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WO2016048104A1 - Électrolyte non aqueux et pile rechargeable au lithium le comprenant - Google Patents

Électrolyte non aqueux et pile rechargeable au lithium le comprenant Download PDF

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Publication number
WO2016048104A1
WO2016048104A1 PCT/KR2015/010239 KR2015010239W WO2016048104A1 WO 2016048104 A1 WO2016048104 A1 WO 2016048104A1 KR 2015010239 W KR2015010239 W KR 2015010239W WO 2016048104 A1 WO2016048104 A1 WO 2016048104A1
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WO
WIPO (PCT)
Prior art keywords
lithium
secondary battery
carbonate
lithium secondary
aqueous electrolyte
Prior art date
Application number
PCT/KR2015/010239
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English (en)
Korean (ko)
Inventor
김슬기
이철행
임영민
김광연
Original Assignee
주식회사 엘지화학
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from KR1020150135260A external-priority patent/KR101797290B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP15844297.0A priority Critical patent/EP3076473B1/fr
Priority to JP2017516685A priority patent/JP6671724B2/ja
Priority to US15/108,981 priority patent/US10090560B2/en
Priority to CN201580005363.7A priority patent/CN105934848B/zh
Publication of WO2016048104A1 publication Critical patent/WO2016048104A1/fr

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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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • 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 is a non-aqueous electrolyte containing lithium bis (fluorosulfonyl) imide (LiFSI) and a fluorinated ether compound additive, comprising lithium-nickel-manganese-cobalt oxide as a positive electrode active material It relates to a lithium secondary battery comprising a positive electrode, a negative electrode, and a separator.
  • LiFSI lithium bis (fluorosulfonyl) imide
  • fluorinated ether compound additive comprising lithium-nickel-manganese-cobalt oxide as a positive electrode active material
  • a lithium secondary battery comprising a positive electrode, a negative electrode, and a separator.
  • lithium secondary batteries having high energy density and voltage among these secondary batteries are commercially used and widely used.
  • Lithium metal oxide is used as a positive electrode active material of a lithium secondary battery, and lithium metal, a lithium alloy, crystalline or amorphous carbon or a carbon composite material is used as a negative electrode active material.
  • the active material is applied to a current collector with a suitable thickness and length, or the active material itself is applied in a film shape to form an electrode group by winding or laminating together with a separator, which is an insulator, and then put it in a can or a similar container, and then injecting an electrolyte solution.
  • a secondary battery is manufactured.
  • lithium secondary battery In such a lithium secondary battery, charging and discharging progress while repeating a process of intercalating and deintercalating lithium ions from a lithium metal oxide of a positive electrode to a graphite electrode of a negative electrode.
  • lithium is highly reactive and reacts with the carbon electrode to generate Li 2 CO 3 , LiO, LiOH and the like to form a film on the surface of the negative electrode.
  • a film is called a solid electrolyte interface (SEI) film, and the SEI film formed at the beginning of charging prevents the reaction between lithium ions and a carbon anode or other material during charging and discharging. It also acts as an ion tunnel, allowing only lithium ions to pass through.
  • the ion tunnel serves to prevent the organic solvents of a large molecular weight electrolyte which solvates lithium ions and move together and are co-intercalated with the carbon anode to decay the structure of the carbon anode.
  • a solid SEI film must be formed on the negative electrode of the lithium secondary battery. Once formed, the SEI membrane prevents the reaction between lithium ions and the negative electrode or other materials during repeated charge / discharge cycles, and serves as an ion tunnel that passes only lithium ions between the electrolyte and the negative electrode. Will be performed.
  • the problem to be solved by the present invention is to provide a non-aqueous electrolyte for lithium secondary battery and a lithium secondary battery comprising the same that can improve the high temperature storage characteristics and lifetime characteristics.
  • the present invention provides a non-aqueous electrolyte containing lithium bis (fluorosulfonyl) imide (LiFSI) and a fluorinated ether compound additive, lithium-nickel-manganese- as a cathode active material. It provides a lithium secondary battery comprising a positive electrode, a negative electrode, and a separator comprising a cobalt-based oxide.
