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WO2018135890A1 - Électrolyte non aqueux pour batterie secondaire au lithium, et batterie secondaire au lithium le comprenant - Google Patents

Électrolyte non aqueux pour batterie secondaire au lithium, et batterie secondaire au lithium le comprenant Download PDF

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Publication number
WO2018135890A1
WO2018135890A1 PCT/KR2018/000874 KR2018000874W WO2018135890A1 WO 2018135890 A1 WO2018135890 A1 WO 2018135890A1 KR 2018000874 W KR2018000874 W KR 2018000874W WO 2018135890 A1 WO2018135890 A1 WO 2018135890A1
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Prior art keywords
carbonate
secondary battery
lithium secondary
aqueous electrolyte
organic solvent
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PCT/KR2018/000874
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English (en)
Korean (ko)
Inventor
김하은
임영민
김민정
이철행
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LG Chem Ltd
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LG Chem Ltd
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Priority claimed from KR1020180006123A external-priority patent/KR102117622B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to EP18741979.1A priority Critical patent/EP3419097B1/fr
Priority to PL18741979T priority patent/PL3419097T3/pl
Priority to CN201880001563.9A priority patent/CN109075386B/zh
Priority to US16/308,724 priority patent/US10950894B2/en
Publication of WO2018135890A1 publication Critical patent/WO2018135890A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • 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 comprising the same.
  • lithium secondary batteries developed in the early 1990s have been spotlighted for their advantages of high operating voltage and high energy density.
  • the lithium secondary battery is composed of a negative electrode such as a carbon material capable of occluding and releasing lithium ions, a positive electrode made of a lithium-containing oxide, and the like, and a nonaqueous electrolyte in which lithium salt is dissolved in a mixed organic solvent.
  • a negative electrode such as a carbon material capable of occluding and releasing lithium ions
  • a positive electrode made of a lithium-containing oxide, and the like
  • a nonaqueous electrolyte in which lithium salt is dissolved in a mixed organic solvent.
  • the lithium secondary battery generates a compound such as Li 2 CO 3 , Li 2 O, LiOH by reacting lithium ions and the electrolyte in the region of 0.5V to 3.5V during the initial charging, by a kind of passivation film (A solid electrolyte interface (SEI) film, which is a passivation layer, is formed.
  • SEI solid electrolyte interface
  • the SEI film formed at the beginning of charging prevents the reaction between lithium ions and carbon anode or lithium ions and other materials during charging and discharging. In addition, it functions as an ion tunnel to pass only lithium ions.
  • the ion tunnel plays a role in preventing the large molecular weight non-aqueous organic solvents that solvate lithium ions and move together to prevent the structure of the carbon anode from collapsing together. Characteristics and output characteristics can be improved.
  • the organic solvent used in the non-aqueous electrolyte of the lithium secondary battery generally causes a side reaction with the transition metal oxide of the cathode active material released when stored for a long time at high temperature to generate a gas.
  • the negative electrode when stored at high temperature in a full charge state (for example, when stored at 60 ° C. after 100% charge at 4.2 V), the negative electrode is exposed while the SEI film gradually collapses, and the exposed negative electrode continuously reacts with the electrolyte, Gases such as CO 2 , CH 4 , and C 2 H 6 are generated.
  • the first technical problem of the present invention is to provide a non-aqueous electrolyte for lithium secondary battery that can form a stable film on the electrode surface and can suppress side reaction of the electrolyte during high temperature storage.
  • the second technical problem of the present invention is to provide a lithium secondary battery having improved high temperature storage characteristics and cycle life characteristics by including the nonaqueous electrolyte solution for lithium secondary batteries.
  • Ionizable lithium salts Organic solvents; And a nonaqueous electrolyte solution for a lithium secondary battery comprising an additive,
  • the organic solvent is ethylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate, vinylene carbonate and fluoroethylene carbonate (FEC)
  • the additive is a mixed additive comprising vinylene carbonate (VC): 1,3-propylene sulfate (PPS): 1,3-propanesultone (PS) in a weight ratio of 1: 0.5 to 1: 0.2 to 1,
  • VC vinylene carbonate
  • PPS 1,3-propylene sulfate
  • PS 1,3-propanesultone
  • the mixed additive provides a nonaqueous electrolyte solution for a lithium secondary battery, which is included in an amount of 1 wt% to 4.5 wt% based on the total weight of the nonaqueous electrolyte solution for a lithium secondary battery.
  • the organic solvent further includes at least one linear ester organic solvent selected from the group consisting of methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, and butyl propionate. can do.
  • the mixed additive vinylene carbonate: 1,3-propylene sulfate: 1,3-propanesultone may be included in a weight ratio of 1: 0.7 to 1: 0.25 to 1.
  • the mixed additive may be included in an amount of 1.5% by weight to 4.5% by weight based on the total weight of the nonaqueous electrolyte solution for a lithium secondary battery.
  • nonaqueous electrolyte solution for lithium secondary batteries of the present invention further includes at least one additional additive selected from the group consisting of fluorobenzene (FB), tertiary butylbenzene (TBB), tertiary pentylbenzene (TPB) and LiBF 4 . can do.
