WO2019013501A1 - Additif de solution d'électrolyte non aqueux, solution d'électrolyte non aqueux destiné à une batterie secondaire au lithium, et batterie secondaire au lithium comprenant un additif de solution d'électrolyte non aqueux - Google Patents

Additif de solution d'électrolyte non aqueux, solution d'électrolyte non aqueux destiné à une batterie secondaire au lithium, et batterie secondaire au lithium comprenant un additif de solution d'électrolyte non aqueux Download PDF

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WO2019013501A1
WO2019013501A1 PCT/KR2018/007729 KR2018007729W WO2019013501A1 WO 2019013501 A1 WO2019013501 A1 WO 2019013501A1 KR 2018007729 W KR2018007729 W KR 2018007729W WO 2019013501 A1 WO2019013501 A1 WO 2019013501A1
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formula
group
aqueous electrolyte
carbon atoms
linear
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PCT/KR2018/007729
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English (en)
Korean (ko)
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김현승
유성훈
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주식회사 엘지화학
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Priority claimed from KR1020180077576A external-priority patent/KR102270869B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US16/340,269 priority Critical patent/US11081729B2/en
Priority to PL18832898T priority patent/PL3518334T3/pl
Priority to CN201880024734.XA priority patent/CN110574210B/zh
Priority to EP18832898.3A priority patent/EP3518334B1/fr
Publication of WO2019013501A1 publication Critical patent/WO2019013501A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • 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 solution for a lithium secondary battery comprising the same, and a lithium secondary battery.
  • the technology based on the secondary battery is the most suitable technology for various applications and can be applied to individual IT devices such as miniaturization and may be applied to large devices such as power storage devices.
  • Lithium-ion batteries which are theoretically the most energy-dense battery system among the secondary battery technologies, are in the spotlight.
  • a lithium ion battery unlike in the early days when a lithium metal was directly applied to a system, it is composed of a positive electrode made of a transition metal oxide containing lithium, a negative electrode capable of storing lithium, an electrolyte, and a separator.
  • the energy is stored through the redox reaction of the transition metal, which means that the transition metal must be essentially included in the anode material.
  • the first is observed when the passivation ability of the coating formed on the anode / cathode surface after the activation process is lowered.
  • the electrode materials of the lithium ion battery use a graphite anode in the case of a cathode, but the operating potential of the graphite is 0.3 V ( vs. Li / Li + ) or less. Because it is lower than the chemical stability window, the electrolyte is first reduced and decomposed. The thus-decomposed electrolytic solution product forms a solid electrolyte interphase (SEI) film that transmits lithium ions but inhibits further decomposition of the electrolyte solution.
  • SEI solid electrolyte interphase
  • the second is when metal impurities are included in the initial electrode slurry preparation.
  • a positive electrode of a lithium ion battery is manufactured by coating a slurry containing a conductive material and a binder together with an electrode active material on a current collector such as aluminum.
  • a current collector such as aluminum.
  • the metal such as iron or copper
  • the powder can be contained in the electrode manufacturing without being removed.
  • the third occurs when the transition metals from the anode are easily eluted into the electrolyte.
  • the transition metals constituting the anode can be easily eluted into the electrolyte due to HF produced in the electrolyte, or formation of an unstable structure due to charging / discharging of the anode.
  • the thus eluted transition metal ions are re-deposited on the anode It is possible to increase the resistance of the anode or, conversely, to move to the cathode through the electrolyte and then electrodeposition to the cathode to self-discharge the cathode, thereby destroying the SEI film which gives the passive ability to the cathode, And it is known as a factor to increase the interfacial resistance of the cathode.
  • Such elution of the transition metal and insufficient passivation ability of the SEI film causes not only the activation step but also deterioration due to the transition metal ion species eluted from the anode at high temperature charge / discharge or high temperature storage.
  • the present invention also provides a nonaqueous electrolyte solution for a lithium secondary battery comprising the nonaqueous electrolyte additive.