  • LiFSI lithium bis (fluorosulfonyl) imide
  • a fluorinated ether compound additive lithium-nickel-manganese- as a cathode active material.
  • the non-aqueous electrolyte solution may further include a lithium salt, the mixing ratio of the lithium salt and lithium bisfluoro sulfonyl imide is 1: 0.01 to 1: 1 in molar ratio, the lithium bisfluoro sulfonyl imide is
  • the concentration of the aqueous electrolyte may be a lithium secondary battery of 0.01 mol / L to 2 mol / L.
  • the lithium-nickel-manganese-cobalt-based oxide may include an oxide represented by Formula 1 below.
  • a solid SEI film is formed at a negative electrode during initial charging of the lithium secondary battery including the same, and the increase in battery thickness is minimized by suppressing gas generation at a high temperature environment.
  • the non-aqueous electrolyte solution according to one embodiment of the present invention includes lithium bisfluorosulfonylimide (LiFSI).
  • the lithium bisfluorosulfonylimide is added to the non-aqueous electrolyte as a lithium salt to form a solid, thin SEI film on the negative electrode to improve low temperature output characteristics, as well as to decompose positive electrode surfaces that may occur during high temperature cycle operation. It can suppress and prevent the oxidation reaction of electrolyte solution.
  • the SEI film generated on the negative electrode has a small thickness so that the movement of lithium ions in the negative electrode can be more smoothly performed, thereby improving the output of the secondary battery.
  • the lithium bisfluorosulfonylimide preferably has a concentration in the non-aqueous electrolyte of 0.01 mol / L to 2 mol / L, more preferably 0.01 mol / L to 1 mol / L. Do.
  • the concentration of the lithium bisfluorosulfonylimide is less than 0.1 mol / L, the effect of improving the low temperature output and the high temperature cycle characteristics of the lithium secondary battery is insignificant, and the concentration of the lithium bisfluorosulfonylimide is When the amount exceeds 2 mol / l, side reactions in the electrolyte may be excessively generated during charging and discharging of the battery, and swelling may occur, and corrosion of the positive electrode or the negative electrode current collector made of metal in the electrolyte may occur.
  • the non-aqueous electrolyte solution of the present invention may further include a lithium salt.
  • the lithium salt may be used a lithium salt commonly used in the art, for example LiPF 6 , LiAsF 6 , LiCF 3 SO 3 , LiBF 6 , LiSbF 6 , LiN (C 2 F 5 SO 2 ) 2 , LiAlO 4 , LiAlCl 4 , LiSO 3 CF 3 and LiClO 4 may be any one selected from the group consisting of or a mixture of two or more thereof.
  • the mixing ratio of the lithium salt and lithium bisfluoro sulfonyl imide is preferably 1: 0.01 to 1 as molar ratio.
  • the mixing ratio of the lithium salt and lithium bisfluoro sulfonyl imide is greater than or equal to the molar ratio, side reactions in the electrolyte may occur excessively during charging and discharging of the battery, and a swelling phenomenon may occur. In this case, output improvement of the generated secondary battery may be reduced.
  • the mixing ratio of the lithium salt and lithium bisfluoro sulfonyl imide is less than 1: 0.01
  • a process of forming an SEI film in a lithium ion battery, and lithium ions solvated by a carbonate solvent In the process of being inserted between the negative electrode, a large number of irreversible reactions may occur, and by the peeling of the negative electrode surface layer (for example, the carbon surface layer) and the decomposition of the electrolyte, the low temperature output of the secondary battery may be improved, the high temperature storage, the cycle characteristics and The effect of improving the dose characteristics may be insignificant.
  • the mixing ratio of the lithium salt and the lithium bisfluoro sulfonyl imide is a molar ratio
  • the ratio is greater than 1: 1
  • lithium bisfluoro sulfonyl imide of excessive capacity is included in the electrolyte to prevent corrosion of the electrode current collector during charging and discharging. This may affect the stability of the secondary battery.