  • FB fluorobenzene
  • TB tertiary butylbenzene
  • TPB tertiary pentylbenzene
  • LiBF 4 LiBF 4
  • Such additional additives may be included in an amount of 0.1 wt% to 5 wt% based on the total weight of the nonaqueous electrolyte solution for the lithium secondary battery.
  • a lithium secondary battery having a negative electrode, a positive electrode, a separator interposed between the negative electrode and the positive electrode and a non-aqueous electrolyte
  • the nonaqueous electrolyte solution includes a nonaqueous electrolyte solution for secondary batteries of the present invention
  • the positive electrode may include a lithium-nickel-manganese-cobalt oxide represented by Chemical Formula 1 as a positive electrode active material.
  • the cathode active material may include at least one of Li (Ni 0.6 Mn 0.2 Co 0.2 ) O 2 and Li (Ni 0.7 Mn 0.15 Co 0.15 ) O 2 .
  • the present invention by including a mixed additive in which three kinds of compounds are mixed in a specific ratio, it is possible to form a stable SEI film on the surface of the negative electrode to prepare a non-aqueous electrolyte for lithium secondary batteries in which side reactions are suppressed during high temperature storage. In addition, by including this, it is possible to manufacture a lithium secondary battery with improved high temperature storage characteristics and cycle life characteristics.
  • Ionizable lithium salts Organic solvents
  • electrolyte solution for a lithium secondary battery comprising an additive
  • the organic solvent is ethylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate, vinylene carbonate and fluoroethylene carbonate (FEC)
  • the additive is a mixed additive comprising vinylene carbonate (VC): 1,3-propylene sulfate (PPS): 1,3-propanesultone (PS) in a weight ratio of 1: 0.5 to 1: 0.2 to 1,
  • VC vinylene carbonate
  • PPS 1,3-propylene sulfate
  • PS 1,3-propanesultone
  • the mixed additive provides a nonaqueous electrolyte solution for a lithium secondary battery, which is included in an amount of 1 wt% to 4.5 wt% based on the total weight of the nonaqueous electrolyte solution for a lithium secondary battery.
  • the ionizable lithium salts may be used without limitation, those conventionally used in the electrolyte solution for lithium secondary batteries, and include, for example, Li + as a cation.
  • anion include F -, Cl -, Br - , I -, NO 3 -, N (CN) 2 -, BF 4 -, ClO 4 -, AlO 4 -, AlCl 4 -, PF 6 -, SbF 6 - , AsF 6 -, B 10 Cl 10 -, BF 2 C 2 O 4 -, BC 4 O 8 -, PF 4 C 2 O 4 -, PF 2 C 4 O 8 -, (CF 3) 2 PF 4 -, (CF 3) 3 PF 3 - , (CF 3) 4 PF 2 -, (CF 3) 5 PF -, (CF 3) 6 P -, CF 3 SO 3 -, C 4 F 9 SO 3 -, CF 3 CF 2 SO 3 -, (CF 3 SO 2) 2 N -, (FSO 2) 2 N -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2) 2 CH -, CH 3 SO 3 -,
  • the lithium salt is LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCH 3 CO 2 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , LiAlO 4 , and LiCH 3 SO 3
  • It may include a single or a mixture of two or more selected from the group consisting of, in addition to these LiBTI (lithium bisperfluoroethanesulfonimide, LiN (SO 2 CF 2 CF) commonly used in the electrolyte of the lithium secondary battery 3 ) lithium salts such as lithium imide salts represented by 2 , LiFSI (lithium fluorosulfonyl imide, LiN (SO 2 F) 2 ), and LiTFSI (lithium (bis) trifluoromethanesulfonimide, LiN (SO 2 CF 3 ) 2 )
  • the lithium salt may be appropriately changed within the range generally available, but specifically, may be included in the electrolyte solution 0.1M to 3M, specifically 0.8M to 2.5M. If the concentration of the lithium salt exceeds 3M, the film forming effect may decrease.
  • the organic solvent does not include propylene carbonate which is a cyclic carbonate organic solvent.
  • the propylene carbonate (PC) has a high output characteristic due to low temperature characteristics and high conductivity, but causes an irreversible decomposition reaction with the carbon-based negative electrode material, to the propylene carbonate during high temperature cycles depending on the electrode thickness Due to the electrode exfoliation phenomenon, a capacity decrease of the lithium secondary battery may occur.
  • a lithium salt such as LiPF 6 as a non-aqueous organic solvent
  • the non-aqueous electrolyte for lithium secondary batteries of the present invention does not contain propylene carbonate as the cyclic carbonate organic solvent, it prevents the performance of the lithium secondary battery from deteriorating during high temperature storage, thereby improving high temperature storage characteristics and cycle characteristics. You can implement the effect.
  • the nonaqueous electrolyte solution for lithium secondary batteries of the present invention may further use a linear ester organic solvent, if necessary.
