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WO2010056064A2 - Solution électrolytique non aqueuse pour pile rechargeable au lithium et pile rechargeable au lithium utilisant une telle solution - Google Patents

Solution électrolytique non aqueuse pour pile rechargeable au lithium et pile rechargeable au lithium utilisant une telle solution Download PDF

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Publication number
WO2010056064A2
WO2010056064A2 PCT/KR2009/006687 KR2009006687W WO2010056064A2 WO 2010056064 A2 WO2010056064 A2 WO 2010056064A2 KR 2009006687 W KR2009006687 W KR 2009006687W WO 2010056064 A2 WO2010056064 A2 WO 2010056064A2
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WIPO (PCT)
Prior art keywords
silanol
allyl
vinyl
formula
lithium secondary
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/KR2009/006687
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English (en)
Korean (ko)
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WO2010056064A3 (fr
Inventor
전종호
김수진
이호춘
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LG Chem Ltd
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LG Chem Ltd
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Publication date
Priority claimed from KR1020090109232A external-priority patent/KR101040464B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to US12/677,934 priority Critical patent/US8268489B2/en
Priority to JP2011536248A priority patent/JP5723778B2/ja
Publication of WO2010056064A2 publication Critical patent/WO2010056064A2/fr
Publication of WO2010056064A3 publication Critical patent/WO2010056064A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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 nonaqueous electrolyte solution for a lithium secondary battery and a lithium secondary battery containing the same.
  • Lithium secondary batteries are the batteries that can best meet these demands, and research on these is being actively conducted.
  • lithium secondary batteries developed in the early 1990s are nonaqueous materials in which lithium salts are dissolved in an appropriate amount of lithium salt in a negative electrode made of carbon material capable of occluding and releasing lithium ions, a positive electrode made of lithium-containing oxide, and a mixed organic solvent. It consists of electrolyte solution.
  • the average discharge voltage of the lithium secondary battery is about 3.6 ⁇ 3.7V, one of the advantages is that the discharge voltage is higher than other alkaline batteries, nickel-cadmium batteries and the like.
  • an electrochemically stable electrolyte composition is required in the charge and discharge voltage range of 0 to 4.2 V.
  • a mixed solvent in which cyclic carbonate compounds such as ethylene carbonate and propylene carbonate and linear carbonate compounds such as dimethyl carbonate, ethylmethyl carbonate and diethyl carbonate are appropriately mixed is used as a solvent of the electrolyte solution.
  • LiPF 6 , LiBF 4 , LiClO 4 , and the like are commonly used as lithium salts as electrolytes, which act as a source of lithium ions in the battery to enable operation of the lithium battery.
  • lithium ions derived from the positive electrode active material such as lithium metal oxide move to the negative electrode active material such as graphite and are inserted between the layers of the negative electrode active material.
  • the electrolyte and the carbon constituting the negative electrode active material react on the surface of the negative electrode active material such as graphite to generate compounds such as Li 2 CO 3 , Li 2 O, and LiOH.
  • SEI Solid Electrolyte Interface
  • the SEI film acts as an ion tunnel to pass only lithium ions.
  • the SEI film is an effect of this ion tunnel, which prevents the breakdown of the negative electrode structure by inserting organic solvent molecules having a high molecular weight moving together with lithium ions in the electrolyte between the layers of the negative electrode active material. Therefore, by preventing contact between the electrolyte solution and the negative electrode active material, decomposition of the electrolyte solution does not occur, and the amount of lithium ions in the electrolyte solution is reversibly maintained to maintain stable charge and discharge.
  • the battery thickness expands during charging due to gases such as CO, CO 2 , CH 4 , and C 2 H 6 generated from decomposition of the carbonate solvent during the above-described SEI formation reaction.
  • gases such as CO, CO 2 , CH 4 , and C 2 H 6 generated from decomposition of the carbonate solvent during the above-described SEI formation reaction.
  • the SEI film gradually collapses due to increased electrochemical energy and thermal energy, so that side reactions in which the exposed cathode surface reacts with the surrounding electrolyte continuously occur.
  • the internal pressure of the battery is increased due to the continuous gas generation.
  • the thickness of the battery increases, causing problems in sets such as mobile phones and notebook computers. That is, high temperature leaving safety is bad.
