WO2021033986A1 - Solution électrolytique pour batterie secondaire et batterie secondaire la comprenant - Google Patents

Solution électrolytique pour batterie secondaire et batterie secondaire la comprenant Download PDF

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WO2021033986A1
WO2021033986A1 PCT/KR2020/010628 KR2020010628W WO2021033986A1 WO 2021033986 A1 WO2021033986 A1 WO 2021033986A1 KR 2020010628 W KR2020010628 W KR 2020010628W WO 2021033986 A1 WO2021033986 A1 WO 2021033986A1
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carbonate
secondary battery
electrolyte
formula
lithium
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PCT/KR2020/010628
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English (en)
Korean (ko)
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신재욱
김재희
최정식
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동화일렉트로라이트 주식회사
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Publication of WO2021033986A1 publication Critical patent/WO2021033986A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—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
    • H01M10/052—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
    • H01M10/0569—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
    • H01M10/05—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
    • 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 an electrolyte for a secondary battery and a secondary battery including the same, and more particularly, to improve the room temperature life and output characteristics by adding a compound represented by Chemical Formula 1 or a phosphate-based lithium salt to a non-aqueous electrolyte for a lithium ion secondary battery. It relates to an effective non-aqueous electrolyte for a secondary battery and a secondary battery including the same.
  • the secondary battery used as a power source can be charged and discharged for a long time with a small size and light weight, and efforts to improve high rate characteristics are being concentrated.
  • Secondary batteries include lead-acid batteries, nickel-cadmium (Ni-Cd) batteries, nickel-hydrogen (Ni-MH) batteries, lithium batteries, etc., depending on the anode material or the cathode material.
  • the potential and energy density are determined by Among these, lithium secondary batteries are widely used as driving power supplies for portable electronic devices such as notebook computers, camcorders, and mobile phones because of their high energy density due to the low oxidation/reduction potential and molecular weight of lithium.
  • a lithium secondary battery using a non-aqueous electrolyte is used as a positive electrode coated with a lithium metal mixed oxide capable of desorbing and intercalating lithium ions as a positive electrode active material on a metal, and a carbon material or metal lithium as a negative electrode active material on the metal as a negative electrode. It is coated and used, and an electrolyte solution in which a lithium salt is suitably dissolved in an organic solvent is placed between the positive electrode and the negative electrode.
  • the organic solvent of the electrolyte may decompose on the electrode surface during charging and discharging of the battery, or co-intercalation between the carbon material negative electrode layers to collapse the negative electrode structure, thereby impairing the stability of the battery.
  • Korean Patent Registration No. 10-1492686 discloses lithium oxalyldifluoroborate (LiODFB), vinylidene carbonate-based compound, sulfate-based compound, and sultone-based compound.
  • LiODFB lithium oxalyldifluoroborate
  • vinylidene carbonate-based compound vinylidene carbonate-based compound
  • sulfate-based compound vinylidene carbonate-based compound
  • sultone-based compound sultone-based compound.
  • Korean Patent Registration No. 10-1538485 discloses a non-aqueous electrolyte solution for secondary batteries containing alkylene sulfate, ammonium compound and vinylene carbonate of a specific formula, but the stability of the positive electrode at a high rate is lowered due to the absence of the positive electrode additive. It is difficult to implement a capacity, and there is a problem in that long-term life efficiency is deteriorated because it is not possible to form a stable anode film and elute transition metals.
  • U.S. Patent Publication 2017/0301952 A1 discloses a non-aqueous electrolyte for a secondary battery containing a cyclic sultonate, a cyclic sulfate, a silane phosphate and/or a silane borate compound and a fluorophosphate salt
  • Korean Patent Laid-Open No. 2016-0144123 Is an electrolyte containing vinylene carbonate and a cyclic sulfate compound, and is known for its effects on high temperature stability, low temperature discharge capacity, and room temperature life characteristics, but the addition of lithium difluorophosphate suppresses the increase in resistance during high temperature storage or , There is no disclosure of the effect of improving the life characteristics at high temperature (70°C).
  • an electrolyte solution containing an optimal additive composition capable of simultaneously satisfying an improved capacity retention rate and a lifetime retention rate while suppressing an increase in resistance during high-temperature storage.
  • the present inventors have made diligent efforts to solve the above problem, and as a result of adding a compound represented by Formula 1 and a phosphate-based lithium salt to an electrolyte for a secondary battery, it has been confirmed that the normal temperature, high temperature life, and output characteristics before and after high temperature are improved. And completed the present invention.