  • the linear ester organic solvent may be any one selected from the group consisting of methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, and butyl propionate. Two or more organic solvents may be used, but is not limited thereto.
  • nonaqueous electrolyte solution for lithium secondary batteries of this invention can mix and use 1 or more types of cyclic ester type organic solvent, ether type organic solvent, or amide type organic solvent as needed.
  • cyclic ester organic solvent examples include any one selected from the group consisting of ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -valerolactone, and ⁇ -caprolactone. Mixtures of more than one species may be used, but are not limited thereto.
  • the ether-based organic solvent may be any one selected from the group consisting of dimethyl ether, diethyl ether, dipropyl ether, methyl ethyl ether, methyl propyl ether and ethyl propyl ether or a mixture of two or more thereof. It is not limited to this.
  • vinylene carbonate represented by the following Chemical Formula 2, which is one of the additive components may be electrochemically decomposed on the surface of the anode and the cathode to form a solid SEI film. It is an ingredient. Therefore, cycle life characteristics and high temperature storage characteristics of the secondary battery can be improved.
  • 1,3-propylene sulfate represented by the following Chemical Formula 3, which is one of the additive components, is also a component for improving the cycle life characteristics improvement effect of the secondary battery.
  • it may be electrically decomposed on the surface of the cathode to form a stable SEI film that does not crack even when stored at high temperatures.
  • the negative electrode coated with the protective film can prevent the generation of gas by suppressing decomposition of the non-aqueous organic solvent by the negative electrode active material during high temperature storage even when a high crystallized carbon material such as natural graphite or artificial graphite is used for the negative electrode. have.
  • the protective film formed by the compound does not interfere with the charge / discharge reaction of the battery. Therefore, the cycle life characteristics, the capacity, the resistance characteristics, and the like can be improved at room temperature and high temperature of the secondary battery.
  • 1,3-propanesultone represented by the following Chemical Formula 4 which is one of the additive components, is a component for implementing the effect of increasing durability during high temperature storage.
  • the blending additive vinylene carbonate: 1,3-propylene sulfate: 1,3-propanesultone has a weight ratio of 1: 0.5 to 1: 0.2 to 1, specifically 1: 0.7 to 1: 0.25 to 1 It can be included as.
  • the content ratio range of the compounds is less than the critical range, a solid SEI film cannot be formed, and if the content exceeds the critical range, excess will remain and cause side reactions inside the battery, resulting in gas generation and performance deterioration.
  • the weight ratio of the 1,3-propylene sulfate is less than 0.5 based on 1 part by weight of the vinylene carbonate, or when the weight ratio of 1,3-propanesultone is less than 0.2 based on 1 part by weight of the vinylene carbonate, SEI
  • the stabilization effect is small when the film is formed, and because the excess vinylene carbonate causes side reactions to increase the resistance of the battery or increase gas generation, the high temperature storage characteristics and the cycle life characteristics may be deteriorated.
  • the weight ratio of the compounds constituting the mixed additive satisfies the above range, a stable SEI film is formed without increasing the resistance, so that the effect of suppressing the side reaction of the electrolyte may be realized, and thus, the cycle life characteristics of the lithium secondary battery and High temperature storage characteristics can be improved.
  • the mixed additive of the present invention may be included in an amount of 1 wt% to 4.5 wt%, specifically 1.5 wt% to 4 wt%, based on the total weight of the nonaqueous electrolyte solution for a lithium secondary battery.
  • the content of the mixed additive in the nonaqueous electrolyte may be determined by the reaction specific surface area of the positive electrode and the negative electrode.
  • the content of the mixed additive is 1% by weight or more, not only a stable (SEI) film may be formed on the surface of the negative electrode, but also the electrolyte solution. It is possible to satisfy the expected effect by adding each component, such as to suppress the decomposition of the electrolyte solution by the reaction with the negative electrode to implement the effect of reducing gas generation.
  • the content of the additive is less than 4.5% by weight, not only the gas generation effect due to the use of the additive can be improved, but also the respective components are prevented from remaining in excess, thereby preventing an increase in resistance due to side reactions, and It is possible to form a stable SEI film. Therefore, the high temperature stability of the lithium secondary battery may be improved.
  • the content of the additive exceeds 4.5% by weight, the gas generation effect may be improved by using the additive excessively, but each component remains in excess, resulting in an excessively thick film, resulting in increased resistance and output degradation. Can be.
  • the nonaqueous electrolyte according to an embodiment of the present invention includes vinylene carbonate: 1,3-propylene sulfate: 1,3-propanesultone as an additive in a weight ratio of 1: 0.5 to 1: 0.2 to 1 1.5 wt% to 4.5 wt% based on the weight of the negative electrode can form a stable SEI film on the surface of the negative electrode, thereby suppressing the decomposition of the electrolyte by the reaction between the electrolyte and the negative electrode, thereby improving the characteristics of the secondary battery Can be.
  • non-aqueous electrolytes do not include additives as an essential component in the manufacture of secondary batteries, but if necessary, additionally implement cycle life characteristics, low temperature high rate discharge characteristics, high temperature safety, overcharge prevention, and high temperature swelling of secondary batteries. To this end, it may further include an additive.