  • the SEI film is unstable, so that the problem of increasing the internal pressure of the battery is more prominent.
  • studies have been conducted to change the aspect of the SEI film formation reaction by adding an additive to a carbonate organic solvent.
  • a certain compound is added to the electrolyte to improve battery performance, the performance of some items is improved, but the performance of other items is often decreased.
  • the problem to be solved by the present invention is to solve the above-mentioned problems of the prior art, not only improve the charge-discharge cycle life characteristics when applied to a lithium secondary battery, the battery is stored at a high temperature in a fully-charged state (fully-charged state)
  • the present invention provides a nonaqueous electrolyte for a lithium secondary battery and a lithium secondary battery having the same, in which the decomposition reaction of the electrolyte is suppressed even when charging or discharging proceeds, thereby improving the swelling phenomenon.
  • the nonaqueous electrolyte solution for a lithium secondary battery including a lithium salt and a carbonate-based organic solvent further includes a silicon-based compound represented by Formula 1 below.
  • X is a hydrogen atom
  • R1, R2 and R3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, at least one of which has a carbon double bond.
  • at least one of R 1, R 2, and R 3 of Formula 1 is a vinyl group or an allyl group.
  • silicone compound examples include dimethyl vinyl silanol, methylethyl vinyl silanol, methylpropyl vinyl silanol, methylbutyl vinyl silanol, methyl cyclohexyl vinyl silanol, methyl phenyl vinyl silanol, methyl benzyl vinyl silanol, and diethyl vinyl.
  • the carbonate organic solvent may be a cyclic carbonate compound, a linear carbonate compound or a mixture thereof, and may further contain a linear ester compound.
  • the carbonate-based organic solvent it is preferable to use a mixture of a cyclic carbonate compound represented by the following formula (2) and a linear carbonate compound represented by the following formula (3), and may further contain a cyclic carbonate compound represented by the following formula (4) as necessary. Can be.
  • R1 to R4 are each independently selected from the group consisting of a hydrogen atom, a fluorine element, and an alkyl group having 1 to 4 carbon atoms.
  • R7 and R8 are each independently an alkyl group having 1 to 4 carbon atoms, and the alkyl group may be optionally substituted with at least one hydrogen atom by fluorine.
  • R5 and R6 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • the carbonate-based organic solvent includes a cyclic carbonate compound represented by Formula 2, and the nonaqueous electrolyte preferably further contains a linear ester compound represented by Formula 5 below.
  • R9 and R10 are each independently an alkyl group having 1 to 4 carbon atoms, and the alkyl group may be optionally substituted with at least one hydrogen atom by fluorine.
  • the nonaqueous electrolyte for lithium secondary batteries described above is usefully applied to conventional lithium secondary batteries having a negative electrode and a positive electrode.
  • lithium cobalt oxide lithium nickel oxide, or a mixture thereof as the positive electrode
  • the nonaqueous electrolyte according to the present invention When the nonaqueous electrolyte according to the present invention is used in a lithium secondary battery, not only the degradation of the charge-discharge cycle life characteristics is improved, but even when the battery is stored at a high temperature in a fully-charged state or charge / discharge proceeds, Since the decomposition reaction is suppressed, the swelling phenomenon can be prevented and the high temperature life characteristics can be improved.
  • the nonaqueous electrolyte solution for a lithium secondary battery including a lithium salt and an organic solvent further includes a silicon-based compound represented by Formula 1 below.
  • X is a hydrogen atom
  • R1, R2 and R3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, at least one of which has a carbon double bond.
  • at least one of R 1, R 2, and R 3 of Formula 1 is a vinyl group or an allyl group.
  • the silicon compound represented by Chemical Formula 1 has a hydroxyl group and a hydrocarbon group having a carbon double bond at the same time. Due to the carbon double bond functional group of the silicon compound, SEI is formed on the surface of the negative electrode before the organic solvent through a reduction reaction with the negative electrode during the initial heavy discharge of the battery. Moreover, the hydroxyl group which a silicone type compound has becomes a stable compound by reacting with hydrofluoric acid which generate
  • the nonaqueous electrolyte containing the silicon-based compound of the present invention when used in a lithium secondary battery, not only the degradation of the charge / discharge cycle life characteristics is improved, but the battery is stored at a high temperature in a fully-charged state or Even when charging and discharging proceeds, the decomposition reaction of the electrolyte is suppressed, so that a swelling phenomenon can be prevented and high temperature life characteristics can be improved.