  • the present invention also provides a lithium secondary battery comprising the non-aqueous electrolyte for the lithium secondary battery.
  • R 1 and R 2 are each independently a linear or non-linear alkyl group having 1 to 5 carbon atoms; and R 3 is a linear or non-linear alkylene group having 1 to 3 carbon atoms.
  • R 4 is a linear or non-linear alkylene group having 1 to 3 carbon atoms
  • A is a substituted or unsubstituted heteroaryl group having 3 to 6 carbon atoms containing at least one of oxygen and nitrogen atoms or a substituted or unsubstituted heteroaryl group having 3 to 6 carbon atoms containing at least one of oxygen and nitrogen A cyclic group,
  • R 5 is hydrogen, an alkyl group having 1 to 3 carbon atoms, oxygen ( ⁇ O), -CN and , Wherein R is a linear or non-linear alkylene group having 1 to 3 carbon atoms,
  • n is an integer of 1 to 6
  • each R 5 may be the same or different from each other.
  • the compound represented by Formula 1 may be at least one selected from the group consisting of compounds represented by Chemical Formulas 1a to 1c.
  • the compound represented by Formula 2 may be at least one selected from the group consisting of compounds represented by Chemical Formulas 2a to 2c.
  • R 6 is a linear or non-linear alkylene group having 1 to 3 carbon atoms
  • R 7 to R 10 are each independently at least one selected from the group consisting of hydrogen, an alkyl group having 1 to 3 carbon atoms, and -CN,
  • R ' is a linear or non-linear alkylene group having 1 to 3 carbon atoms.
  • R 11 is a linear or non-linear alkylene group having 1 to 3 carbon atoms
  • R 12 to R 15 are each independently at least one selected from the group consisting of hydrogen, an alkyl group having 1 to 3 carbon atoms, and -CN.
  • R 16 is a linear or non-linear alkylene group having 1 to 3 carbon atoms
  • R 17 to R 19 are each independently at least one selected from the group consisting of hydrogen, an alkyl group having 1 to 3 carbon atoms and -CN,
  • D is CH, or N
  • the compound represented by Formula 2 may be at least one selected from the group consisting of compounds represented by Formula 2b and 2c, and more specifically, a compound represented by Formula 2c.
  • the compound represented by the formula (2a) may be at least one selected from the group consisting of compounds represented by the following formulas (2a-1) to (2a-7).
  • the compound represented by Formula 2b may be a compound represented by Formula 2b-1.
  • the compound represented by Formula 2c may be a compound represented by Formula 2c-1.
  • Nonaqueous electrolyte additive is at least one compound selected from the group consisting of the compounds represented by the formulas (1) and (2), wherein the nonaqueous electrolyte solution is a nonaqueous electrolyte solution for a lithium secondary battery.
  • the non-aqueous electrolyte additive may be included in an amount of 0.05 wt% to 5 wt%, specifically 0.5 wt% to 3 wt% based on the total amount of the non-aqueous electrolyte.
  • the positive electrode comprises at least one positive electrode active material selected from the group consisting of lithium-nickel-manganese-cobalt oxide and lithium-manganese oxide,
  • non-aqueous electrolyte is a non-aqueous electrolyte for the lithium secondary battery of the present invention.
  • the cathode active material may include a lithium-manganese-based oxide, and the lithium-manganese-based oxide may be LiMn 2 O 4 .
  • a Lewis base-based compound containing a nitrogen element and a propargyl group as a non-aqueous electrolyte additive to improve the low-voltage phenomenon of a lithium ion battery
  • Lewis acid can be removed and a more stable SEI film can be formed on the surfaces of the cathode and the anode, so that the elution of the transition metal from the anode can be suppressed due to the decomposition product of the lithium salt.
  • the nonaqueous electrolyte solution containing the nonaqueous electrolyte solution it is possible to manufacture a lithium secondary battery in which defective low voltage is improved and leakage of transition metal in the positive electrode is suppressed.