  • an additive capable of suppressing decomposition reaction of the non-aqueous electrolyte during high temperature storage and forming a stable film on the surface of the positive electrode and the negative electrode is used.
  • the non-aqueous electrolyte of the present invention is a fluorobenzene (FB), tertiary butyl benzene (TBB), tertiary pentyl benzene (TPB) and LiBF 4 as an additive additive in order to improve the high temperature storage characteristics and gas reduction effect It may further comprise at least one additional additive selected from the group consisting of.
  • the additional additive may include 0.1 wt% to 5 wt% based on the total weight of the nonaqueous electrolyte solution for a lithium secondary battery. If the content of the additional additive is less than 0.1% by weight, the effect to be realized from the additional additive is insignificant, and when the content of the additional additive is more than 5% by weight, the excess additional additive causes side reactions to increase the resistance of the battery. The cycle life of the secondary battery is reduced.
  • LiODFB oxalyldifluoroborate
  • Lithium secondary batteries are intercalated by moving lithium ions from lithium metal oxides used as positive electrodes during initial charging to carbon-based electrodes used as negative electrodes.
  • lithium reacts with the carbon negative electrode and the electrolyte because Li is highly reactive.
  • 2 CO 3 , Li 2 O, LiOH and the like are formed and these form an SEI film on the surface of the cathode.
  • an ion tunnel that passes only lithium ions between the electrolyte and the cathode while preventing a reaction between lithium ions and a carbon negative electrode or another material during repeated charge / discharge cycles by using a battery. It will serve as a role.
  • the SEI membrane blocks the migration of the organic solvent for electrolyte having a large molecular weight, for example, EC, DMC, DEC, etc. to the carbon cathode, so that they are co-intercalated with lithium ions to the carbon cathode. Prevents the structure of the cathode from being collapsed.
  • the carbon material of the negative electrode reacts with the electrolyte during initial charging to form a passivation layer on the negative electrode surface to maintain stable charge and discharge without further decomposition of the electrolyte, wherein the film on the negative electrode surface
  • the amount of charge consumed in the formation is an irreversible capacity, which is characterized by not reversibly reacting at the time of discharge, and for this reason, the lithium ion battery can maintain a stable life cycle without exhibiting any irreversible reaction after the initial charge reaction.
  • lithium ion batteries can be slowly decayed by increased electrochemical and thermal energy over time when stored at high temperature in full charge (eg, stored at 60 ° C after charging 4.2V 100%).
  • This SEI film collapse exposes the negative electrode surface, and the exposed negative electrode surface decomposes while reacting with a carbonate-based solvent in the electrolyte, causing a continuous side reaction.
  • These side reactions continue to generate gas, and the main gases generated are CO, CO 2 , CH 4 , and C 2 H 6 , which expand the cell thickness by increasing the internal pressure of the lithium ion battery regardless of its type. It causes.
  • the electrolyte side reaction during high temperature storage By suppressing this, it is possible to prevent battery expansion during high temperature storage and to improve high temperature storage safety.
  • a lithium secondary battery having a negative electrode, a positive electrode, a separator interposed between the negative electrode and the positive electrode and a non-aqueous electrolyte
  • the nonaqueous electrolyte solution includes a nonaqueous electrolyte solution for secondary batteries of the present invention
  • the positive electrode may include a lithium-nickel-manganese-cobalt oxide represented by Chemical Formula 1 as a positive electrode active material.
  • the lithium secondary battery of the present invention may be prepared by injecting the nonaqueous electrolyte of the present invention into an electrode assembly consisting of a cathode, a cathode, and a separator interposed between the cathode and the anode.
  • the positive electrode, the negative electrode, and the separator constituting the electrode assembly may be used all those conventionally used in the manufacture of a lithium secondary battery.
  • the positive electrode may be manufactured by forming a positive electrode mixture layer on a positive electrode current collector.
  • the cathode mixture layer may be formed by coating a cathode slurry including a cathode active material, a binder, a conductive material, a solvent, and the like on a cathode current collector, followed by drying and rolling.
  • the positive electrode current collector is not particularly limited as long as it has conductivity without causing chemical changes in the battery.
  • the positive electrode current collector may be formed of stainless steel, aluminum, nickel, titanium, calcined carbon, or carbon on the surface of aluminum or stainless steel. Surface treated with nickel, titanium, silver, or the like may be used.
  • the cathode active material may include a lithium-nickel-manganese-cobalt-based oxide represented by Chemical Formula 1, and representative examples thereof include Li (Ni 0.6 Mn 0.2 Co 0.2 ) O 2 , Or Li (Ni 0.7 Mn 0.15 Co 0.15 ) O 2 .
  • the lithium-nickel-manganese-cobalt-based oxide represented by Chemical Formula 1 is known to have a high capacity per weight due to its high nickel content of 0.55 or more. Therefore, it can be used as a preferred cathode material when manufacturing a secondary battery having a high energy density per weight or volume. However, since the lithium-nickel-manganese-cobalt oxide represented by Chemical Formula 1 has low thermal stability, it is very important to ensure durability of the secondary battery at a high temperature during manufacturing of the secondary battery.