  • the positive electrode active material which is the lithium-nickel-manganese-cobalt-based oxide may include an oxide represented by Formula 1 below.
  • the positive electrode active material which is the lithium-nickel-manganese-cobalt-based oxide
  • the positive electrode active material which is the lithium-nickel-manganese-cobalt-based oxide
  • it may be combined with lithium bisfluoro sulfonyl imide to have a synergistic effect.
  • Li + 1 ions and Ni + 2 ions in the layered structure of the cathode active material change as the amount of Ni in the transition metal increases. mixing) occurs and the structure thereof collapses, and the cathode active material causes side reactions with the electrolyte, or dissolution of transition metals. This occurs because Li +1 ions and Ni +2 ions have similar sizes.
  • the performance of the battery is easily degraded due to electrolyte depletion and structural collapse of the positive electrode active material inside the secondary battery.
  • LiFSI applied electrolyte to the positive electrode active material of Formula 1 to form a layer layer of the LiFSI-based components on the surface of the anode cation mixing of Li + 1 ions and Ni + 2 ions While suppressing the phenomenon, a range was found in which sufficient nickel transition metal amount for securing the capacity of the positive electrode active material could be secured.
  • the positive electrode active material including the oxide according to Chemical Formula 1 of the present invention when using a LiFSI-applied electrolyte, it is possible to effectively suppress the electrolyte, side reactions, metal dissolution and the like.
  • Li + 1 is also ionized by the layer layer formed of LiFSI on the electrode surface described above. And Ni +2 may not suppress cation mixing of ions.
  • the nickel transition metal having a d-orbit should have an octahedral structure in coordination bond under high temperature or the like due to the variation in the oxidation number of Ni, but in order of energy level by external energy supply. Is reversed, or the oxidation number is varied (disproportionation reaction) to form a distorted octahedron. As a result, the crystal structure of the positive electrode active material including the nickel transition metal is deformed to increase the probability of eluting nickel metal in the positive electrode active material.
  • the present inventors have confirmed that while producing a high output when the positive electrode active material including the oxide according to the formula (1) range and the LiFSI salt combination, it shows excellent efficiency in high temperature stability and capacity characteristics.
  • the electrolyte additive according to an embodiment of the present invention may include a fluorinated ether compound. Specifically, at least one selected from the group consisting of compounds represented by Formula 2 below.
  • R 1 and R 2 are each independently a linear or branched alkyl group having 2 to 6 carbon atoms containing 5 or more fluorine, and specifically, the fluorinated ether compound is di (1,1,1,2,2 Group consisting of 3,3,4,4-nonafluoropentyl) ether and di (1,1,1,2,2,3,3,4,4,5,5-undecafluoropentyl) ether It may be one or more selected from.
  • the fluorinated ether compound has a fluorine substituent added to the electrolyte as a flame retardant compound, and reacts with the surface of the cathode and anode at high temperature in the battery and reacts with the electrolyte to suppress the gas generated by decomposition of the electrolyte, and has a low viscosity.
  • the content of the fluorinated ether compound may be used without limitation so long as it is an amount necessary to achieve the effects of the present invention, such as improving the high temperature storage characteristics and life characteristics of the battery, for example 1 to 20 based on the total amount of the electrolyte It may be weight percent, preferably 3.0 to 15% by weight.
  • the amount of the fluorinated ether compound is less than 1% by weight, it is difficult to sufficiently exhibit the effect of suppressing gas generation, flame retardancy and resistance with addition, and when the amount of the fluorinated ether compound exceeds 20% by weight. While the degree of effect increase is limited, problems may arise such as an increase in irreversible capacity or an increase in the resistance of the cathode.
  • the fluorinated ether compound can be adjusted according to the amount of lithium bis fluoro sulfonyl imide added. This is to more effectively prevent side reactions that may occur with the addition of a large amount of lithium bis fluorosulfonyl imide.