  • the content of the silicon compound of Formula 1 is preferably 0.1 to 12 parts by weight based on 100 parts by weight of the nonaqueous electrolyte. If the content of the silicon-based compound is less than 0.1 parts by weight can not be formed sufficient solid-electrolyte interface (SEI) at the electrode it can be difficult to expect the effect of the present invention, if it exceeds 12 parts by weight of the prepared non-aqueous electrolyte Increasing the viscosity and increasing the resistance of the formed SEI can reduce the effects of the present invention.
  • SEI solid-electrolyte interface
  • silicone compound of Formula 1 examples include dimethyl vinyl silanol, methylethyl vinyl silanol, methylpropyl vinyl silanol, methylbutyl vinyl silanol, methyl cyclohexyl vinyl silanol, methyl phenyl vinyl silanol, methyl benzyl vinyl silanol, Diethyl vinyl silanol, ethylpropyl vinyl silanol, ethylbutyl vinyl silanol, ethyl cyclohexyl vinyl silanol, ethyl phenyl vinyl silanol, ethyl benzyl vinyl silanol, dipropyl vinyl silanol, propylbutyl vinyl silanol, propyl Cyclohexyl vinyl silanol, propyl phenyl vinyl silanol, propyl benzyl vinyl silanol, dibutyl vinyl silanol, butyl cyclol
  • a carbonate organic solvent commonly used as the carbonate organic solvent for example, a cyclic carbonate compound, a linear carbonate compound, or a mixture thereof may be used, and may further contain a linear ester compound.
  • a carbonate-based organic solvent it is preferable to use a mixture of a cyclic carbonate compound represented by the following formula (2) and a linear carbonate compound represented by the following formula (3), and may further contain a cyclic carbonate compound represented by the following formula (4) as necessary. Can be.
  • R1 to R4 are each independently selected from the group consisting of a hydrogen atom, a fluorine element, and an alkyl group having 1 to 4 carbon atoms.
  • R7 and R8 are each independently an alkyl group having 1 to 4 carbon atoms, and the alkyl group may be optionally substituted with at least one hydrogen atom by fluorine.
  • R5 and R6 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • the carbonate-based organic solvent includes a cyclic carbonate compound represented by Formula 2, and the nonaqueous electrolyte preferably further contains a linear ester compound represented by Formula 5 below.
  • R9 and R10 are each independently an alkyl group having 1 to 4 carbon atoms, and the alkyl group may be optionally substituted with at least one hydrogen atom by fluorine.
  • the cyclic carbonate compound dissociates the lithium salt in the electrolyte well and contributes to the improvement of the charge / discharge capacity of the battery.
  • the carbonate compound represented by the formula (2) ethylene carbonate, propylene carbonate, fluoroethylene carbonate, butylene carbonate and the like may be used alone or in combination of two or more thereof.
  • ethylene carbonate or a mixture of ethylene carbonate and propylene carbonate has a high dielectric constant, which dissociates lithium salts in the electrolyte better.
  • the preferred mixing volume ratio of propylene carbonate is 1/4 to 1 of ethylene carbonate.
  • linear carbonate compound of Formula 3 may contribute to the improvement of the charge and discharge efficiency of the lithium secondary battery and the optimization of battery characteristics, such as dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methylpropyl carbonate, etc. It can mix and use species.
  • the cyclic carbonate compound of Formula 4 includes vinylene carbonate.
  • the linear ester compound of formula (5) is a low viscosity, low melting point organic solvent showing a low freezing point, a relatively high boiling point, excellent low temperature properties. Moreover, the reactivity with respect to a carbon material negative electrode is comparatively low.
  • the linear ester compound may be mixed with the above-described cyclic carbonate compound to contribute to low temperature discharge characteristics and life improvement of the lithium secondary battery. That is, the linear ester-based compound appropriately coordinates lithium ions and exhibits high ionic conductivity at room temperature and low temperature, thereby improving low temperature discharge characteristics and high rate discharge characteristics of the battery.
  • the oxidation voltage which is an intrinsic property of the solvent, is 4.5 V or more, thereby improving the life performance of the battery by making it resistant to the electrolyte decomposition reaction at the anode during charging.