  • Example 1 is a graph showing a change in voltage of a coin half cell according to time in Experimental Example 1 of the present invention.
  • the present invention has an excellent adsorption effect with metal impurities, To provide an additive that can be reinforced.
  • the SEI film which is the cathode coating can be strengthened by containing the triple bond, and the metal leaching can be inhibited by being adsorbed on the metal foreign matter.
  • non-aqueous electrolyte additive of the present invention since it has a functional group containing a nitrogen element which is a Lewis base function, decomposition products such as HF and PF 5 formed due to decomposition of the lithium salt can be removed.
  • the present invention provides a non-aqueous electrolyte and a lithium secondary battery which can improve low voltage defects by including the non-aqueous electrolyte additive.
  • R 1 and R 2 are each independently a linear or non-linear alkyl group having 1 to 5 carbon atoms; and R 3 is a linear or non-linear alkylene group having 1 to 3 carbon atoms.
  • R 4 is a linear or non-linear alkylene group having 1 to 3 carbon atoms
  • A is a substituted or unsubstituted heteroaryl group having 3 to 6 carbon atoms containing at least one of oxygen and nitrogen atoms or a substituted or unsubstituted heteroaryl group having 3 to 6 carbon atoms containing at least one of oxygen and nitrogen A cyclic group,
  • R 5 is hydrogen, an alkyl group having 1 to 3 carbon atoms, oxygen ( ⁇ O), -CN and , Wherein R is a linear or non-linear alkylene group having 1 to 3 carbon atoms,
  • n is an integer of 1 to 6
  • each R 5 may be the same or different from each other.
  • the compounds represented by Chemical Formulas 1 and 2 contain a functional group functioning as a Lewis base containing a nitrogen element in the structure. Therefore, decomposition of anions such as PF 6 - of a lithium salt can not be inhibited,
  • the Lewis acid such as HF and PF 5 which are decomposition products to be produced can be removed from the inside of the electrolytic solution and thus the deterioration behavior due to the chemical reaction of the surface coating of the anode or the cathode due to such Lewis acid can be suppressed.
  • deterioration of the coating film can be suppressed and further decomposition of the electrolyte in the battery due to destruction of the coating film can be prevented, so that the self-discharge of the battery can be prevented finally.
  • the compounds represented by Chemical Formulas 1 and 2 have a prophylactic functional group in the structure, it is possible to improve the high temperature durability of the cathode itself by forming a SEI film having high passivation ability on the surface of the cathode, In addition, it is possible to reduce the amount of the transition metal electrodeposited on the cathode itself.
  • the prophage may adsorb on the surface of the metallic impurities contained in the anode to make the elution of the impurities difficult, and the internal short-circuit that may occur due to the precipitation of the eluted metal ions on the anode .
  • the prophage is easy to be reduced on the surface of the anode, it is possible to form a stable film on the surface of the anode. Therefore, it is possible to use a graphite system due to the additional reduction decomposition reaction of the electrolyte caused by the instability of the SEI film, Can be prevented.
  • the nonaqueous electrolyte additive containing the compound represented by the general formulas (1) and (2) of the present invention can be adsorbed on the metal surface to inhibit the metal from leaching into ions, Since the SEI film can be formed stably and breakdown of the positive / negative electrode coating due to decomposition of the lithium salt can be prevented, the self-discharge reaction of the battery can be suppressed and the low voltage failure of the lithium ion battery can be improved have.
  • the compound represented by Formula 1 may be at least one selected from the group consisting of compounds represented by Chemical Formulas 1a to 1c.
  • the compound represented by Formula 2 may be at least one selected from the group consisting of compounds represented by Chemical Formulas 2a to 2c.
  • R 6 is a linear or non-linear alkylene group having 1 to 3 carbon atoms
  • R 7 to R 10 are each independently at least one selected from the group consisting of hydrogen, an alkyl group having 1 to 3 carbon atoms, and -CN,
  • R ' is a linear or non-linear alkylene group having 1 to 3 carbon atoms.