  • the non-aqueous electrolyte solution includes a non-aqueous organic solvent, the non-aqueous organic solvent that may be included in the non-aqueous electrolyte, the decomposition by the oxidation reaction, etc. in the charge and discharge of the battery can be minimized, with an additive
  • a non-aqueous organic solvent the non-aqueous organic solvent that may be included in the non-aqueous electrolyte, the decomposition by the oxidation reaction, etc. in the charge and discharge of the battery can be minimized, with an additive
  • an additive There is no restriction as long as it can exhibit the desired properties, and for example, it may be a nitrile solvent, a cyclic carbonate, a linear carbonate, an ester, an ether or a ketone, or the like. These may be used alone, or two or more thereof may be used in combination.
  • Carbonate-based organic solvents of the organic solvents can be easily used, the cyclic carbonate is any one selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC) and butylene carbonate (BC) or two of them A mixture of two or more species, the linear carbonate consists of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), ethylmethyl carbonate (EMC), methylpropyl carbonate (MPC) and ethylpropyl carbonate (EPC) It may be any one selected from the group or a mixture of two or more thereof.
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • DPC dipropyl carbonate
  • EMC ethylmethyl carbonate
  • MPC methylpropyl carbonate
  • EPC ethylpropyl carbonate
  • the nitrile solvents include acetonitrile, propionitrile, butyronitrile, valeronitrile, caprylonitrile, heptanenitrile, cyclopentane carbonitrile, cyclohexane carbonitrile, 2-fluorobenzonitrile and 4-fluorobenzonitrile , Difluorobenzonitrile, trifluorobenzonitrile, phenylacetonitrile, 2-fluorophenylacetonitrile, 4-fluorophenylacetonitrile may be one or more selected from the group consisting of, one embodiment of the present invention Acetonitrile may be used as the non-aqueous solvent according to the example.
  • the lithium secondary battery according to an embodiment of the present invention may include a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode and the non-aqueous electrolyte.
  • the positive electrode and the negative electrode may each include a positive electrode active material and a negative electrode active material according to an embodiment of the present invention.
  • the negative electrode active material includes amorphous carbon or crystalline carbon, specifically, carbon such as non-graphitized carbon, graphite-based carbon; LixFe 2 O 3 (0 ⁇ x ⁇ 1), LixWO 2 (0 ⁇ x ⁇ 1 ), SnxMe 1 - x Me ' y O z (Me: Mn, Fe, Pb, Ge; Me': Al, B, P , Metal complex oxides such as Si, Group 1, 2, 3 Group elements of the periodic table, halogen, 0 ⁇ x ⁇ 1, 1 ⁇ y ⁇ 3, 1 ⁇ z ⁇ 8); Lithium metal; Lithium alloys; Silicon-based alloys; Tin-based alloys; SnO, SnO 2 , 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
  • the separator is a porous polymer film, for example, a porous polymer film made of a polyolefin-based polymer such as ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymer and ethylene / methacrylate copolymer This may be a single or two or more laminated.
  • a porous nonwoven fabrics such as high-melting glass fibers, polyethylene terephthalate fibers, and the like may be used, but are not limited thereto.
  • the secondary battery is various according to the purpose of performing the cylindrical, square, pouch type and the like, and is not limited to the configuration known in the art.
  • Lithium secondary battery according to an embodiment of the present invention may be a pouch-type secondary battery.
  • a non-aqueous electrolyte was prepared by adding 5 wt% based on the weight.
  • Li (Ni 0.6 Co 0.2 Mn 0.2 ) O 2 as a positive electrode active material
  • carbon black as a conductive agent
  • PVdF polyvinylidene fluoride
  • NMP 2-pyrrolidone
  • the positive electrode mixture slurry was applied to a thin film of aluminum (Al), which is a positive electrode current collector having a thickness of about 20 ⁇ m, dried to prepare a positive electrode, and then subjected to roll press to prepare a positive electrode.
  • a negative electrode mixture slurry was prepared by adding carbon powder as a negative electrode active material, PVdF as a binder, and carbon black as a conductive agent at 96 wt%, 3 wt%, and 1 wt%, respectively, to NMP as a solvent.
  • the negative electrode mixture slurry was applied to a copper (Cu) thin film, which is a negative electrode current collector having a thickness of 10 ⁇ m, dried to prepare a negative electrode, and then roll-rolled to prepare a negative electrode.