  • the wettability with respect to the electrode is improved compared to when only the carbonate ester solvent is used as the nonaqueous electrolyte, thereby suppressing the formation of lithium dendrite on the electrode surface, thereby contributing to the improvement of battery safety.
  • linear ester compound of Formula 5 examples include methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, and more preferably ethyl propionate and ethyl 3-fluoro.
  • Roprophanoate, Ethyl 3,3-difluoropropanoate, Ethyl 3,3,3-trifluoropropanoate, 2-fluoroethyl propionate, 2,2-difluoroethyl propio Nate, 2,2,2-trifluoroethyl propionate, 2,2,2-trifluoroethyl 3-fluoropropanoate, 2,2,2-trifluoroethyl 3,3-difluoro Lorophanoate, 2,2,2-trifluoroethyl 3,3,3-trifluoropropanoate, and the like can be used alone or in combination of two or more thereof.
  • the lithium salt included as an electrolyte in the nonaqueous electrolyte may be used without limitation those conventionally used in the nonaqueous electrolyte for lithium secondary batteries.
  • Representative examples of the lithium salt include LiPF 6, LiBF 4, LiSbF 6, LiAsF 6, LiClO 4 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) 2 , CF 3 SO 3 Li, LiC (CF 3 SO 2 ) 3 , and the like.
  • the nonaqueous electrolyte of the present invention includes vinyl ethylene carbonate, succinonitrile, cyclohexyl benzene, biphenyl, 1,3-dioxolane-2-onylmethyl allyl sulfonate, and the like. Of course, it can contain further within the limit unless it is inhibited.
  • nonaqueous electrolyte is used as a nonaqueous electrolyte of a conventional lithium secondary battery having a negative electrode, a positive electrode, and a nonaqueous electrolyte.
  • a material made of carbon material is usually used as a material capable of occluding and releasing lithium ions, and a material made of a lithium-containing oxide is usually used as the positive electrode.
  • both low crystalline carbon and high crystalline carbon may be used.
  • Soft crystalline carbon and hard carbon are typical low crystalline carbon, and high crystalline carbon is natural graphite, Kish graphite, pyrolytic carbon, liquid crystal pitch-based carbon fiber.
  • High temperature calcined carbon such as (mesophase pitch based carbon fiber), meso-carbon microbeads, Mesophase pitches and petroleum or coal tar pitch derived cokes.
  • the negative electrode may include a binder
  • the binder may include vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidene fluoride, polyacrylonitrile, Various kinds of binder polymers, such as polymethylmethacrylate, may be used.
  • a lithium-containing transition metal oxide can be preferably used as the anode made of a lithium-containing oxide. More preferably, lithium cobalt oxide (LiCoO 2 ) and lithium nickel-based oxide may be used alone or in combination thereof.
  • the nonaqueous electrolyte of the present invention exhibits remarkable effects when the lithium nickel oxide is used as the positive electrode. That is, the battery using lithium nickel-based oxide as a positive electrode has the advantage that can be manufactured as a high capacity battery, but the degradation of the charge-discharge cycle life characteristics and the solution of the swelling of the battery should be preceded. According to the present invention, when the nonaqueous electrolyte solution including the silicon compound of Chemical Formula 1 is applied to a lithium secondary battery having lithium nickel oxide as a positive electrode, the above-described problems caused by using lithium nickel oxide may be greatly improved.
  • the electrode of the lithium secondary battery of the present invention is a conventional method, for example, the electrode active material particles and the binder polymer is added to the solvent with a conductive material and a dispersant as necessary to prepare a slurry, and then coated and pressed on a current collector It can be prepared by drying.
  • the positive electrode can be easily manufactured by those skilled in the art by adjusting the thickness of the positive electrode active material layer coated on the current collector, the amount of the binder polymer, the process conditions, and the like.
  • a separator is usually interposed between the positive electrode and the negative electrode, and conventional porous polymer films conventionally used as separators, for example, ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymer and ethylene Porous polymer films made of polyolefin-based polymers such as / methacrylate copolymers may be used alone or in a stack of them.
  • a non-woven fabric of high melting glass fibers, polyethylene terephthalate fibers and the like can be used, but is not limited thereto.
  • the external shape of the lithium secondary battery of the present invention is not particularly limited, but may be cylindrical, square, pouch type, or coin type using a can.