  • An object of the present invention is to provide a non-aqueous electrolyte for a secondary battery with improved life characteristics at room temperature and high temperature and output characteristics before and after high temperature.
  • Another object of the present invention is to provide a secondary battery having excellent life characteristics at room temperature and high temperature at high temperature and output characteristics before and after high temperature.
  • R 1 to R 6 are each independently an unsubstituted C 1 to C 9 alkyl group or a C 1 to C 9 alkyl group substituted with a halogen atom, an unsubstituted C 2 to C 9 alkenyl group or C 1 substituted with a halogen atom ⁇ C 9 is an alkenyl group, X is , or Where n is an integer from 1 to 4; Z is a group 6A element.
  • the present invention also includes (a) a positive electrode comprising a positive electrode active material capable of occluding and releasing lithium; (b) a negative electrode including a negative electrode active material capable of storing and releasing lithium; (c) the electrolyte for the secondary battery; And (d) a separator to provide a lithium secondary battery.
  • the non-aqueous electrolyte according to the present invention has the effect of improving the life characteristics at room temperature and high temperature and output characteristics before and after high temperature by adding the compound represented by Formula 1 and a phosphate-based lithium salt.
  • the present invention in one aspect, (A) lithium salt; (B) a non-aqueous organic solvent; (C) a compound represented by Formula 1; And (D) a phosphate-based lithium salt additive.
  • R 1 to R 6 are each independently an unsubstituted C 1 to C 9 alkyl group or a C 1 to C 9 alkyl group substituted with a halogen atom, an unsubstituted C 2 to C 9 alkenyl group or C 1 substituted with a halogen atom ⁇ C 9 is an alkenyl group, X is , or Where n is an integer from 1 to 4; Z is a group 6A element.
  • the present invention includes: (a) a positive electrode including a positive electrode active material capable of storing and releasing lithium; (b) a negative electrode including a negative electrode active material capable of storing and releasing lithium; (c) the electrolyte for the secondary battery; And (d) the separator relates to a lithium secondary battery.
  • the electrolyte for a secondary battery according to the present invention includes (A) a lithium salt; (B) a non-aqueous organic solvent; (C) a compound represented by Formula 1; And (D) a phosphate-based lithium salt additive.
  • R 1 to R 6 are each independently an unsubstituted C 1 to C 9 alkyl group or a C 1 to C 9 alkyl group substituted with a halogen atom, an unsubstituted C 2 to C 9 alkenyl group or C 1 substituted with a halogen atom ⁇ C 9 is an alkenyl group, X is , or Where n is an integer from 1 to 4; Z is a group 6A element.
  • the electrolyte for a secondary battery according to the present invention contains lithium salt as a solute of the electrolyte.
  • Lithium salts 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 and LiC(CF 3 SO 2 ) It may be one or more selected from the group consisting of 3.
  • the concentration of the lithium salt is preferably used within the range of 0.6M to 2.0M, more preferably 0.7M to 1.6M, and if it is less than 0.6M, the conductivity of the electrolyte decreases, resulting in poor electrolyte performance, and 2.0M If it is exceeded, there is a problem in that the viscosity of the electrolyte solution increases and the mobility of lithium ions decreases.
  • These lithium salts act as a source of lithium ions in the battery, thereby enabling the operation of a basic lithium secondary battery.
  • the electrolyte for a secondary battery according to the present invention includes a non-aqueous organic solvent.
  • the non-aqueous organic solvent may be at least one selected from the group consisting of linear carbonates, cyclic carbonates, linear esters and cyclic esters.
  • the linear carbonate may be one or more carbonates selected from the group consisting of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, ethyl methyl carbonate, and mixtures thereof, but is not limited thereto.
  • the cyclic carbonates are ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate, vinylene carbonate, vinylethylene carbonate, and It may be one or more carbonates selected from the group consisting of fluoroethylene carbonate, but is not limited thereto.
  • the linear ester may be one or more esters selected from the group consisting of methyl propionate, ethyl propionate, propyl acetate, butyl acetate, and ethyl acetate, but is not limited thereto.
  • the cyclic ester may be one or more esters selected from the group consisting of gamma butyrolactone, caprolactone, and valerolactone, but is not limited thereto.
  • the non-aqueous organic solvent is a mixed solvent of a cyclic carbonate solvent and a linear carbonate solvent
  • the mixing volume ratio of the linear carbonate solvent: the cyclic carbonate solvent is 1:9 to 9:1 days. It can be used, preferably by mixing in a volume ratio of 1.5:1 to 4:1.
