WO2017074027A1 - Additif d'électrolyte non aqueux, électrolyte non aqueux le comprenant et batterie secondaire au lithium le contenant - Google Patents

Additif d'électrolyte non aqueux, électrolyte non aqueux le comprenant et batterie secondaire au lithium le contenant Download PDF

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WO2017074027A1
WO2017074027A1 PCT/KR2016/012093 KR2016012093W WO2017074027A1 WO 2017074027 A1 WO2017074027 A1 WO 2017074027A1 KR 2016012093 W KR2016012093 W KR 2016012093W WO 2017074027 A1 WO2017074027 A1 WO 2017074027A1
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formula
aqueous electrolyte
secondary battery
lithium secondary
additive
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PCT/KR2016/012093
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English (en)
Korean (ko)
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유성훈
강유선
이경미
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주식회사 엘지화학
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Priority claimed from KR1020160139012A external-priority patent/KR101937898B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201680037297.6A priority Critical patent/CN108370068B/zh
Priority to EP16860210.0A priority patent/EP3370296B1/fr
Priority to US15/735,741 priority patent/US10454138B2/en
Priority to PL16860210T priority patent/PL3370296T3/pl
Priority to JP2018528930A priority patent/JP6656717B2/ja
Publication of WO2017074027A1 publication Critical patent/WO2017074027A1/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
    • H01M10/052—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
    • 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
    • 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 additive, a nonaqueous electrolyte including the same, and a lithium secondary battery having the same, and specifically, a nonaqueous electrolyte additive capable of improving performance while ensuring stability at high voltage, a nonaqueous electrolyte including the same, and the same It relates to a lithium secondary battery.
  • Electrochemical devices are the most attracting field in this respect, and among them, interest in secondary batteries capable of charging and discharging has emerged.
  • lithium secondary batteries developed in the early 1990s among the currently applied secondary batteries have been in the spotlight for their advantages of high operating voltage and high energy density.
  • the lithium secondary battery is composed of a negative electrode made of a carbon material or the like capable of occluding and releasing lithium ions, a positive electrode made of a lithium transition metal oxide and the like, and a nonaqueous electrolyte.
  • the lithium secondary battery includes a lithium ion liquid battery (LiLB) using a liquid electrolyte, a lithium ion polymer battery (LiPB) using a gel polymer electrolyte, and a LPB (lithium) using a solid polymer electrolyte according to the type of electrolyte used. polymer battery).
  • LiLB lithium ion liquid battery
  • LiPB lithium ion polymer battery
  • LPB lithium
  • lithium secondary batteries that can be safely charged even at high voltages while maintaining excellent cycle life characteristics even in harsh environments such as high temperature, low temperature, and high voltage charging.
  • the cathode active material is structurally collapsed, thereby degrading the performance of the cathode.
  • metal ions eluted from the surface of the anode deteriorate the cathode while electrodeposition (electrodeposition) on the cathode.
  • electrodeposition electrodeposition
  • the first technical problem of the present invention is to provide a non-aqueous electrolyte additive excellent in the adsorption effect with the metal ions eluted from the anode.
  • Another object of the present invention is to provide a nonaqueous electrolyte solution for a lithium secondary battery that can improve overcharge safety of an electrolyte by including the nonaqueous electrolyte additive.
  • a third technical object of the present invention is to provide a lithium secondary battery having improved cycle characteristics and high temperature storage performance even at high voltage charging by including the nonaqueous electrolyte.
  • nonaqueous electrolyte additive comprising a compound represented by the following formula (1):
  • R is an alkyl group having 1 to 3 carbon atoms substituted or unsubstituted with at least one fluorine element
  • A is an alkyl group having 1 to 4 carbon atoms in which at least one fluorine element and cyano group (-CN) are substituted.
  • Ionizable lithium salts Organic solvents; And it provides a non-aqueous electrolyte for lithium secondary battery comprising the non-aqueous electrolyte additive.
  • a negative electrode a positive electrode, a separator interposed between the negative electrode and the positive electrode, and a lithium secondary battery having a nonaqueous electrolyte of the present invention.