  • the positive electrode active material is a lithium-manganese oxide in addition to the lithium transition metal oxide represented by the formula (1, for example, LiMnO 2 , LiMn 2 O 4 Etc.), lithium-cobalt-based oxides (e.g., LiCoO 2, etc.), lithium-nickel-based oxides (e.g., LiNiO 2, etc.), lithium-nickel-manganese-based oxides (e.g., LiNi 1 - Y Mn Y O 2 (where, 0 ⁇ Y ⁇ 1), LiMn 2-z Ni z O 4 (where, 0 ⁇ z ⁇ 2) and the like), lithium-nickel-cobalt-based oxide (for example, LiNi 1- Y1 Co Y1 O 2 (here, 0 ⁇ Y1 ⁇ 1), etc., lithium-manganese-cobalt based oxides (eg, LiCo 1 -Y2 Mn Y2 O 2 (here, 0 ⁇ Y1
  • the cathode active material may be LiCoO 2 , LiMnO 2 , LiNiO 2 , or lithium nickel cobalt aluminum oxide (eg, Li (Ni 0.8 Co 0.15 Al 0.05 ) O 2, etc.).
  • the cathode active material may be included in an amount of 80 wt% to 99 wt%, specifically 93 wt% to 98 wt%, based on the total weight of solids in the cathode slurry. At this time, when the amount of the positive electrode active material is 80% by weight or less, the energy density may be lowered, thereby lowering the capacity.
  • the binder is a component that assists in bonding the active material and the conductive material to the current collector, and is generally added in an amount of 1 to 30 wt% based on the total weight of solids in the positive electrode slurry.
  • binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, Polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene-butadiene rubber, fluorine rubber, various copolymers, and the like.
  • the conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery.
  • Examples of the conductive material include carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black.
  • Carbon powder Graphite powders such as natural graphite, artificial graphite, or graphite with very advanced crystal structure; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
  • the conductive material is typically added in an amount of 1 to 30% by weight based on the total weight of solids in the positive electrode slurry.
  • the conductive material is Chevron Chemical Company, Denka Singapore Private Limited, Gulf Oil Company, etc., Ketjenblack, EC series (Armak Company) Armak Company), Vulcan XC-72 (Cabot Company), and Super P (manufactured by Timcal) can also be used.
  • the solvent may include an organic solvent such as N-methyl-2-pyrrolidone (NMP), and may be used in an amount that becomes a desirable viscosity when including the positive electrode active material and optionally a binder and a conductive material.
  • NMP N-methyl-2-pyrrolidone
  • the solid content concentration in the positive electrode slurry including the positive electrode active material, and optionally the binder and the conductive material may be 10 to 70% by weight, preferably 20 to 60% by weight.
  • the negative electrode may be prepared by forming a negative electrode mixture layer on the negative electrode current collector.
  • the negative electrode mixture layer may be formed by coating a negative electrode slurry including a negative electrode active material, a binder, a conductive material, a solvent, and the like on a negative electrode current collector, followed by drying and rolling.
  • the negative electrode current collector generally has a thickness of 3 to 500 ⁇ m.
  • a negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery.
  • copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel Surface-treated with carbon, nickel, titanium, silver, and the like on the surface, aluminum-cadmium alloy and the like can be used.
  • fine concavities and convexities may be formed on the surface to enhance the bonding strength of the negative electrode active material, and may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
  • the negative electrode active material may be lithium metal, a carbon material capable of reversibly intercalating / deintercalating lithium ions, a metal or an alloy of these metals and lithium, a metal complex oxide, and may dope and undo lithium. Materials, and at least one selected from the group consisting of transition metal oxides.
  • any carbon-based negative electrode active material generally used in a lithium ion secondary battery may be used without particular limitation.
  • Examples thereof include crystalline carbon, Amorphous carbons or these may be used together.
  • Examples of the crystalline carbon include graphite such as amorphous, plate, flake, spherical or fibrous natural graphite or artificial graphite, and examples of the amorphous carbon include soft carbon (soft carbon) Or hard carbon, mesophase pitch carbide, calcined coke, or the like.
  • the metals or alloys of these metals with lithium include Cu, Ni, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al And a metal selected from the group consisting of Sn or an alloy of these metals with lithium may be used.
  • the metal complex oxide may include PbO, PbO 2 , Pb 2 O 3 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , GeO, GeO 2 , Bi 2 O 3 , Bi 2 O 4 , Bi 2 O 5 , Li x Fe 2 O 3 (0 ⁇ x ⁇ 1), Li x WO 2 (0 ⁇ x ⁇ 1), and Sn x Me 1- x Me ' y O z (Me: Mn, Fe Me ': Al, B, P, Si, Group 1, Group 2, Group 3 elements of the periodic table, halogen; 0 ⁇ x ⁇ 1;1 ⁇ y ⁇ 3; 1 ⁇ z ⁇ 8 Any one selected from the group can be used.