  • the electrolyte solution for a secondary battery according to the present invention includes a compound represented by Formula 1.
  • R 1 to R 6 are each independently an unsubstituted C 1 to C 9 alkyl group or a C 1 to C 9 alkyl group substituted with a halogen atom, an unsubstituted C 2 to C 9 alkenyl group or C 1 substituted with a halogen atom ⁇ C 9 is an alkenyl group, X is , or Where n is an integer from 1 to 4; Z is a group 6A element.
  • the compound represented by Formula 1 is bis(trimethylsilyl) fumarate (BTMSF), which is a compound represented by Formula 2, and bis(trimethylsilyl) 2 which is a compound represented by Formula 3 ,2'-thiodiacetate (bis(trimethylsilyl) 2,2'-thiodiacetate, BTMSTDA) or a mixture of a compound represented by Formula 2 and a compound represented by Formula 3.
  • BTMSF bis(trimethylsilyl) fumarate
  • BTMSTDA bis(trimethylsilyl) 2,2'-thiodiacetate
  • the content of the compound represented by Formula 1 may be added in an amount of 0.05 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.2 to 3% by weight, based on the electrolyte solution for secondary batteries. If it is less than 0.05% by weight, the effect of forming a stable SEI film on the electrode is insignificant and it is insufficient to suppress the deterioration of the battery.If it exceeds 10% by weight, the electrode film is formed too thick to increase the electrode interface resistance. There is a problem that characteristics are deteriorated.
  • the electrolyte for a secondary battery according to the present invention includes a phosphate-based lithium salt.
  • the phosphoric acid-based lithium salt is lithium difluorophosphate (LFP), lithium tetrafluoro oxalate phosphate (LTFOP), and lithium difluoro bisoxalato phosphate.
  • LFP lithium difluorophosphate
  • LPFOP lithium tetrafluoro oxalate phosphate
  • LDFBOP lithium difluoro bisoxalato phosphate.
  • phosphate, LDFBOP may be one or more selected from the group consisting of.
  • the content of the phosphate-based lithium salt additive may be added in an amount of 0.05 to 10% by weight, preferably 0.05 to 5% by weight, more preferably 0.05 to 3% by weight, based on the electrolyte solution for a secondary battery, If it is less than 0.05% by weight, there is a problem that it is insufficient to transform the structure of the SEI film into a high ion permeable SEI layer, and if it exceeds 10% by weight, it causes resistance due to an increase in the viscosity of the electrolyte, and the life and output characteristics of the secondary battery There is a problem of this deterioration.
  • the electrolyte solution of the lithium ion secondary battery of the present invention maintains stable characteristics in a temperature range of -20 to 50°C.
  • the electrolyte solution of the present invention can be applied to a lithium ion secondary battery, a lithium ion polymer battery, or the like.
  • the cathode material of the lithium secondary battery is LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , or LiNi 1 -x- y Co x M y O 2 (0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1 , 0 ⁇ x+y ⁇ 1, M is a metal such as Al, Sr, Mg, La, etc.), and a lithium metal oxide such as crystalline or amorphous carbon, carbon composite, lithium metal, or lithium alloy Use.
  • the active material is applied to the current collector of a thin plate with an appropriate thickness and length, or the active material itself is applied in the form of a film to form an electrode group by winding or laminating together with a separator, which is an insulator, and then put in a can or similar container, and then trialkyl.
  • a lithium ion secondary battery is prepared by injecting a non-aqueous electrolyte solution to which silyl sulfate and a phosphite stabilizer are added. Resins such as polyethylene and polypropylene may be used as the separator.
  • Li (Ni 0.6 Co 0.2 Mn 0.2 ) O 2 as a positive electrode active material, polyvinylidene fluoride (PVdF) as a binder, and carbon black as a conductive material were mixed in a weight ratio of 92:4:4, and then N-methyl-2- Disperse in pyrrolidone to prepare a positive electrode slurry.
  • the slurry was coated on an aluminum foil having a thickness of 20 ⁇ m, dried, and rolled to prepare a positive electrode.
  • Negative active material slurry by mixing crystalline artificial graphite as an anode active material, acetylene black as a conductive material, and polyvinylidene fluoride (PVdF) as a binder in a weight ratio of 92:1:7 and dispersing in N-methyl-2-pyrrolidone was prepared.