  • R 11 is a linear or non-linear alkylene group having 1 to 3 carbon atoms
  • R 12 to R 15 are each independently at least one selected from the group consisting of hydrogen, an alkyl group having 1 to 3 carbon atoms, and -CN.
  • R 16 is a linear or non-linear alkylene group having 1 to 3 carbon atoms
  • R 17 to R 19 are each independently at least one selected from the group consisting of hydrogen, an alkyl group having 1 to 3 carbon atoms and -CN,
  • D is CH, or N
  • the non-aqueous electrolyte additive of the present invention is characterized in that the compound represented by the general formula (2b) or (2c), particularly the compound represented by the general formula (2c)
  • the Lewis acid which is the decomposition product of the lithium salt, can be effectively removed by the imidazole functional group.
  • the compound represented by the formula (2) may be at least one selected from the group consisting of compounds represented by the following formulas (2a-1) to (2a-7).
  • the compound represented by Formula 2b may be a compound represented by Formula 2b-1.
  • the compound represented by Formula 2c may be a compound represented by Formula 2c-1.
  • a nonaqueous electrolyte solution for a lithium secondary battery comprising a nonaqueous electrolyte additive
  • non-aqueous electrolyte additive is at least one compound selected from the group consisting of the compounds represented by the formulas (1) and (2).
  • the compounds represented by the formulas (1) and (2) may be contained in an amount of 0.05 wt% to 5 wt%, specifically 0.5 wt% to 3 wt%, more specifically 0.8 wt% to 1.2 wt% have.
  • a secondary battery having improved performance can be manufactured.
  • the content of the additive is within the range of 0.05 wt% to 5 wt%, the effect of stabilizing the SEI film and the effect of inhibiting metal dissolution are excellent, and the effect of controlling the resistance of the coating due to decomposition of the additive is excellent.
  • the lithium salt contained as an electrolyte may be any of those conventionally used in an electrolyte for a lithium secondary battery, and examples thereof include Li + as a cation of the lithium salt, is F -, Cl -, Br - , I -, NO 3 -, N (CN) 2 -, BF 4 -, ClO 4 -, AlO 4 -, BF 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 -
  • the organic solvent may be any one that minimizes degradation due to an oxidation reaction or the like during charging and discharging of the secondary battery, none.
  • an ether solvent, an ester solvent or an amide solvent may be used alone or in combination of two or more.
  • any one selected from the group consisting of dimethyl ether, diethyl ether, dipropyl ether, methyl ethyl ether, methyl propyl ether and ethyl propyl ether, or a mixture of two or more thereof may be used , But is not limited thereto.
  • the ester solvent may include at least one compound selected from the group consisting of a cyclic carbonate compound, a linear carbonate compound, a linear ester compound, and a cyclic ester compound.
  • 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), or a mixture of two or more thereof.
  • EC ethylene carbonate
  • PC propylene carbonate
  • 1,2-butylene carbonate 2,3-butylene carbonate
  • 1,2-pentylene carbonate 2,3-pentylene carbonate
  • vinylene carbonate and fluoroethylene carbonate (FEC)
  • FEC fluoroethylene carbonate
  • linear carbonate compound examples include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, ethyl methyl carbonate (EMC), methyl propyl carbonate and ethyl propyl carbonate , Or a mixture of two or more thereof, but the present invention is not limited thereto.
  • linear ester compound examples include any one selected from the group consisting of methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, and butyl propionate, And mixtures thereof, but the present invention is not limited thereto.
  • cyclic ester compound examples include any one selected from the group consisting of? -Butyrolactone,? -Valerolactone,? -Caprolactone,? -Valerolactone and? -Caprolactone, or two or more Mixtures may be used, but are not limited thereto.
  • the cyclic carbonate-based compound in the ester-based solvent is a highly viscous organic solvent having a high dielectric constant and can dissociate the lithium salt in the electrolyte well.