  • a nonaqueous electrolyte was prepared by adding 0.05 parts by weight of dimethyl vinyl silanol relative to parts by weight.
  • the battery was manufactured by pouring the above-mentioned nonaqueous electrolyte into a pouch-type battery having a positive electrode made of LiCoO 2 and a negative electrode made of artificial graphite.
  • a pouch-type battery was manufactured in the same manner as in Example 1, except that the content of dimethylvinyl silanol was changed to 0.1 part by weight based on 100 parts by weight of the nonaqueous electrolyte.
  • a pouch type battery was manufactured in the same manner as in Example 1, except that the content of dimethylvinyl silanol was changed to 0.5 part by weight based on 100 parts by weight of the nonaqueous electrolyte.
  • a pouch type battery was manufactured in the same manner as in Example 1, except that the content of dimethylvinyl silanol was changed to 1.0 part by weight based on 100 parts by weight of the nonaqueous electrolyte.
  • a pouch type battery was manufactured in the same manner as in Example 1, except that the content of dimethylvinyl silanol was changed to 5.0 parts by weight based on 100 parts by weight of the nonaqueous electrolyte.
  • a pouch-type battery was manufactured in the same manner as in Example 1, except that the content of dimethylvinyl silanol was changed to 8.0 parts by weight based on 100 parts by weight of the nonaqueous electrolyte.
  • a pouch-type battery was manufactured in the same manner as in Example 1, except that the content of dimethylvinyl silanol was changed to 12.0 parts by weight based on 100 parts by weight of the nonaqueous electrolyte.
  • a pouch-type battery was manufactured in the same manner as in Example 1, except that 1.0 part by weight of vinylene carbonate (VC) was added to 100 parts by weight of the nonaqueous electrolyte.
  • VC vinylene carbonate
  • a pouch-type battery was manufactured in the same manner as in Example 2, except that 1.0 part by weight of vinylene carbonate (VC) was added to 100 parts by weight of the non-aqueous electrolyte.
  • VC vinylene carbonate
  • a pouch-type battery was manufactured in the same manner as in Example 3, except that 1.0 part by weight of vinylene carbonate (VC) was added to 100 parts by weight of the non-aqueous electrolyte.
  • VC vinylene carbonate
  • a pouch-type battery was manufactured in the same manner as in Example 4, except that 1.0 part by weight of vinylene carbonate (VC) was added to 100 parts by weight of the nonaqueous electrolyte.
  • VC vinylene carbonate
  • a pouch-type battery was manufactured in the same manner as in Example 5, except that 1.0 part by weight of vinylene carbonate (VC) was added to 100 parts by weight of the non-aqueous electrolyte.
  • VC vinylene carbonate
  • a pouch-type battery was manufactured in the same manner as in Example 6, except that 1.0 part by weight of vinylene carbonate (VC) was added to 100 parts by weight of the non-aqueous electrolyte.
  • VC vinylene carbonate
  • a pouch-type battery was manufactured in the same manner as in Example 7, except that 1.0 part by weight of vinylene carbonate (VC) was added to 100 parts by weight of the nonaqueous electrolyte.
  • VC vinylene carbonate
  • Ethylene carbonate (EC): Ethyl propionate (EP) 1: 2 (v: v) as a non-aqueous electrolyte, except that 1M LiPF 6 was mixed with a mixed organic solvent
  • Ethylene carbonate (EC): Ethyl propionate (EP) 1: 2 (v: v) as a non-aqueous electrolyte, except that 1M LiPF 6 was mixed with a mixed organic solvent
  • a pouch type battery was manufactured in the same manner as in Example 1.
  • Ethylene carbonate (EC): Ethyl propionate (EP) 1: 2 (v: v) as a non-aqueous electrolyte, except that 1M LiPF 6 was mixed with a mixed organic solvent
  • Ethylene carbonate (EC): Ethyl propionate (EP) 1: 2 (v: v) as a non-aqueous electrolyte, except that 1M LiPF 6 was mixed with a mixed organic solvent
  • a pouch type battery was manufactured in the same manner as in Example 2.