  • the slurry was coated on a 15 ⁇ m-thick copper foil, dried and rolled to prepare a negative electrode.
  • the separator was stacked, wound, and compressed to form a cell using a pouch having a thickness of 6 mm x 35 mm x 60 mm in length, and a lithium secondary battery was manufactured by injecting the following non-aqueous electrolyte.
  • LiPF 6 1.0 M was added to a non-aqueous organic solvent in which ethylene carbonate (EC) and ethyl methyl carbonate (EMC) were mixed at 3:7 (v/v), and 1% by weight of BTMSF and 1% by weight of LiPO 2 F 2 was added to prepare an electrolyte for a secondary battery.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • a lithium secondary battery was manufactured in the same manner as in Example 1, except that 1% by weight of BTMSTDA was added instead of 1% by weight of BTMSF in the electrolyte for a secondary battery.
  • a lithium secondary battery was manufactured in the same manner as in Example 1 except for adding 0.25% by weight of BTMSF and 0.25% by weight of BTMSTDA instead of 1% by weight of BTMSF in the electrolyte solution for a secondary battery of Example 1.
  • a lithium secondary battery was manufactured in the same manner as in Example 1 except for adding 1% by weight of LTFOP instead of 1% by weight of LiPO 2 F 2 in the electrolyte for a secondary battery.
  • a lithium secondary battery was manufactured in the same manner as in Example 2, except that 1% by weight of LTFOP was added instead of 1% by weight of LiPO 2 F 2 in the electrolyte for a secondary battery.
  • a lithium secondary battery was manufactured in the same manner as in Example 3 except for adding 1% by weight of LTFOP instead of 1% by weight of LiPO 2 F 2 in the electrolyte for a secondary battery of Example 3.
  • a lithium secondary battery was manufactured in the same manner as in Example 1 except that 1% by weight of LDFBOP was added instead of 1% by weight of LiPO 2 F 2 in the electrolyte for a secondary battery.
  • a lithium secondary battery was manufactured in the same manner as in Example 2 except for adding 1% by weight of LDFBOP instead of 1% by weight of LiPO 2 F 2 in the electrolyte for a secondary battery of Example 2.
  • a lithium secondary battery was manufactured in the same manner as in Example 3 except that 1% by weight of LDFBOP was added instead of 1% by weight of LiPO 2 F 2 in the electrolyte for a secondary battery.
  • a lithium secondary battery was manufactured in the same manner as in Example 1 except that BTMSF and LiPO 2 F 2 were not added to the electrolyte solution for a secondary battery.
  • a lithium secondary battery was manufactured in the same manner as in Example 1, except that LiPO 2 F 2 was not added to the electrolyte for a secondary battery.
  • a lithium secondary battery was manufactured in the same manner as in Example 2 except that LiPO 2 F 2 was not added to the electrolyte for a secondary battery.
  • a lithium secondary battery was manufactured in the same manner, except that LiPO 2 F 2 was not added to the electrolyte solution for a secondary battery of Example 3.
  • a lithium secondary battery was manufactured in the same manner except that BTMSF was not added to the electrolyte solution for a secondary battery of Example 1.
  • a lithium secondary battery was manufactured in the same manner as in Example 4 except that BTMSF was not added to the electrolyte for a secondary battery.
  • a lithium secondary battery was manufactured in the same manner as in Example 7 except that BTMSF was not added to the electrolyte for a secondary battery.
  • compositions of the electrolyte solutions of Examples 1 to 9 and Comparative Examples 1 to 7 are shown in Table 1.
  • Electrolyte composition (100wt%)
  • Example 1 BTMSF 1% + LiPO 2 F 2 1%
  • Example 2 BTMSTDA 1% + LiPO 2 F 2 One%
  • Example 3 BTMSF 0.25% + BTMSTDA 0.25% + LiPO 2 F 2 1%
  • Example 4 BTMSF 1% + LTFOP 1%
  • Example 5 BTMSTDA 1% + LTFOP 1%
  • Example 6 BTMSF 0.25% + BTMSTDA 0.25% + LTFOP 1%
  • Example 7 BTMSF 1% + LDFBOP 1%
  • Example 8 BTMSTDA 1% + LDFBOP 1%
  • Example 9 BTMSF 0.25% + BTMSTDA 0.25% + LDFBOP 1% Comparative Example 1 - Comparative Example 2 BTMSF 1% Comparative Example 3 BTMSTDA 1% Comparative Example 4 BTMSF 0.5% + BTMSTDA 0.5% Comparative Example 5 LiPO 2 F 2 1% Comparative Example 6 LTFOP 1% Comparative Example 7 LDFBOP
  • Example 3 the electrolytic solution of Example 3 in which 0.25% by weight of bis(trimethylsilyl) fumarate, 0.25% by weight of bis(trimethylsilyl) 2,2'-thiodiacetate, and 1% by weight of lithium difluorophosphate was added was Comparative Example 5. It showed about 3% improved life characteristics than that of Examples 1 to 2, about 1.5%.