  • the present invention provides a non-aqueous electrolyte additive that can form a more stable ionic conductive film on the surface of the anode to suppress the decomposition reaction of the electrolyte, thereby suppressing the decomposition reaction during overcharging or suppressing elution and movement of metal ions.
  • the lithium secondary battery electrolyte which can be made, and the lithium secondary battery which improved the lifetime characteristic and high temperature safety under high voltage can be manufactured.
  • Example 1 is a graph showing the life characteristics of a lithium secondary battery according to Experimental Example 1 of the present invention.
  • one embodiment of the present invention to provide a non-aqueous electrolyte additive that can form a complex with the metal ions eluted from the anode.
  • the present invention provides a nonaqueous electrolyte solution for a lithium secondary battery that can improve the overcharge safety of the electrolyte by including the nonaqueous electrolyte additive.
  • the present invention provides a lithium secondary battery having improved cycle characteristics and high temperature storage performance even at high voltage charging by including the nonaqueous electrolyte.
  • nonaqueous electrolyte additive comprising a compound represented by the following Formula 1 in which a cyano group and at least one fluorine element are present as a substituent:
  • R is an alkyl group having 1 to 3 carbon atoms substituted or unsubstituted with at least one fluorine element
  • A is an alkyl group having 1 to 4 carbon atoms in which at least one fluorine element and cyano group (-CN) are substituted.
  • Specific examples of the compound represented by Formula 1 include at least one compound selected from the group consisting of the following Formulas 1a to 1i.
  • Ionizable lithium salts Organic solvents; And nonaqueous electrolyte additives,
  • non-aqueous electrolyte lithium secondary battery containing the compound represented by the formula (1) as the non-aqueous electrolyte additive.
  • the nonaqueous electrolyte additive may be included in about 0.5 to 5% by weight, specifically 1 to 5% by weight, based on the total weight of the nonaqueous electrolyte. If the content of the additive is less than 0.5% by weight, the stabilizing effect of the SEI film described later is insufficient, and if the content of the additive is more than 5% by weight, at least one fluorine element substituted at the terminal of the compound of Formula 1 included in the additive Or increased resistance due to cyano groups.
  • lithium secondary battery forms a passivation film by electrochemical oxidative decomposition reaction of electrolyte at the surface of the battery's positive electrode, especially in the presence of surface bond or activation position. Increase impedance to co-intercalation.
  • structural dissolution of the cathode active material or chemical dissolution reaction occurs by the electrolytic solution, so that ions of Co, Mn, and Ni are eluted.
  • ions of Co, Mn, and Ni are eluted.
  • These reactions lead to a decrease in the performance of the anode itself, and at the same time, eluted metal ions are electrodeposited on the surface of the cathode.
  • the metal electrodeposited on the negative electrode generally exhibits great reactivity with the electrolyte. Therefore, the amount of reversible lithium is increased, thereby increasing the irreversible reaction according to the progress of charging and discharging, which results in deterioration of the capacity and life characteristics of the battery.
  • the present invention provides a cyano group (-CN) -containing compound having a high tendency to form a complex with metal ions such as Co, Mn, and Ni as an electrolyte additive.
  • the non-aqueous electrolyte additive made of the compound represented by Chemical Formula 1 of the present invention contains eluted metal ions and a cyano group of good adsorption, the non-aqueous electrolyte additive has a structural breakdown of the positive electrode active material during charge and discharge of the battery.
  • the complexes may be combined with the metal ions eluted from the anode to form a stable ion conductive film on the surface of the anode.
  • the non-aqueous electrolyte additive composed of the compound represented by Formula 1 of the present invention includes at least one or more fluorine elements as a substituent, not only is it easier to form a film, but also the ion conductive effect of the resulting film can be enhanced.
  • the compound represented by the formula (1) of the present invention can suppress the electrodeposition of the metal ions eluted from the positive electrode to the negative electrode even in a state where no film is formed. Therefore, the lithium secondary battery of the present invention having the nonaqueous electrolyte containing such additives can significantly improve overall performance such as room temperature and high temperature life characteristics of the secondary battery by allowing the negative electrode to smoothly occlude and release lithium even at high temperatures.