  • Cu copper
  • the positive electrode and the negative electrode prepared as described above were manufactured with a polymer battery by a conventional method with a separator composed of three layers of polypropylene / polyethylene / polypropylene (PP / PE / PP), followed by pouring the prepared non-aqueous electrolyte solution into a lithium secondary battery. The manufacture of the battery was completed.
  • LiPF 6 based on the total amount of the non-aqueous electrolyte A non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1 except that 0.7 mol / l and 0.3 mol / l of lithium bisfluorosulfonylimide were used.
  • LiPF 6 based on the total amount of the non-aqueous electrolyte A non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1 except that 0.6 mol / l and 0.4 mol / l of lithium bisfluorosulfonylimide were used.
  • LiPF 6 based on the total amount of the non-aqueous electrolyte A non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1 except that 0.5 mol / l and 0.5 mol / l of lithium bisfluorosulfonylimide were used.
  • Example 1 in place of di (1,1,1,2,2,3,3,4,4-nonafluoropentyl) ether, di (1,1,1,2,2,3,3, A non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1 except that 4,4,5,5-undecafluoropentyl) ether was used.
  • Example 1 D (1,1,1,2,2,3,3,4,4- nonafluoro a pentyl) in place of the ether CF 3 CH 2 OCF 2 CF 2 H (AE3000, manufactured by Asahi Glass Co., Ltd.) Except for using, in the same manner as in Example 1 to prepare a non-aqueous electrolyte solution and a lithium secondary battery.
  • LiPF 6 based on the total amount of the non-aqueous electrolyte A non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1 except that 0.4 mol / l and 0.6 mol / l of lithium bisfluorosulfonylimide were used.
  • a non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 2 except that the additive was not used.
  • a non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 2 except for Li (Ni 0.5 Co 0.3 Mn 0.2 ) O 2 as the cathode active material.
  • the secondary battery prepared in Examples 1 to 6 and Comparative Examples 1 to 3 was calculated using the voltage difference generated when charging and discharging the secondary battery prepared for 60 weeks at 60 °C for 10 seconds at 23 °C 5C.
  • Table 1 shows the results of calculating the output amount after 16 weeks as a percentage based on the initial output amount (16 weeks output (W) / initial output (W) * 100 (%)). The test was performed at 50% SOC (state of charge).
  • the secondary batteries manufactured in Examples 1 to 6 and Comparative Examples 1 to 3 were charged at 1 C up to 4.2 V / 38 mA under constant current / constant voltage (CC / CV) conditions, and then discharged at 3 C up to 2.5 V under constant current (CC) conditions. And the discharge capacity was measured. Then, after storing the secondary batteries prepared in Examples 1 to 6 and Comparative Examples 1 to 3 for 16 weeks at 60 ° C., the secondary batteries were again 4.2 V / 38 mA at 23 ° C. under constant current / constant voltage (CC / CV) conditions. After charging to 1C, and discharged at 3C to 2.5V under constant current (CC) conditions, the discharge capacity was measured. The results obtained by calculating the discharge capacity after 16 weeks based on the initial discharge capacity as a percentage (discharge capacity after 16 weeks / initial discharge capacity * 100 (%)) are shown in Table 1 below.
  • the secondary battery of Example 6 used a fluorinated ether compound as an additive, but showed a relatively low output characteristics and capacity characteristics compared to the secondary batteries of Examples 1 to 5, which is the secondary of Examples 1 to 5
  • the fluorinated ether compound included in the battery is an alkyl group including five or more fluorine on each side with respect to the oxygen atom
  • the fluorinated ether compound included in the secondary battery of Example 6 is based on the oxygen atom. It is believed that this is because alkyl groups containing less than 5 fluorine are positioned on each side independently.