  • Example 4 913.47 846.66 92.69 4.13
  • Example 5 913.83 847.79 92.77 4.22
  • Example 6 914.22 856.51 93.69 5.13
  • Example 7 914.11 855.49 93.59 5.03
  • Example 8 914.69 857.25 93.72 5.16
  • Example 9 915.82 867.17 94.69 6.13
  • Comparative Example 1 894.94 792.54 88.56 - Comparative Example 2 903.19 803.67 88.98 0.42
  • Comparative Example 3 904.45 805.13 89.02 0.46
  • Comparative Example 4 904.88 807.81 89.27 0.71
  • Comparative Example 6 910.56 820.71 90.13 1.57
  • the electrolyte solution of Examples 4 to 9 of the present invention at a high temperature (45° C.) has a cycle capacity ratio of 4.2 V to 300 cycles compared to Comparative Examples 1 to 4 and Comparative Examples 6 to 7 Showed.
  • Example 6 and lithium in which 1% by weight of lithium tetrafluorooxalate phosphate was added to 0.25% by weight of bis(trimethylsilyl) fumarate and 0.25% by weight of bis(trimethylsilyl) 2,2'-thiodiacetate, respectively.
  • Example 9 electrolytic solution to which 1% by weight of difluoro bis (oxalato) phosphate was added showed improved lifespan characteristics of about 4% or more compared to Comparative Examples 2 to 4.
  • Each of the secondary batteries prepared in Examples 1 to 9 and Comparative Examples 1 to 7 was charged to 4.2V at 1C and then discharged to 475mA at a constant current of 2C, and then the charge/discharge rates were 0.5C, 1C, 2C, 4C.
  • the initial discharge output was measured by discharging each for 10 seconds.After charging 1C to 4.2V, storing at high temperature (70°C) for 7 days, charging 1C to 4.2V and performing 1C discharge twice in the same way as the initial output measurement method. The output was measured after storage at high temperature (70° C.), and the measured output values are shown in Table 4 below.
  • Examples 1 to 3 had excellent initial output characteristics before storage at high temperature (70°C), and among them, 0.25% by weight of bis(trimethylsilyl) fumarate and 0.25% by weight of bis(trimethylsilyl) 2,2'-thiodiacetate ,
  • the secondary battery of Example 3 to which 1% by weight of lithium difluorophosphate was added showed the best initial output characteristics with an output value of 79.95W.
  • Examples 4 to 9 were excellent in output characteristics after storage at high temperature (70°C), and among them, 0.25% by weight of bis(trimethylsilyl) fumarate, 0.25% by weight of bis(trimethylsilyl) 2,2'-thiodiacetate, lithium
  • the secondary battery of Example 9 to which 1% by weight of difluorobis(oxalato) phosphate was added showed the best output characteristics after storage at high temperature (70°C) with an output value of 48.49W.
  • the secondary battery electrolyte according to the present invention provides a solid electrolyte interface (SEI) film on the electrode surface formed of the compound represented by Formula 1, rather than the secondary battery electrolyte in which the compound represented by Formula 1 or a phosphate-based lithium salt is added alone.
  • SEI solid electrolyte interface
  • the phosphate-based lithium salt transforms the structure of the SEI film into a highly ion-permeable SEI layer, thereby further improving the output characteristics at room temperature and high temperature life and before and after high temperature.

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Abstract

La présente invention concerne une solution électrolytique non aqueuse pour une batterie secondaire et une batterie secondaire la comprenant. L'ajout d'un composé représenté par la formule chimique 1 et d'un sel de lithium à base de phosphate à la solution électrolytique non aqueuse pour une batterie secondaire selon la présente invention a pour effet d'améliorer les caractéristiques de durée de vie et les caractéristiques de sortie.
PCT/KR2020/010628 2019-08-16 2020-08-11 Solution électrolytique pour batterie secondaire et batterie secondaire la comprenant WO2021033986A1 (fr)

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