  • Examples of materials capable of doping and undoping lithium include Si, SiO x (0 ⁇ x ⁇ 2), Si—Y alloys (wherein Y is an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, a transition metal, Is an element selected from the group consisting of rare earth elements and combinations thereof, not Si), Sn, SnO 2 , Sn-Y (Y is an alkali metal, alkaline earth metal, group 13 element, group 14 element, transition metal, rare earth) An element selected from the group consisting of elements and combinations thereof, and not Sn; and at least one of these and SiO 2 may be mixed and used.
  • transition metal oxide examples include lithium-containing titanium composite oxide (LTO), vanadium oxide, lithium vanadium oxide, and the like.
  • the negative active material may be included in an amount of 80 wt% to 99 wt% based on the total weight of solids in the negative electrode slurry.
  • the binder is a component that assists the bonding between the conductive material, the active material and the current collector, and is typically added in an amount of 1 to 30 wt% based on the total weight of solids in the negative electrode slurry.
  • binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, Polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene-butadiene rubber, fluorine rubber, various copolymers thereof, and the like.
  • the conductive material is a component for further improving the conductivity of the negative electrode active material, and may be added in an amount of 1 to 20 wt% based on the total weight of solids in the negative electrode slurry.
  • the conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery.
  • carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, or thermal black may be used.
  • Carbon powder such as natural graphite, artificial graphite, or graphite with very advanced crystal structure
  • Conductive fibers such as carbon fibers and metal fibers
  • Metal powders such as carbon fluoride powder, aluminum powder and nickel powder
  • Conductive whiskeys such as zinc oxide and potassium titanate
  • Conductive metal oxides such as titanium oxide
  • Conductive materials such as polyphenylene derivatives and the like can be used.
  • the solvent may include an organic solvent such as water or NMP, alcohol, etc., and may be used in an amount that becomes a desirable viscosity when including the negative electrode active material and optionally a binder and a conductive material.
  • concentration of the solids in the slurry including the negative electrode active material and, optionally, the binder and the conductive material may be 50 wt% to 75 wt%, preferably 50 wt% to 65 wt%.
  • porous polymer films conventionally used as separators for example, polyolefins such as ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymer and ethylene / methacrylate copolymer, etc.
  • the porous polymer film made of the polymer may be used alone or by laminating them, or a conventional porous nonwoven fabric, for example, a non-woven fabric made of high melting point glass fiber, polyethylene terephthalate fiber, or the like may be used. It is not.
  • 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.
  • Cathode active material Li (Ni 0.6 Mn 0.2 Co 0.2 ) O 2 ): conductive material (carbon black): binder (polyvinylidene fluoride) in a 90: 5: 5 weight ratio N-methyl-2-pyrrolidone as a solvent (NMP) was added to prepare a positive electrode slurry (40 wt% solids).
  • the positive electrode slurry was applied to one surface of a positive electrode current collector (Al thin film) having a thickness of 20 ⁇ m, and dried and roll pressed to prepare a positive electrode.
  • a negative electrode active material artificial graphite: conductive material (carbon black): binder (polyvinylidene fluoride) was added to N-methyl-2-pyrrolidone (NMP) as a solvent in a 90: 5: 5 weight ratio to give a negative electrode.
  • NMP N-methyl-2-pyrrolidone
  • a slurry 40 wt% solids was prepared. The negative electrode slurry was applied to one surface of a negative electrode current collector (Cu thin film) having a thickness of 20 ⁇ m, and dried and roll pressed to prepare a negative electrode.
  • a coin-type battery is manufactured by a conventional method of sequentially stacking the prepared positive electrode and the negative electrode together with a polyethylene porous film, followed by pouring the prepared non-aqueous electrolyte to prepare a lithium secondary battery (battery capacity 340 mAh). It was.
  • Example 1 except that 0.5g of vinylene carbonate, 0.5g of 1,3-propylene sulfate, and 0.5g of 1,3-propanesultone were added to 98.5g of the non-aqueous organic solvent in the preparation of the non-aqueous electrolyte. In the same manner as in the non-aqueous electrolyte and a lithium secondary battery comprising the same was prepared (see Table 1 below).
  • non-aqueous electrolyte solution except that 95.5 g of the non-aqueous organic solvent includes 1.5 g of vinylene carbonate, 1.5 g of 1,3-propylene sulfate, and 1.5 g of 1,3-propanesultone as additives.
  • 95.5 g of the non-aqueous organic solvent includes 1.5 g of vinylene carbonate, 1.5 g of 1,3-propylene sulfate, and 1.5 g of 1,3-propanesultone as additives.
  • a non-aqueous electrolyte and a lithium secondary battery including the same were prepared (see Table 1 below).
  • Example 1 in preparing the non-aqueous electrolyte except that 98.2 g of the non-aqueous organic solvent contained 0.8 g of vinylene carbonate, 0.6 g of 1,3-propylene sulfate, and 0.2 g of 1,3-propanesultone as additives.