  • the lithium salt included as an electrolyte may be used without limitation those conventionally used in the electrolyte for lithium secondary batteries, for example, Li + as a cation of the lithium salt, an anion is F -, Cl -, Br - , I -, NO 3 -, N (CN) 2 -, BF 4 -, ClO 4 -, AlO 4 -, AlCl 4 -, PF 6 -, SbF 6 -, AsF 6 -, BF 2 C 2 O 4 -, BC 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 -, (CF 3 SO 2) 2 N -, (CN) 2 -, BF 4
  • the said lithium salt can also be used 1 type or in mixture of 2 or more types as needed.
  • the lithium salt may be appropriately changed within a range generally available, but may be included in an electrolyte solution at a concentration of 0.8 M to 1.5 M in order to obtain an effect of forming an anti-corrosion coating on the surface of the electrode.
  • the organic solvent included in the nonaqueous electrolyte of the present invention may be used without limitation those conventionally used in the lithium secondary battery electrolyte, for example, ether compounds, ester compounds, amide compounds, linear carbonate compounds, or cyclic carbonate compounds These may be used alone or in combination of two or more thereof. Representatively, it may include a cyclic carbonate compound, a linear carbonate compound, or a mixture thereof.
  • cyclic carbonate compound examples include ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate, vinylene carbonate and fluoroethylene carbonate (FEC) are any one selected from the group consisting of or mixtures of two or more thereof.
  • linear carbonate compound examples include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, ethylmethyl carbonate (EMC), methylpropyl carbonate and ethylpropyl carbonate. Any one selected from, or a mixture of two or more thereof may be representatively used, but is not limited thereto.
  • ethylene carbonate and propylene carbonate which are cyclic carbonates among the carbonate-based organic solvents, are highly viscous organic solvents, and thus may be preferably used because they dissociate lithium salts in the electrolyte well.
  • an electrolyte having high electrical conductivity can be made, and thus it can be used more preferably.
  • any one selected from the group consisting of dimethyl ether, diethyl ether, dipropyl ether, methylethyl ether, methylpropyl ether and ethylpropyl ether, or a mixture of two or more thereof may be used.
  • the present invention is not limited thereto.
  • ester compounds in the organic solvent include linear esters such as methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate; And cyclic esters such as ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -valerolactone, and ⁇ -caprolactone, or a mixture of two or more thereof may be used.
  • the present invention is not limited thereto.
  • the secondary battery comprising a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode and a non-aqueous electrolyte
  • a lithium secondary battery comprising the electrolyte of the present invention as the electrolyte.
  • the lithium secondary battery of the present invention may be prepared by injecting the nonaqueous electrolyte of the present invention into an electrode structure 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 structure may be used all those conventionally used in the manufacture of a lithium secondary battery.
  • the positive electrode may be prepared by coating a positive electrode mixture including a positive electrode active material, a binder, a conductive material and a solvent on a positive electrode current collector.
  • 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 positive electrode active material is a compound capable of reversible intercalation and deintercalation of lithium, and may specifically include a lithium composite metal oxide containing lithium and one or more metals such as cobalt, manganese, nickel or aluminum. have. More specifically, the lithium composite metal oxide may be lithium-manganese oxides (eg, LiMnO 2 , LiMn 2 O 4, etc.), lithium-cobalt oxides (eg, LiCoO 2, etc.), lithium-nickel oxides, and the like.
  • the lithium composite metal oxide may be lithium-manganese oxides (eg, LiMnO 2 , LiMn 2 O 4, etc.), lithium-cobalt oxides (eg, LiCoO 2, etc.), lithium-nickel oxides, and the like.