  • the cyclic carbonate-based compound has a low viscosity such as dimethyl carbonate and diethyl carbonate,
  • the dielectric constant linear carbonate compound and the linear ester compound are mixed in an appropriate ratio, an electrolyte having a high electric conductivity can be prepared, and thus it can be more preferably used.
  • the non-aqueous electrolyte of the present invention may further comprise an additive for forming an SEI film, if necessary.
  • an additive for forming the SEI film examples include silicone-based compounds including vinyl groups, vinylene carbonate, vinylethylene carbonate, fluoroethylene carbonate, vinylethylene carbonate, cyclic sulfite, saturated sulphone, unsaturated sulphone, They may be used alone or in combination of two or more.
  • cyclic sulfite examples include ethylene sulfite, methyl ethylene sulfite, ethyl ethylene sulfite, 4,5-dimethyl ethylene sulfite, 4,5-diethyl ethylene sulfite, propylene sulfite, 4,5-dimethyl Propylene sulfite, 4,5-diethylpropylene sulfite, 4,6-dimethylpropylene sulfite, 4,6-diethylpropylene sulfite, and 1,3-butylene glycol sulfite. 1,3-propane sultone, 1,4-butane sultone, and the like.
  • Unsaturated sulphones include ethene sultone, 1,3-propenesultone, 1,4-butene sultone, -Propenesultone, and the non-cyclic sulfone includes divinyl sulfone, dimethyl sulfone, diethyl sulfone, methyl ethyl sulfone, and methyl vinyl sulfone.
  • a 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
  • non-aqueous electrolyte solution for a lithium secondary battery of the present invention as the non-aqueous electrolyte.
  • the lithium secondary battery of the present invention can be manufactured by injecting the non-aqueous electrolyte of the present invention into an electrode assembly in which a cathode, a cathode, and a separation membrane interposed between the anode and the cathode are sequentially laminated.
  • the positive electrode, negative electrode, and separator forming the electrode assembly may be those conventionally used in the manufacture of the lithium secondary battery.
  • the positive electrode and the negative electrode constituting the lithium secondary battery of the present invention can be manufactured and used by a conventional method.
  • the positive electrode may be manufactured by forming a positive electrode mixture layer on the positive electrode current collector.
  • the positive electrode mixture layer may be formed by coating a positive electrode slurry containing a positive electrode active material, a binder, a conductive material and a solvent on a positive electrode collector, followed by drying and rolling.
  • the positive electrode collector is not particularly limited as long as it has electrical conductivity without causing chemical change in the battery.
  • the positive electrode collector may be formed of a metal such as carbon, stainless steel, aluminum, nickel, titanium, sintered carbon, , Nickel, titanium, silver, or the like may be used.
  • a lithium-transition metal oxide including lithium and at least one metal selected from cobalt, manganese, nickel, or aluminum Specifically, a lithium-nickel-manganese-cobalt oxide (for example, Li (Ni p Co q Mn r1 ) O 2 (where 0 ⁇ p
  • the lithium-nickel-manganese-cobalt-based oxide includes Li (Ni 1/3 Mn 1/3 Co 1/3 ) O 2 , Li (Ni 0.6 Mn 0.2 Co 0.2 ) O 2 , Li (Ni 0.5 Mn 0.3 Co 0.2 ) O 2, Li (Ni 0.7 Mn 0.15 Co 0.15) O 2 and Li (Ni 0.8 Mn 0.1 Co 0.1 ) O may be mentioned 2, wherein the lithium-manganese-based oxide is LiMn 2 O 4 .
  • a lithium-manganese-based oxide having a high Mn content which is a lithium-nickel-manganese-cobalt oxide and a lithium-manganese-based oxide, particularly, a transition metal is eluted from the active material and the transition metal is electrodeposited It is possible to realize a better metal dissolution inhibiting effect.
  • the positive electrode active material of the present invention may contain, in addition to the lithium-manganese-based oxide, a lithium-cobalt oxide (such as LiCoO 2 ), a lithium-nickel oxide (such as LiNiO 2 ) oxide (e.