  • 98.2 g of the non-aqueous organic solvent contained 0.8 g of vinylene carbonate, 0.6 g of 1,3-propylene sulfate, and 0.2 g of 1,3-propanesultone as additives.
  • non-aqueous electrolyte solution except that 96.8 g of the non-aqueous organic solvent includes 1.6 g of vinylene carbonate, 1.2 g of 1,3-propylene sulfate, and 0.4 g of 1,3-propanesultone as additives.
  • a non-aqueous electrolyte and a lithium secondary battery including the same were prepared (see Table 1 below).
  • non-aqueous electrolyte solution except that 96 g of the non-aqueous organic solvent includes 2.0 g of vinylene carbonate, 1.5 g of 1,3-propylene sulfate, and 0.5 g of 1,3-propanesultone as additives.
  • a non-aqueous electrolyte and a lithium secondary battery including the same were prepared (see Table 1 below).
  • Example 1 In preparing the non-aqueous electrolyte, Example 1 and the above except that 97 g of the non-aqueous organic solvent includes 1.5 g of vinylene carbonate, 1.0 g of 1,3-propylene sulfate, and 0.5 g of 1,3-propanesultone as additives.
  • 97 g of the non-aqueous organic solvent includes 1.5 g of vinylene carbonate, 1.0 g of 1,3-propylene sulfate, and 0.5 g of 1,3-propanesultone as additives.
  • a non-aqueous electrolyte and a lithium secondary battery including the same were prepared (see Table 1 below).
  • LiDFP lithium difluorophosphate
  • EC ethylene carbonate
  • EMC ethylmethyl carbonate
  • a non-aqueous electrolyte and a lithium secondary battery including the same were prepared in the same manner as in Comparative Example 1, except that 2.0 g of LiBF 4 was added to the non-aqueous organic solvent as an additive (Table 1 below). Reference).
  • non-aqueous electrolyte solution In the preparation of the non-aqueous electrolyte solution, the same procedure as in Comparative Example 1 was conducted except that 96 g of non-aqueous organic solvent contained 0.5 g of vinylene carbonate, 3.0 g of 1,3-propylene sulfate, and 0.5 g of 1,3-propanesultone.
  • 96 g of non-aqueous organic solvent contained 0.5 g of vinylene carbonate, 3.0 g of 1,3-propylene sulfate, and 0.5 g of 1,3-propanesultone.
  • non-aqueous electrolyte solution In preparing the non-aqueous electrolyte solution, the same procedure as in Comparative Example 1 was performed except that 96 g of non-aqueous organic solvent contained 0.5 g of vinylene carbonate, 0.5 g of 1,3-propylene sulfate, and 3.0 g of 1,3-propanesultone.
  • 96 g of non-aqueous organic solvent contained 0.5 g of vinylene carbonate, 0.5 g of 1,3-propylene sulfate, and 3.0 g of 1,3-propanesultone.
  • non-aqueous electrolyte In the preparation of the non-aqueous electrolyte, the non-aqueous electrolyte and the same method as in Comparative Example 1 except that 97 g of the non-aqueous organic solvent contains 2.0 g of 1,3-propylene sulfate and 1.0 g of 1,3-propanesultone as additives.
  • a lithium secondary battery including the same was prepared (see Table 1 below).
  • non-aqueous electrolyte In preparing the non-aqueous electrolyte, the non-aqueous electrolyte and the same were prepared in the same manner as in Comparative Example 1 except that 97 g of vinylene carbonate and 1.0 g of 1,3-propanesultone were added as additives to 97 g of the non-aqueous organic solvent.
  • a lithium secondary battery was prepared (see Table 1 below).
  • non-aqueous electrolyte In preparing the non-aqueous electrolyte, the non-aqueous electrolyte and the same were prepared in the same manner as in Comparative Example 1 except that 97 g of vinylene carbonate and 1.5 g of 1,3-propylene sulfate were added as additives to 97 g of the non-aqueous organic solvent.
  • a lithium secondary battery was prepared (see Table 1 below).
  • a lithium secondary battery was manufactured in the same manner as in Example 7, except that lithium cobalt composite oxide (LiCoO 2 ) was used as the cathode active material (see Table 1 below).
  • LiCoO 2 lithium cobalt composite oxide
  • non-aqueous electrolyte Comparative Example 1 and the above except that 96.8 g of the non-aqueous organic solvent includes 2.2 g of vinylene carbonate, 0.5 g of 1,3-propylene sulfate, and 0.5 g of 1,3-propanesultone as additives.
  • a non-aqueous electrolyte and a lithium secondary battery including the same were prepared (see Table 1 below).
  • Comparative Example 1 In preparing the non-aqueous electrolyte, Comparative Example 1 except that 96.8 g of the non-aqueous organic solvent includes 2.0 g of vinylene carbonate, 1.0 g of 1,3-propylene sulfate, and 0.2 g of 1,3-propanesultone as additives. In the same manner, a non-aqueous electrolyte and a lithium secondary battery including the same were prepared (see Table 1 below).