  • lithium-nickel-manganese-based oxide for example, LiNi 1-Y Mn Y O 2 (where, 0 ⁇ Y ⁇ 1), LiMn 2-z Ni z O 4 ( here, 0 ⁇ Z ⁇ 2) and the like
  • lithium-nickel-cobalt oxide e.g., LiNi 1-Y1 Co Y1 O 2 (here, 0 ⁇ Y1 ⁇ 1) and the like
  • lithium-manganese-cobalt oxide e.
  • LiCoO 2 , LiMnO 2 , LiNiO 2 , and lithium nickel manganese cobalt oxides may be improved in capacity and stability of the battery.
  • Li (Ni 0.5 Mn 0.3 Co 0.2 ) O 2 Li (Ni 0.7 Mn 0.15 Co 0.15 ) O 2 or Li (Ni 0.8 Mn 0.1 Co 0.1 ) O 2, etc.), or lithium nickel cobalt aluminum oxide (eg, Li (Ni 0.8 Co 0.15 Al 0.05 ) O 2, etc.), and the lithium composite metal oxide may be Li (Ni) in consideration of the remarkable improvement effect by controlling the type and content ratio of the constituent elements forming the lithium composite metal oxide.
  • the cathode active material may be included in an amount of 80 wt% to 99 wt% based on the total weight of the cathode mixture.
  • the conductive material is typically added in an amount of 1 to 30% by weight based on the total weight of the positive electrode mixture.
  • Such a conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery, and examples thereof include graphite; Carbon-based materials such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black; 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. Specific examples of commercially available conductive materials include Chevron Chemical Company, Denka Singapore Private Limited, Gulf Oil Company, Ketjenblack and EC, which are acetylene black series. Family (Armak Company), Vulcan XC-72 (manufactured by Cabot Company) and Super P (manufactured by Timcal).
  • the binder is a component that assists in bonding the active material and the conductive material and bonding to the current collector, and is generally added in an amount of 1 to 30 wt% based on the total weight of the positive electrode mixture.
  • 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 negative electrode may be prepared by, for example, coating a negative electrode mixture including a negative electrode active material, a binder, a conductive material, a solvent, and the like on a negative electrode current collector.
  • 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 natural graphite, artificial graphite, carbonaceous material; Metals (Me) that are lithium-containing titanium composite oxide (LTO), Si, Sn, Li, Zn, Mg, Cd, Ce, Ni, or Fe; Alloys composed of the metals (Me); Oxides of the metals (Me) (MeOx); And one or two or more negative electrode active materials selected from the group consisting of a complex of the metals (Me) and carbon.
  • Metals (Me) that are lithium-containing titanium composite oxide (LTO), Si, Sn, Li, Zn, Mg, Cd, Ce, Ni, or Fe
  • Oxides of the metals (Me) (MeOx) Oxides of the metals (Me) (MeOx)
  • one or two or more negative electrode active materials selected from the group consisting of a complex of the metals (Me) and carbon.
  • the negative active material may be included in an amount of 80 wt% to 99 wt% based on the total weight of the negative electrode mixture.
  • the binder is a component that assists the bonding between the conductive material, the active material and the current collector, and is usually added in an amount of 1 to 30 wt% based on the total weight of the negative electrode mixture.
  • binders include polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoro Low ethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene-butadiene rubber, fluorine rubber, various copolymers thereof, and the like.
  • PVDF polyvinylidene fluoride
  • CMC carboxymethyl cellulose
  • EPDM ethylene-propylene-diene polymer
  • sulfonated-EPDM styrene-butadiene rubber
  • fluorine rubber
  • 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 the negative electrode mixture.
  • a conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery, and examples thereof include graphite such as natural graphite and artificial graphite; Carbon blacks such as acetylene black, Ketjen black, channel black, furnace black, lamp black and thermal black; 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 (N-methyl-2-pyrrolidone), 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 negative electrode active material and, optionally, the solid content including the binder and the conductive material may be 50 wt% to 95 wt%, preferably 70 wt% to 90 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.