  • Ethylene carbonate (EC): Ethyl propionate (EP) 1: 2 (v: v) as a non-aqueous electrolyte, except that 1M LiPF 6 was mixed with a mixed organic solvent
  • Ethylene carbonate (EC): Ethyl propionate (EP) 1: 2 (v: v) as a non-aqueous electrolyte, except that 1M LiPF 6 was mixed with a mixed organic solvent
  • a pouch type battery was manufactured in the same manner as in Example 3.
  • Ethylene carbonate (EC): Ethyl propionate (EP) 1: 2 (v: v) as a non-aqueous electrolyte, except that 1M LiPF 6 was mixed with a mixed organic solvent
  • Ethylene carbonate (EC): Ethyl propionate (EP) 1: 2 (v: v) as a non-aqueous electrolyte, except that 1M LiPF 6 was mixed with a mixed organic solvent
  • a pouch type battery was manufactured in the same manner as in Example 4.
  • Ethylene carbonate (EC): Ethyl propionate (EP) 1: 2 (v: v) as a non-aqueous electrolyte, except that 1M LiPF 6 was mixed with a mixed organic solvent
  • Ethylene carbonate (EC): Ethyl propionate (EP) 1: 2 (v: v) as a non-aqueous electrolyte, except that 1M LiPF 6 was mixed with a mixed organic solvent
  • a pouch type battery was manufactured in the same manner as in Example 5.
  • Ethylene carbonate (EC): Ethyl propionate (EP) 1: 2 (v: v) as a non-aqueous electrolyte, except that 1M LiPF 6 was mixed with a mixed organic solvent
  • Ethylene carbonate (EC): Ethyl propionate (EP) 1: 2 (v: v) as a non-aqueous electrolyte, except that 1M LiPF 6 was mixed with a mixed organic solvent
  • a pouch type battery was manufactured in the same manner as in Example 6.
  • Ethylene carbonate (EC): Ethyl propionate (EP) 1: 2 (v: v) as a non-aqueous electrolyte, except that 1M LiPF 6 was mixed with a mixed organic solvent
  • Ethylene carbonate (EC): Ethyl propionate (EP) 1: 2 (v: v) as a non-aqueous electrolyte, except that 1M LiPF 6 was mixed with a mixed organic solvent
  • a pouch-type battery was manufactured in the same manner as in Example 7.
  • Ethylene carbonate (EC): Ethyl propionate (EP) 1: 2 (v: v) as a non-aqueous electrolyte, except that 1M LiPF 6 was mixed with a mixed organic solvent
  • Ethylene carbonate (EC): Ethyl propionate (EP) 1: 2 (v: v) as a non-aqueous electrolyte, except that 1M LiPF 6 was mixed with a mixed organic solvent
  • a pouch type battery was manufactured in the same manner as in Example 8.
  • Ethylene carbonate (EC): Ethyl propionate (EP) 1: 2 (v: v) as a non-aqueous electrolyte, except that 1M LiPF 6 was mixed with a mixed organic solvent
  • Ethylene carbonate (EC): Ethyl propionate (EP) 1: 2 (v: v) as a non-aqueous electrolyte, except that 1M LiPF 6 was mixed with a mixed organic solvent
  • a pouch type battery was manufactured in the same manner as in Example 9.
  • Ethylene carbonate (EC): Ethyl propionate (EP) 1: 2 (v: v) as a non-aqueous electrolyte, except that 1M LiPF 6 was mixed with a mixed organic solvent
  • Ethylene carbonate (EC): Ethyl propionate (EP) 1: 2 (v: v) as a non-aqueous electrolyte, except that 1M LiPF 6 was mixed with a mixed organic solvent
  • a pouch type battery was manufactured in the same manner as in Example 10.
  • Ethylene carbonate (EC): Ethyl propionate (EP) 1: 2 (v: v) as a non-aqueous electrolyte, except that 1M LiPF 6 was mixed with a mixed organic solvent
  • Ethylene carbonate (EC): Ethyl propionate (EP) 1: 2 (v: v) as a non-aqueous electrolyte, except that 1M LiPF 6 was mixed with a mixed organic solvent
  • a pouch type battery was manufactured in the same manner as in Example 11.
  • Ethylene carbonate (EC): Ethyl propionate (EP) 1: 2 (v: v) as a non-aqueous electrolyte, except that 1M LiPF 6 was mixed with a mixed organic solvent
  • Ethylene carbonate (EC): Ethyl propionate (EP) 1: 2 (v: v) as a non-aqueous electrolyte, except that 1M LiPF 6 was mixed with a mixed organic solvent
  • a pouch type battery was manufactured in the same manner as in Example 12.