  • 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.g., LiCo 1-Y2 Mn Y2 O 2 (herein, 0 ⁇ Y2 ⁇ 1), LiMn 2-z1 Co z1 O 4 ( here, 0 ⁇ z1 ⁇ 2) and the like
  • the cathode active material may be contained in an amount of 80% by weight to 99% by weight based on the total weight of solids in the cathode slurry.
  • the binder is a component that assists in bonding of the active material to the conductive material and bonding to the current collector, and is usually added in an amount of 1 to 30 wt% based on the total weight of the solid content in the positive electrode slurry.
  • binders include polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene (Ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene-butadiene rubber, fluorine rubber, various copolymers and the like.
  • PVDF polyvinylidene fluoride
  • CMC carboxymethylcellulose
  • EPDM tetrafluoroethylene
  • EPDM tetrafluoroethylene
  • EPDM sulfonated EPDM
  • the conductive material is usually added in an amount of 1 to 30% by weight based on the total weight of the solid content in the positive electrode slurry.
  • Such a conductive material is not particularly limited as long as it has electrical conductivity without causing chemical changes in the battery, and examples thereof include carbon black, acetylene black (or denka black), Ketjenblack, channel black, furnace black, Carbon black such as lamp black or thermal black; Graphite powder such as natural graphite, artificial graphite, or graphite with a highly developed crystal structure; Conductive fibers such as carbon fiber and metal fiber; Metal powders such as carbon fluoride, aluminum, and nickel powder; Conductive whiskers 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 N-methyl-2-pyrrolidone (NMP), and may be used in an amount that provides a preferable viscosity when the positive electrode active material and optionally a binder and a conductive material are included.
  • NMP N-methyl-2-pyrrolidone
  • the solid content in the slurry containing the positive electrode active material, and optionally the binder and the conductive material may be in the range of 50 wt% to 95 wt%, preferably 70 wt% to 90 wt%.
  • the negative electrode may be manufactured by forming a negative electrode mixture layer on the negative electrode collector.
  • the negative electrode material mixture layer may be formed by coating a negative electrode current collector with a slurry containing a negative electrode active material, a binder, a conductive material, a solvent, and the like, followed by drying and rolling.
  • the anode current collector generally has a thickness of 3 to 500 mu m.
  • the negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery.
  • Examples of the negative electrode current collector include copper, stainless steel, aluminum, nickel, titanium, sintered carbon, copper or stainless steel Surface-treated with carbon, nickel, titanium, silver or the like, aluminum-cadmium alloy, or the like can be used.
  • fine unevenness can be formed on the surface to enhance the bonding force of the negative electrode active material, and it can be used in various forms such as films, sheets, foils, nets, porous bodies, foams and nonwoven fabrics.
  • the negative electrode active material may be a lithium metal, a carbon material capable of reversibly intercalating / deintercalating lithium ions, a metal or an alloy of these metals and lithium, a metal complex oxide, lithium capable of doping and dedoping lithium Materials, and transition metal oxides.
  • the carbonaceous material capable of reversibly intercalating / deintercalating lithium ions is not particularly limited as long as it is a carbonaceous anode active material generally used in a lithium ion secondary battery.
  • the carbonaceous material include crystalline carbon, Amorphous carbon or any combination thereof.
  • the crystalline carbon include graphite such as natural graphite or artificial graphite in the form of amorphous, plate-like, flake, spherical or fiber, and examples of the amorphous carbon include soft carbon (soft carbon) Or hard carbon, mesophase pitch carbide, fired coke, and the like.
  • the metal or an alloy of these metals and lithium may be selected from the group consisting of Cu, Ni, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, And Sn, or an alloy of these metals and lithium may be used.
