%. It is characterized by low.
  • the high voltage lithium secondary battery of the present invention includes a positive electrode and a negative electrode.
  • the positive electrode includes a positive electrode active material capable of occluding and desorbing lithium ions, and the positive electrode active material is preferably at least one selected from cobalt, manganese, nickel, and a composite metal oxide with lithium.
  • the solid solution ratio between the metals may be various, and in addition to these metals, Mg, Al, Co, K, Na, Ca, Si, Ti, Sn, V, Ge, Ga, B, As, Zr, Mn, Cr, Fe, An element selected from the group consisting of Sr, V and rare earth elements may be further included.
  • Specific examples of the positive electrode active material may be a compound represented by any one of the following formula:
  • Li a A 1-b B b D 2 (wherein 0.90 ⁇ a ⁇ 1.8, and 0 ⁇ b ⁇ 0.5); Li a E 1-b B b 0 2-c D c (wherein 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05); LiE 2-b B b 0 4-c D c (wherein 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05); Li a Ni 1-bc Co b B c D ⁇ (wherein 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05, and 0 ⁇ ⁇ 2); Li a Ni 1-bc Co b B c 0 2- ⁇ F ⁇ (wherein 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05, and 0 ⁇ ⁇ 2);
  • A is Ni, Co, Mn or a combination thereof
  • B is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, rare earth elements or combinations thereof
  • D is O, F, S, P, or a combination thereof
  • E is Co, Mn or a combination thereof
  • F is F, S, P or a combination thereof
  • G is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V or a combination thereof
  • Q is Ti, Mo, Mn or a combination thereof
  • I is Cr, V, Fe, Sc, Y or a combination thereof
  • J may be V, Cr, Mn, Co, Ni, Cu or a combination thereof.
  • the negative electrode includes a negative electrode active material capable of occluding and desorbing lithium ions
  • examples of the negative electrode active material include carbon materials such as crystalline carbon, amorphous carbon, carbon composite, carbon fiber, lithium metal, alloys of lithium and other elements, and the like.
  • amorphous carbon includes hard carbon, coke, mesocarbon microbeads (MCMB) fired at 1500 ° C. or lower, mesophase pitch-based carbon fibers (MPCF), and the like.
  • the crystalline carbon includes a graphite material, and specific examples thereof include natural graphite, graphitized coke, graphitized MCMB, graphitized MPCF, and the like.
  • the carbonaceous material is preferably a material having an d002 interplanar distance of 3.35 to 3.38 kPa and an Lc (crystallite size) of at least 20 nm by X-ray diffraction.
  • Other elements alloyed with lithium may be aluminum, zinc, bismuth, cadmium, antimony, silicon, lead, tin, gallium or indium.
  • the positive electrode or the negative electrode may be prepared by dispersing an electrode active material, a binder and a conductive material, if necessary, a thickener in a solvent to prepare an electrode slurry composition, and applying the slurry composition to an electrode current collector.
  • an electrode current collector aluminum or an aluminum alloy may be commonly used
  • the negative electrode current collector copper or a copper alloy may be commonly used.
  • the positive electrode current collector and the negative electrode current collector may be in the form of a foil or a mesh.
  • the binder is a material that plays a role of pasting the active material, mutual adhesion of the active material, adhesion with the current collector, buffering effect on the expansion and contraction of the active material, and the like, for example, polyvinylidene fluoride (PVdF), polyhexafluoro Copolymer of propylene-polyvinylidene fluoride (PVdF / HFP)), poly (vinylacetate), polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, alkylated polyethylene oxide, polyvinyl ether, poly (methylmeth) Acrylate), poly (ethyl acrylate), polytetrafluoroethylene, polyvinylchloride, polyacrylonitrile, polyvinylpyridine, styrene-butadiene rubber, acrylonitrile-butadiene rubber, and the like.
  • PVdF polyvinylidene fluoride
  • PVdF / HFP polyhe
  • the content of the binder is 0.1 to 30% by weight, preferably 1 to 10% by weight based on the electrode active material.