  • Ethylene carbonate (EC): Ethyl propionate (EP) 1: 2 (v: v) as a non-aqueous electrolyte, except that 1M LiPF 6 was mixed with a mixed organic solvent
  • Ethylene carbonate (EC): Ethyl propionate (EP) 1: 2 (v: v) as a non-aqueous electrolyte, except that 1M LiPF 6 was mixed with a mixed organic solvent
  • a pouch type battery was manufactured in the same manner as in Example 13.
  • Ethylene carbonate (EC): Ethyl propionate (EP) 1: 2 (v: v) as a non-aqueous electrolyte, except that 1M LiPF 6 was mixed with a mixed organic solvent
  • Ethylene carbonate (EC): Ethyl propionate (EP) 1: 2 (v: v) as a non-aqueous electrolyte, except that 1M LiPF 6 was mixed with a mixed organic solvent
  • a pouch type battery was manufactured in the same manner as in Example 14.
  • a pouch type battery was manufactured in the same manner as in Example 4, except that only LiNi 0.5 Mn 0.3 Co 0.2 O 2 was used as the positive electrode.
  • a pouch type battery was manufactured in the same manner as in Example 18, except that only LiNi 0.5 Mn 0.3 Co 0.2 O 2 was used as the positive electrode.
  • a pouch-type battery was manufactured in the same manner as in Example 1, except that dimethyl vinyl silanol was not added.
  • a pouch-type battery was manufactured in the same manner as in Example 8, except that dimethyl vinyl silanol was not added.
  • a pouch-type battery was manufactured in the same manner as in Example 15, except that dimethyl vinyl silanol was not added.
  • a pouch-type battery was manufactured in the same manner as in Example 22, except that dimethyl vinyl silanol was not added.
  • a pouch-type battery was manufactured in the same manner as in Comparative Example 1, except that 1.0 part by weight of tetramethylsilane was added to 100 parts by weight of the nonaqueous electrolyte.
  • a pouch-type battery was manufactured in the same manner as in Comparative Example 1 except that only LiNi 0.5 Mn 0.3 Co 0.2 O 2 was used as the positive electrode.
  • a pouch-type battery was manufactured in the same manner as in Comparative Example 3 except that only LiNi 0.5 Mn 0.3 Co 0.2 O 2 was used as the positive electrode.
  • the pouch-type batteries prepared in Examples and Comparative Examples were aged at room temperature for 2 days after the electrolyte injection, and then charged with 0.2 C-rate for 50 minutes. Subsequently, degas / reseal was charged at a constant temperature / constant voltage condition up to 4.2V at 0.2C at room temperature, and discharged at a constant current condition up to 3.0V at 0.2C to perform initial charge and discharge.
  • the ratio of charge capacity to discharge capacity is called initial efficiency. After the initial charge and discharge, the charge and discharge was performed 400 times with 1.0 C-rate in the same voltage region, and the capacity retention ratio was 400 times compared to the initial discharge capacity.
  • Example 1 Initial Efficiency (%) 400 capacity retention rate (%) High temperature thickness change (mm)
  • Example 1 90.1 76.7 2.72
  • Example 2 90.2 80.3 1.98
  • Example 3 90.1 83.3 1.58
  • Example 4 90.2 85.6 0.93
  • Example 5 90.0 82.2 0.57
  • Example 6 90.0 80.1 0.42
  • Example 7 89.6 70.3 0.33
  • Example 8 90.3 79.5 2.55
  • Example 9 90.3 81.2 1.81
  • Example 10 90.4 83.4 1.49
  • Example 11 90.3 85.7 0.88
  • Example 12 90.1 82.0 0.55
  • Example 13 90.0 80.0 0.40
  • Example 14 89.4 71.5 0.32
  • Example 15 90.1 78.8 2.60
  • Example 16 90.3 80.6 1.74
  • Example 17 90.3 84.0 1.35
  • Example 18 90.3 86.5 0.87
  • Example 19 90.2 84.1 0.51
  • Example 20 90.0 81.7 0.36
  • Example 21 90.0 81.7 0.36
  • Example 21 90.5 79.9 2.53
  • Example 23 90.5 8

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Abstract

L'invention concerne un solution électrolytique non aqueuse pour pile rechargeable au lithium et une pile rechargeable au lithium utilisant une telle solution. La solution électrolytique non aqueuse pour pile au lithium de la présente invention est exprimée dans une formule chimique spécifique et renferme en outre des composés à base de silicium contenant un groupe hydroxyle et un groupe hydrocarbure possédant une double liaison carbone en même temps. Lorsque l'on utilise la solution électrolytique non aqueuse de la présente invention dans une pile rechargeable au lithium, on peut obtenir une amélioration du nombre de cycles de charge/décharge et une suppression de la réaction de décomposition de la solution électrolytique, même lorsque la pile complètement chargée est conservée à une température élevée ou est chargée/déchargée, empêchant ainsi le gonflement et améliorant ainsi les caractéristiques de la durée de service de la pile, même à haute température.