  • PC propylene carbonate
  • EMC ethylmethyl carbonate
  • a non-aqueous electrolyte and a lithium secondary battery including the same were prepared in the same manner as in Comparative Example 1 except that 1.0 g of LiODFB was additionally added as an additive (see Table 1 below).
  • each of the secondary batteries manufactured in Examples 1 to 7 and Comparative Examples 1 to 13 was charged at 1C to 4.25V / 55mA at 45 ° C under CC / CV conditions, and then discharged at 2C to 3.0V under CC conditions ( 1,000 cycles / 1 cycle x 100), and the life after 1,000 cycles at high temperature was measured, and the results are shown in Table 1 below.
  • the battery After storing the secondary batteries prepared in Examples 1 to 7 and Comparative Examples 1 to 13 at a high temperature of 60 ° C. for 16 weeks, the battery was charged at 1 C to 4.25V / 55 mA at room temperature and then subjected to CC conditions. Discharged to 2.5V at 2 C, and the discharge capacity after 16 weeks was calculated as a percentage (capacity / initial discharge capacity x 100 (%) after 16 weeks), and the capacity after high temperature storage was measured. The results are shown in Table 1 below.
  • the secondary batteries manufactured in Examples 1 to 7 and Comparative Examples 1 to 13 were stored at 60 ° C. for 16 weeks at high temperature, and then discharged at 10 ° C. for 10 seconds at 50% of normal temperature SOC for 16 seconds.
  • the post output was calculated as a percentage (16 weeks output / initial output x 100 (%)) and the results are shown in Table 1 below.
  • the stability of the SEI film formed on the surface of the cathode is relatively higher than that of the secondary batteries of Examples 1 to 7 including lithium-nickel-manganese-cobalt oxide. It can be seen that the cycle life characteristics and high temperature storage characteristics are deteriorated due to the low value.
  • the PC solvent is carbon-based (graphite) because repetitive desorption of lithium is impossible due to peeling due to negative electrode penetration of the PC. It was confirmed that cell driving was impossible in the secondary battery using the negative electrode.

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Abstract

La présente invention concerne un électrolyte non aqueux pour une batterie secondaire au lithium et une batterie secondaire au lithium le comprenant et, en particulier, à un électrolyte non aqueux pour une batterie secondaire au lithium et à une batterie secondaire au lithium le comprenant, l'électrolyte non aqueux pour une batterie secondaire au lithium comprenant un sel de lithium ionisable, un solvant organique et un additif. Le solvant organique comprend : au moins un solvant organique à base de carbonate annulaire choisi dans le groupe constitué par le carbonate d'éthylène, le carbonate de 1,2-butylène, le carbonate de 2,3-butylène, le carbonate de 1,2-pentylène, le carbonate de 2,3-pentylène, le carbonate de vinylène et le carbonate de fluoroéthylène (FEC); et au moins un solvant organique choisi dans le groupe constitué par un ou plusieurs solvants organiques à base de carbonate linéaire choisis dans le groupe constitué par le carbonate de diméthyle, le carbonate de diéthyle, le carbonate de dipropyle, le carbonate d'éthyle méthyle, le carbonate de méthyle propyle, et le carbonate d'éthyle propyle. L'additif comprend du carbonate de vinylène, du sulfate de 1,3-propylène et du 1,3-propane sultone selon le rapport pondéral de 1 : 0,5 à 1 : 0,1 à 1, et la teneur totale de l'additif est de 1 % en poids à 4 % en poids par rapport au poids total de l'électrolyte non aqueux pour une batterie secondaire au lithium.
PCT/KR2018/000874 2017-01-20 2018-01-18 Électrolyte non aqueux pour batterie secondaire au lithium, et batterie secondaire au lithium le comprenant Ceased WO2018135890A1 (fr)

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PL18741979T PL3419097T3 (pl) 2017-01-20 2018-01-18 Roztwór niewodnego elektrolitu dla akumulatora litowego i zawierający go akumulator litowy
CN201880001563.9A CN109075386B (zh) 2017-01-20 2018-01-18 用于锂二次电池的非水电解质溶液和包括该非水电解质溶液的锂二次电池
US16/308,724 US10950894B2 (en) 2017-01-20 2018-01-18 Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery including the same

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KR102697788B1 (ko) * 2019-08-30 2024-08-23 주식회사 엘지에너지솔루션 리튬 이차 전지용 전해질 및 이를 포함하는 리튬 이차 전지
KR102845706B1 (ko) * 2019-12-13 2025-08-12 현대자동차주식회사 리튬 이차전지용 전해액 및 이를 포함하는 리튬 이차전지
CN113130890B (zh) * 2019-12-31 2023-01-17 深圳新宙邦科技股份有限公司 一种锂离子电池
CN114946066A (zh) * 2020-09-03 2022-08-26 株式会社Lg新能源 锂二次电池
WO2023184126A1 (fr) * 2022-03-29 2023-10-05 宁德新能源科技有限公司 Batterie au lithium-ion et dispositif électronique

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