  • metal composite oxide is PbO, PbO 2, Pb 2 O 3, Pb 3 O 4, Sb 2 O 3, Sb 2 O 4, Sb 2 O 5, GeO, GeO 2, Bi 2 O 3, Bi 2 O 4 , Bi 2 O 5 , Li x Fe 2 O 3 (0? X? 1), Li x WO 2 (0? X? 1), and Sn x Me 1-x Me y y z , Pb, Ge, Me ': Al, B, P, Si, Group 1, Group 2, Group 3 elements of the periodic table, Halogen: 0 ⁇ x? 1; 1? Y? May be used.
  • Si As the material capable of doping and dedoping lithium, Si, SiO x (0 ⁇ x? 2), Si-Y alloy (Y is an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, Rare earth elements and combinations thereof, but not Si), Sn, SnO 2 , Sn-Y (wherein Y is at least one element selected from the group consisting of alkali metals, alkaline earth metals, Group 13 elements, Group 14 elements, Element and an element selected from the group consisting of combinations thereof, and not Sn), and at least one of them may be mixed with SiO 2 .
  • Si-Y alloy Y is an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, Rare earth elements and combinations thereof, but not Si
  • Sn, SnO 2 Sn-Y (wherein Y is at least one element selected from the group consisting of alkali metals, alkaline earth metals, Group 13 elements, Group 14 elements, Element
  • the element Y may be at least one element selected from the group consisting of Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Se, Te, Po, and combinations thereof.
  • transition metal oxide examples include lithium-containing titanium composite oxide (LTO), vanadium oxide, lithium vanadium oxide, and the like.
  • the negative active material may be contained in an amount of 80% by weight to 99% by weight based on the total weight of the solid content in the negative electrode slurry.
  • the binder is a component that assists in bonding between the conductive material, the active material and the current collector, and is usually added in an amount of 1 to 30% by weight based on the total weight of the solid content in the negative electrode slurry.
  • binders include polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • CMC carboxymethylcellulose
  • EPDM ethylene-propylene-diene polymer
  • sulfonated-EPDM styrene-butadiene rubber
  • fluorine rubber various copolymers thereof.
  • 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 solid content in the negative electrode slurry.
  • Such a conductive material is not particularly limited as long as it has electrical conductivity without causing chemical changes in the battery.
  • the solvent may include water or an organic solvent such as NMP, alcohol, etc., and may be used in an amount in which the negative electrode active material and, optionally, a binder, a conductive material, and the like are contained in a desired viscosity.
  • the slurry containing the negative electrode active material and, optionally, the binder and the conductive material may be contained to have a solid concentration of 50 wt% to 95 wt%, preferably 70 wt% to 90 wt%.
  • the separation membrane blocks the internal short circuit of both electrodes and impregnates the electrolyte.
  • the separation membrane composition is prepared by mixing a polymer resin, a filler and a solvent, and then the separation membrane composition is directly coated on the electrode and dried Or may be formed by casting and drying the separation membrane composition on a support, and then laminating the separation membrane film peeled off from the support on the electrode.
  • the separator may be a porous polymer film commonly used, such as a porous polymer film made of a polyolefin-based polymer such as an ethylene homopolymer, a propylene homopolymer, an ethylene / butene copolymer, an ethylene / hexene copolymer, and an ethylene / methacrylate copolymer
  • the polymer film may be used alone or as a laminate thereof, or may be a nonwoven fabric made of a conventional porous nonwoven fabric, for example, glass fiber of high melting point, polyethylene terephthalate fiber or the like, but is not limited thereto.
  • the pore diameter of the porous separation membrane is generally 0.01 to 50 ⁇ m, and the porosity may be 5 to 95%.
  • the thickness of the porous separator may be generally in the range of 5 to 300 mu m.
  • the external shape of the lithium secondary battery of the present invention is not particularly limited, but may be a cylindrical shape, a square shape, a pouch shape, a coin shape, or the like using a can.
  • a Li half cell using Li metal as a positive electrode and a negative electrode containing impurities prepared by the above-mentioned method was prepared, and then a coin half cell was manufactured using a porous polyethylene separator.