  • Fluoroethylene carbonate (FEC), propylene carbonate (PC) and ethylene carbonate (EMC) were mixed in a ratio of 30:10:60 (vol%) to prepare an organic solvent mixture. Thereafter, 0.5 wt% of the compound of Chemical Formula 1a was further added based on the total content of the prepared organic solvent mixture, and LiPF 6 was dissolved to a concentration of 1 M to prepare a nonaqueous electrolyte.
  • NMP N-methyl-2-pyrrolidone
  • LiCO 2 lithium cobalt composite oxide
  • carbon black carbon black
  • PVDF polyvinylidene fluoride
  • the positive electrode mixture was prepared by adding 40 parts by weight of the positive electrode mixture mixed at a ratio of 5: 5 (wt%).
  • the positive electrode mixture was applied to a positive electrode current collector (Al thin film) having a thickness of 100 ⁇ m, dried, and roll pressed to prepare a positive electrode.
  • NMP N-methyl-2-pyrrolidone
  • natural graphite as a negative electrode active material
  • PVDF as a binder
  • carbon black as a conductive material at a ratio of 95: 2: 3 (wt%) 80 Part by weight was added to prepare a negative electrode mixture.
  • the negative electrode mixture was applied to a negative electrode current collector (Cu thin film) having a thickness of 90 ⁇ m, dried, and roll pressed to prepare a negative electrode.
  • the positive electrode and the negative electrode prepared by the above-described method was prepared with a polyethylene porous film by a conventional method, and then the non-aqueous electrolyte was prepared by pouring the lithium secondary battery.
  • an electrolyte solution and a battery including the same were prepared in the same manner as in Example 1 except that the compound of Formula 1b was used instead of the compound of Formula 1a as an additive.
  • an electrolyte solution and a battery including the same were prepared in the same manner as in Example 1 except that the compound of Formula 1c was used instead of the compound of Formula 1a as an additive.
  • an electrolyte solution and a battery including the same were prepared in the same manner as in Example 1 except that the compound of Formula 1d was used instead of the compound of Formula 1a as an additive.
  • an electrolyte solution and a battery including the same were prepared in the same manner as in Example 1 except that the compound of Formula 1e was used instead of the compound of Formula 1a as an additive.
  • an electrolyte solution and a battery including the same were prepared in the same manner as in Example 1 except that the compound of Formula 1f was used instead of the compound of Formula 1a as an additive.
  • an electrolyte and a battery including the same were prepared in the same manner as in Example 1, except that the additive contained the compound of Formula 1g instead of the compound of Formula 1a.
  • an electrolyte solution and a battery including the same were prepared in the same manner as in Example 1, except that the compound of Formula 1h was used instead of the compound of Formula 1a as an additive.
  • an electrolyte solution and a battery including the same were prepared in the same manner as in Example 1, except that 5 wt% of the compound of Formula 1a was used as an additive.
  • An electrolyte and a battery including the same were prepared in the same manner as in Example 1, except that the compound of Formula 1a was not added as an additive.
  • an electrolyte solution and a battery including the same were prepared in the same manner as in Example 1 except that the compound of Formula 2a was used instead of the compound of Formula 1a as an additive.
  • An electrolyte and a battery including the same were prepared in the same manner as in Example 1, except that 7 wt% of the compound of Formula 1a was added as an additive when preparing the non-aqueous electrolyte.
  • the batteries (battery capacity 5.5 mAh) prepared in Examples 1 to 9 and Comparative Examples 1 to 5 were charged at 60 ° C. to 0.7C constant current until 4.35V, and then charged at a constant voltage of 4.35V to charge current 0.275. Charging was terminated when mA reached. Then, it was left for 10 minutes and then discharged until it became 3.0V at 0.5C constant current. After 100 cycles of charging and discharging, the battery capacity was measured and shown in FIG. 1.
  • C represents the charge / discharge current rate and C-rate of the battery represented by ampere (A) and is usually expressed as a ratio of battery capacity. That is, 1C of the cells manufactured previously means 5.5 mA current.
  • the batteries of Examples 1 to 9 are superior in cycle life characteristics to those of the secondary batteries of 1 to 5 in comparison.