PCT/KR2009/006687 2008-11-13 2009-11-13 Solution électrolytique non aqueuse pour pile rechargeable au lithium et pile rechargeable au lithium utilisant une telle solution Ceased WO2010056064A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US12/677,934 US8268489B2 (en) 2008-11-13 2009-11-13 Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery comprising the same
JP2011536248A JP5723778B2 (ja) 2008-11-13 2009-11-13 リチウム二次電池用非水電解液及びこれを備えたリチウム二次電池

Applications Claiming Priority (4)

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KR20080112724 2008-11-13
KR10-2008-0112724 2008-11-13
KR1020090109232A KR101040464B1 (ko) 2008-11-13 2009-11-12 리튬 이차전지용 비수 전해액 및 이를 구비한 리튬 이차전지
KR10-2009-0109232 2009-11-12

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US10714337B2 (en) 2015-07-31 2020-07-14 Crayonano As Process for growing nanowires or nanopyramids on graphitic substrates
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US11239391B2 (en) 2017-04-10 2022-02-01 Norwegian University Of Science And Technology (Ntnu) Nanostructure
US11261537B2 (en) 2013-06-21 2022-03-01 Norwegian University Of Science And Technology (Ntnu) III-V or II-VI compound semiconductor films on graphitic substrates
US11594657B2 (en) 2015-07-13 2023-02-28 Crayonano As Nanowires/nanopyramids shaped light emitting diodes and photodetectors
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Publication number Priority date Publication date Assignee Title
DE19612769A1 (de) * 1996-03-29 1997-10-02 Basf Ag Als Trägermaterial für Festelektrolyten oder Separatoren für elektrochemische Zellen geeignete Gemische
JP2008235090A (ja) * 2007-03-22 2008-10-02 Matsushita Electric Ind Co Ltd リチウムイオン二次電池用正極およびそれを用いたリチウムイオン二次電池

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US10861696B2 (en) 2010-12-13 2020-12-08 Norwegian University Of Science And Technology Compositions comprising epitaxial nanowires on graphene substrates and methods of making thereof
US10347781B2 (en) 2012-06-21 2019-07-09 Norwegian University Of Science And Technology (Ntnu) Solar cells
US11257967B2 (en) 2012-06-21 2022-02-22 Norwegian University Of Science And Technology (Ntnu) Solar cells
US11261537B2 (en) 2013-06-21 2022-03-01 Norwegian University Of Science And Technology (Ntnu) III-V or II-VI compound semiconductor films on graphitic substrates
US10347791B2 (en) 2015-07-13 2019-07-09 Crayonano As Nanowires or nanopyramids grown on graphitic substrate
US11264536B2 (en) 2015-07-13 2022-03-01 Crayonano As Nanowires or nanopyramids grown on a graphene substrate
US11594657B2 (en) 2015-07-13 2023-02-28 Crayonano As Nanowires/nanopyramids shaped light emitting diodes and photodetectors
US10714337B2 (en) 2015-07-31 2020-07-14 Crayonano As Process for growing nanowires or nanopyramids on graphitic substrates
US11450528B2 (en) 2015-07-31 2022-09-20 Crayonano As Process for growing nanowires or nanopyramids on graphitic substrates
US11239391B2 (en) 2017-04-10 2022-02-01 Norwegian University Of Science And Technology (Ntnu) Nanostructure
US12471405B2 (en) 2019-09-23 2025-11-11 Squidled SAS Composition of matter

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