  • the content of the binder is too small, the adhesion between the electrode active material and the current collector is insufficient, and when the content of the binder is too large, the adhesion is improved, but the content of the electrode active material decreases by that amount, which is disadvantageous in increasing the capacity of the battery.
  • the conductive material is used to impart conductivity to the electrode, and any battery can be used as long as it is an electronic conductive material without causing chemical change in the battery constituted, and may be a graphite-based conductive agent, a carbon black-based conductive agent, a metal or a metal compound-based compound. At least one selected from the group consisting of conductive agents can be used.
  • the graphite conductive agent include artificial graphite and natural graphite
  • examples of the carbon black conductive agent include acetylene black, ketjen black, denka black, thermal black, and channel black.
  • the metal or metal compound conductive agent examples include tin, tin oxide, tin phosphate (SnPO 4 ), titanium oxide, potassium titanate, LaSrCoO 3 , and perovskite such as LaSrMnO 3 .
  • the conductive agents listed above include tin, tin oxide, tin phosphate (SnPO 4 ), titanium oxide, potassium titanate, LaSrCoO 3 , and perovskite such as LaSrMnO 3 .
  • the content of the conductive agent is preferably 0.1 to 10% by weight based on the electrode active material.
  • the content of the conductive agent is less than 0.1% by weight, the electrochemical properties are lowered, and when the content of the conductive agent is greater than 10% by weight, the energy density per weight decreases.
  • the thickener is not particularly limited as long as it can play a role of controlling the viscosity of the active material slurry.
  • carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, or the like may be used.
  • a non-aqueous solvent or an aqueous solvent is used as a solvent in which an electrode active material, a binder, a conductive material, etc. are disperse
  • distributed a non-aqueous solvent or an aqueous solvent is used.
  • the non-aqueous solvent include N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide, N, N-dimethylaminopropylamine, ethylene oxide and tetrahydrofuran.
  • the high voltage lithium secondary battery of the present invention may include a separator that prevents a short circuit between the positive electrode and the negative electrode and provides a movement path of lithium ions, and the separator may be polypropylene, polyethylene, polyethylene / polypropylene, polyethylene / polypropylene.
  • Polyolefin-based polymer membranes such as polyethylene, polypropylene / polyethylene / polypropylene, or multiple membranes thereof, microporous films, woven fabrics and nonwoven fabrics can be used.
  • a film coated with a resin having excellent stability in a porous polyolefin film may be used.
  • the high voltage lithium secondary battery of the present invention may be formed in other shapes, such as cylindrical, pouch type, in addition to the square.
  • a mixture of cyanoacetic acid (51 g), sodium hydroxide (24 g), ethane bromide (327 g) and tetrabutylammonium bromide (19 g) was added to a mixture of chlorobenzene and water (volume ratio 2/1) (450 mL). It was added and the temperature was raised and stirred at 100 °C for 4 hours. After completion of the reaction, the mixture was cooled to room temperature, and the aqueous layer was separated and extracted with t-butylmethylether. Magnesium sulfate was added and dried, and purified cyanoacetic acid ethyl ester (44 g) was obtained by distillation under reduced pressure.
  • the battery to which the non-aqueous electrolyte was applied was prepared as follows.
  • LiNiCoMnO 2 and LiMn 2 O 4 as a positive electrode active material were mixed at a weight ratio of 1: 1, polyvinylidene fluoride (PVdF) as a binder and carbon as a binder were mixed at a weight ratio of 92: 4: 4, and then N- A positive electrode slurry was prepared by dispersing in methyl-2-pyrrolidone. The slurry was coated on an aluminum foil having a thickness of 20 ⁇ m, dried, and rolled to prepare a positive electrode.
  • PVdF polyvinylidene fluoride
  • Synthetic graphite as a negative electrode active material, styrene-butadiene rubber as a binder, and carboxymethyl cellulose as a thickener were mixed in a weight ratio of 96: 2: 2, and then dispersed in water to prepare a negative electrode active material slurry.