  • Example 1 1a 0.5 wt% 45
  • Example 2 1b 0.5 wt% 48
  • Example 3 1c 0.5 wt% 44
  • Example 4 1d 0.5 wt% 48
  • Example 5 1e 0.5 wt% 52
  • Example 6 1f 0.5 wt% 75
  • Example 7 1 g 0.5 wt% 63
  • Example 8 1h 0.5 wt% 57
  • Example 9 1a 5 wt% 55 Comparative Example 1 - - 255 Comparative Example 2 2a 0.5 wt% 208 Comparative Example 3 2b 0.5 wt% 190 Comparative Example 4 1a 7 wt% 144 Comparative Example 5 2c 0.5 wt% 131
  • Example 1 The lithium secondary batteries of Example 1, Example 9, and Comparative Example 4 were placed at 25 ° C. under SOC at 0% for 1 hour, and then the AC impedance of the battery was measured while scanning to 50 mHz-100 kHz. At this time, the amplitude of the alternating current was 10mV, and the DC potential of the battery was 3.74V. The results are shown in FIG.
  • the intersection point with the X-axis in the graph of Figure 2 means Ohm resistance of the battery
  • the half circle (half circle) at the rear means the resistance by the SEI formed on the surface of the electrode plate.
  • Comparative Example 4 which has a large amount of addition compared to Examples 1 and 9, has greatly increased resistance.
  • Comparative Example 4 the amount of Co eluted is large and the life is also reduced.

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Abstract

La présente invention concerne : un additif d'électrolyte non aqueux comprenant, en tant que substituant, un groupe cyano et au moins un élément fluoré ; un électrolyte non aqueux pour batterie secondaire au lithium le comprenant ; et une batterie secondaire au lithium le contenant.
PCT/KR2016/012093 2015-10-29 2016-10-26 Additif d'électrolyte non aqueux, électrolyte non aqueux le comprenant et batterie secondaire au lithium le contenant WO2017074027A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CN201680037297.6A CN108370068B (zh) 2015-10-29 2016-10-26 非水电解质添加剂、包括该非水电解质添加剂的非水电解质和包括该非水电解质的锂二次电池
EP16860210.0A EP3370296B1 (fr) 2015-10-29 2016-10-26 Additif d'électrolyte non aqueux, électrolyte non aqueux le comprenant et batterie secondaire au lithium contenant cet électrolyte non aqueux
US15/735,741 US10454138B2 (en) 2015-10-29 2016-10-26 Non-aqueous electrolyte additive, non-aqueous electrolyte comprising the same, and lithium secondary battery including non-aqueous electrolyte
PL16860210T PL3370296T3 (pl) 2015-10-29 2016-10-26 Dodatek do niewodnego elektrolitu, niewodny elektrolit go zawierający i akumulator litowy zawierający niewodny elektrolit
JP2018528930A JP6656717B2 (ja) 2015-10-29 2016-10-26 非水電解液添加剤、これを含む非水電解液、及びこれを備えたリチウム二次電池

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US20120171581A1 (en) * 2009-09-15 2012-07-05 Ube Industries, Ltd. Nonaqueous electrolyte solution and electrochemical element using same
KR20140037622A (ko) * 2012-09-19 2014-03-27 에스케이케미칼주식회사 이차 전지용 전해액 조성물 및 그 제조방법
KR20140067242A (ko) * 2012-11-26 2014-06-05 에스케이이노베이션 주식회사 리튬 이차전지용 전해액 및 이를 포함하는 리튬 이차전지

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JP2008179622A (ja) * 2006-12-25 2008-08-07 Nichicon Corp イオン性化合物
US20120171581A1 (en) * 2009-09-15 2012-07-05 Ube Industries, Ltd. Nonaqueous electrolyte solution and electrochemical element using same
KR20110119054A (ko) * 2010-04-26 2011-11-02 삼성에스디아이 주식회사 리튬 폴리머 전지
KR20140037622A (ko) * 2012-09-19 2014-03-27 에스케이케미칼주식회사 이차 전지용 전해액 조성물 및 그 제조방법
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