  • the lithium secondary batteries of Examples 1 to 6 and Comparative Examples 1 to 3 were charged at 1 C to 4.2 V / 38 mA in constant current / constant voltage (CC / CV) conditions at 23 ° C., and then to 2.5 V in constant current (CC) conditions. It discharged at 3C and the discharge capacity was measured. This was repeated 1 to 800 cycles, and the discharge capacity measured by calculating the percentage of the 800th cycle as a percentage (800th capacity / 1st capacity * 100 (%)) based on the first cycle is shown in Table 2.
  • the lithium secondary batteries of Examples 1 to 6 and Comparative Examples 1 to 3 were charged at 1 C to 4.2 V / 38 mA at constant current / constant voltage (CC / CV) conditions at 45 ° C., and then to 2.5 V at constant current (CC) conditions. It discharged at 3C and the discharge capacity was measured. This was repeated 1 to 800 cycles, and the discharge capacity measured by calculating the percentage of the 800th cycle as a percentage (800th capacity / 1st capacity * 100 (%)) based on the first cycle is shown in Table 2.
  • the secondary battery of Example 6 has an alkyl group containing less than 5 fluorine on each side independently of the oxygen atoms, respectively, room temperature and high temperature life characteristics compared to the lithium secondary battery of Examples 1 to 5 This was relatively low.

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Abstract

La présente invention concerne une pile rechargeable au lithium comprenant : un électrolyte non aqueux comprenant du bis(fluorosulfonyl)imide de lithium (LiFSI) et un additif composé éther fluoré ; une électrode positive contenant un oxyde de lithium-nickel-manganèse-cobalt comme matériau actif d'électrode positive ; une électrode négative ; et une membrane de séparation. L'électrolyte non aqueux pour pile rechargeable au lithium, selon la présente invention, forme un film d'interface électrolytique solide (SEI) sur l'électrode négative pendant la charge initiale d'une pile rechargeable au lithium comprenant l'électrolyte non aqueux, améliorant les propriétés de sortie de la pile rechargeable au lithium, et améliore également les propriétés de sortie et les propriétés de capacité après stockage à haute température.
PCT/KR2015/010239 2014-09-26 2015-09-25 Électrolyte non aqueux et pile rechargeable au lithium le comprenant WO2016048104A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP15844297.0A EP3076473B1 (fr) 2014-09-26 2015-09-25 Électrolyte non-aqueux et batterie secondaire au lithium le comprenant
JP2017516685A JP6671724B2 (ja) 2014-09-26 2015-09-25 非水性電解液リチウム二次電池
US15/108,981 US10090560B2 (en) 2014-09-26 2015-09-25 Non-aqueous liquid electrolyte and lithium secondary battery comprising the same
CN201580005363.7A CN105934848B (zh) 2014-09-26 2015-09-25 非水电解液及包含所述非水电解液的锂二次电池

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20140128880 2014-09-26
KR10-2014-0128880 2014-09-26
KR10-2015-0135260 2015-09-24
KR1020150135260A KR101797290B1 (ko) 2014-09-26 2015-09-24 비수성 전해액 및 이를 포함하는 리튬 이차 전지

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017191740A (ja) * 2016-04-15 2017-10-19 国立大学法人 東京大学 リチウムイオン二次電池
CN113097566A (zh) * 2021-04-01 2021-07-09 山东海科新源材料科技股份有限公司 含磺化侧链的酰亚胺类添加剂、电解液及其锂离子电池
CN115360429A (zh) * 2022-09-30 2022-11-18 苏州德加能源科技有限公司 一种新型低温电池电解液及其制备方法和应用

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Publication number Priority date Publication date Assignee Title
JP2017191740A (ja) * 2016-04-15 2017-10-19 国立大学法人 東京大学 リチウムイオン二次電池
CN113097566A (zh) * 2021-04-01 2021-07-09 山东海科新源材料科技股份有限公司 含磺化侧链的酰亚胺类添加剂、电解液及其锂离子电池
CN113097566B (zh) * 2021-04-01 2022-04-05 山东海科新源材料科技股份有限公司 含磺化侧链的酰亚胺类添加剂、电解液及其锂离子电池
CN115360429A (zh) * 2022-09-30 2022-11-18 苏州德加能源科技有限公司 一种新型低温电池电解液及其制备方法和应用

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