  • the slurry was coated on a copper foil having a thickness of 15 ⁇ m, dried, and rolled to prepare a negative electrode.
  • a cell separator was formed by stacking a 25 ⁇ m thick polyethylene (PE) film separator between the electrodes, using a pouch having a thickness of 8 mm x 270 mm x 185 mm. Injecting the non-aqueous electrolyte, a 25Ah lithium secondary battery for EV was prepared.
  • PE polyethylene
  • Capacity recovery rate after 30 days at 60 ° C (high temperature storage efficiency): After charging for 3 hours at 4.4V and 12.5A CC-CV at room temperature, and after 30 days at 60 ° C, discharged to CC at 25A and CC to 2.7V. The usable capacity (%) relative to the initial dose was measured.
  • Thickness increase after 30 days at 60 °C After charging for 3 hours at 4.4V and 12.5A CC-CV at room temperature, the thickness of the battery is called A and the temperature is exposed to 30 °C at 60 °C and atmospheric pressure using a sealed thermostat. When the thickness of the battery, which was left unattended, the increase rate of the thickness was calculated as in Equation 1 below.
  • the high voltage lithium secondary battery including the high voltage lithium secondary battery electrolyte according to the present invention showed a low-temperature discharge efficiency of 72% or more and a high temperature storage efficiency of 70% or more.
  • the increase rate of the battery is very low as 3 to 14%, and the capacity retention rate during the lifetime is excellent to 64% or more (Examples 1 to 7).
  • Comparative Examples 1 to 3 showed a low-temperature discharge efficiency of less than 58% and a high-temperature storage efficiency of less than 37%, and the thickness increase rate of the battery was very high at 30 to 90% when left at a high temperature for a long time.
  • the retention rate was 20% in Comparative Example 1, but was not measured in Comparative Examples 2 and 3.
  • Example 2 In order to measure the oxidative decomposition voltages of Example 2 and Comparative Example 1, a linear sweep was performed by using a Pt electrode on a working electrode and a Li-metal as a counter electrode and a reference electrode. As a result of measuring the voltametry, 10 wt% PHE16 was added to the electrolyte solution of Example 2 (basic electrolyte solution + 10 wt% PHE16) compared to the basic electrolyte solution of Comparative Example 1, resulting in high oxidation potential (Oxidation Potential) and decomposition at high voltage. It was confirmed that the less [Fig. 1].
  • Example 2 when comparing Example 2 with Comparative Examples 2 and 3, the high temperature storage efficiency (Example 2: 78%, Comparative Example 2: 12%, Comparative Example 3: according to the structure of the nitrile ester compound added to the basic electrolyte solution) 8%), the increase rate of the battery when left at high temperature for a long time (Example 2: 10%, Comparative Example 2: 85%, Comparative Example 3: 90%), low temperature discharge efficiency (Example 2: 75%, Comparative Example 2 : 58%, Comparative Example 3: 52%), it can be seen that a significant difference remains.
  • the electrolyte solution for a high voltage lithium secondary battery according to the present invention contains a nitrile ester compound having a structure having 2 or more carbon atoms of an alkylene group present between the nitrile group and carbonyl. Since the hydrogen atoms are stably bound, side reactions in the battery are suppressed, and the electrolyte oxidizes and decomposes at high voltage, thereby greatly improving the swelling of the battery, thereby exhibiting excellent high temperature storage characteristics and excellent discharge even at low temperatures. Characteristics.
  • the electrolyte solution for a high voltage lithium secondary battery according to the present invention includes a nitrile ester compound having a specific structure in which the number of carbon atoms of an alkylene group existing between nitrile and carbonyl is changed to two or more, so that the electrolyte is oxidized / decomposed at high voltage. Swelling is remarkably improved to show excellent high temperature storage characteristics as well as excellent discharge characteristics even at low temperatures.
  • the high-voltage lithium secondary battery including the high-voltage lithium secondary battery electrolyte according to the present invention is a phenomenon that the battery swells due to oxidation and decomposition of the electrolyte in a high voltage state while maintaining the basic performance such as high efficiency charge and discharge characteristics, life characteristics, etc.
  • the swelling is remarkably improved to show excellent high temperature storage characteristics as well as excellent discharge characteristics even at low temperatures.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
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Abstract

La présente invention porte sur un électrolyte pour une batterie secondaire au lithium à haute tension et une batterie secondaire au lithium à haute tension le contenant, et plus précisément sur un électrolyte pour une batterie secondaire au lithium à haute tension et une batterie secondaire au lithium à haute tension le contenant dans lesquels l'électrolyte ne s'oxyde pas ou ne se décompose pas sous une pression élevée lorsqu'il est laissé à une température élevée, ce qui permet de supprimer une génération de gaz pour empêcher la dilatation de la batterie, ce qui à son tour réduit le taux d'augmentation d'épaisseur de la batterie et confère à la batterie une superbe propriété de stockage à haute température, et de plus la présente invention possède une excellente propriété de décharge à basse température.
PCT/KR2013/011339 2013-12-09 2013-12-09 Électrolyte pour batterie secondaire au lithium et batterie secondaire au lithium le comprenant Ceased WO2015088051A1 (fr)

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Cited By (6)

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CN105789696A (zh) * 2016-04-22 2016-07-20 中山大学 一种含有新型硼酸锂的电解液及使用该锂盐的电池
CN106299474A (zh) * 2016-09-20 2017-01-04 东莞市航盛新能源材料有限公司 钛酸锂电池用电解液及其电池制品
CN112993398A (zh) * 2019-12-13 2021-06-18 张家港市国泰华荣化工新材料有限公司 一种锂离子电池电解液及锂电池
CN113241478A (zh) * 2021-05-08 2021-08-10 宁德新能源科技有限公司 电解液、电化学装置以及用电设备
CN114792838A (zh) * 2021-01-26 2022-07-26 通用汽车环球科技运作有限责任公司 用于含磷橄榄石正电极的三元盐电解质
US11742522B2 (en) 2018-12-27 2023-08-29 Murata Manufacturing Co., Ltd. Non-aqueous electrolytic solution and non-aqueous electrolyte secondary battery

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JP2010165653A (ja) * 2008-02-29 2010-07-29 Equos Research Co Ltd リチウムイオン電池用電解液
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US20060035144A1 (en) * 2004-08-03 2006-02-16 Ryuichi Shimizu Lithium rechargeable battery and lithium rechargeable battery pack
KR20060095221A (ko) * 2005-02-28 2006-08-31 삼성에스디아이 주식회사 리튬 전지용 전해질 및 그를 포함하는 리튬 전지
KR100810634B1 (ko) * 2006-11-30 2008-03-06 삼성에스디아이 주식회사 리튬 이차 전지용 전해액 및 이를 포함하는 리튬 이차 전지
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105789696A (zh) * 2016-04-22 2016-07-20 中山大学 一种含有新型硼酸锂的电解液及使用该锂盐的电池
CN105789696B (zh) * 2016-04-22 2018-05-04 中山大学 一种含有新型硼酸锂的电解液及使用该锂盐的电池
CN106299474A (zh) * 2016-09-20 2017-01-04 东莞市航盛新能源材料有限公司 钛酸锂电池用电解液及其电池制品
US11742522B2 (en) 2018-12-27 2023-08-29 Murata Manufacturing Co., Ltd. Non-aqueous electrolytic solution and non-aqueous electrolyte secondary battery
CN112993398A (zh) * 2019-12-13 2021-06-18 张家港市国泰华荣化工新材料有限公司 一种锂离子电池电解液及锂电池
CN112993398B (zh) * 2019-12-13 2023-01-13 张家港市国泰华荣化工新材料有限公司 一种锂离子电池电解液及锂电池
CN114792838A (zh) * 2021-01-26 2022-07-26 通用汽车环球科技运作有限责任公司 用于含磷橄榄石正电极的三元盐电解质
CN113241478A (zh) * 2021-05-08 2021-08-10 宁德新能源科技有限公司 电解液、电化学装置以及用电设备

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