  • a nonaqueous electrolytic solution and a coin half cell comprising the nonaqueous electrolytic solution were prepared in the same manner as in Example 1, except that 0.04 g of the compound of the formula (2c-1) was added to 4.96 g of the organic solvent during the preparation of the nonaqueous electrolyte solution.
  • a nonaqueous electrolytic solution and a coin half cell comprising the same were prepared in the same manner as in Example 1, except that 0.006 g of the compound of the formula (2c-1) was added to 4.94 g of the organic solvent in the preparation of the nonaqueous electrolyte.
  • a nonaqueous electrolytic solution and a coin half cell comprising the nonaqueous electrolytic solution were prepared in the same manner as in Example 1 except that the additive was not included in the preparation of the nonaqueous electrolyte (see Table 1 below).
  • a nonaqueous electrolytic solution and a coin half cell comprising the nonaqueous electrolytic solution were prepared in the same manner as in Example 1 except that the nonaqueous electrolytic solution additive was used as a nonaqueous electrolyte additive in the preparation of the nonaqueous electrolytic solution (see Table 1 below).
  • a nonaqueous electrolytic solution and a coin half cell comprising the nonaqueous electrolytic solution were prepared in the same manner as in Example 1 except that the nonaqueous electrolytic solution additive was used as a nonaqueous electrolyte additive in the preparation of the nonaqueous electrolytic solution (see Table 1 below).
  • a nonaqueous electrolytic solution and a coin half including the same were prepared in the same manner as in Example 1, except that the nonaqueous electrolytic solution additive used in the preparation of the nonaqueous electrolyte solution was a lithium salt compound, lithium oxalyldifluoroborate (LiODFB) (See Table 1 below).
  • LiODFB lithium oxalyldifluoroborate
  • a nonaqueous electrolytic solution and a coin half cell containing the same were prepared in the same manner as in Example 1 except that succinonitrile (SN) was included as a nonaqueous electrolyte additive in the preparation of the nonaqueous electrolyte (see Table 1 below) .
  • succinonitrile SN
  • Example Lithium salt Organic solvent additive Configuration Addition amount (g) The Addition amount (g) (wt%)
  • Example 3 4.94 2c-1 0.06 1.2 Comparative Example 1 5 - - - Comparative Example 2 4.95 3 0.05 One Comparative Example 3 4.95 4 0.05 One Comparative Example 4 4.95 LiODFB 0.05 One Comparative Example 5 4.95 SN 0.05
  • LiODFB lithium oxalyldifluoroborate SN: succinonitrile
  • the coin half cell manufactured in Example 1 and the coin half cell manufactured in Comparative Example 1 were each prepared in a dry room and then allowed to stand in a 25 ° C thermostat for 24 hours and then subjected to 0.1 C CC- The change in the voltage of the coin half cell with time was measured while proceeding in the voltage range of 4.25 V ( vs. Li / Li + ). At this time, the CV current termination condition was set at 0.05 C.
  • the coin half cell of Example 1 contains a compound containing a nitrogen atom and a propargyl group in a non-aqueous electrolyte as an additive, it is adsorbed by metallic impurities to prevent elution of impurities, the acid is removed and the resin phase is prevented from being formed on the surface of the negative electrode, so that internal short-circuit is hardly generated. Therefore, it can be seen that a graph can be confirmed that normal charging / discharging is proceeding normally as shown in Fig.
  • LiMn 2 O 4 LiMn 2 O 4
  • carbon black as a conductive material
  • PVDF polyvinylidene fluoride
  • the resultant was applied to a current collector (Al foil), dried, and subjected to a roll press to produce a positive electrode.
  • the positive electrode was charged into the non-aqueous electrolyte prepared in Example 1 and each of the non-aqueous electrolytes (5 mL) prepared in Comparative Example 1, Comparative Example 4 and Comparative Example 5, After storing the electrode, the concentration of metal (Mn) dissolved in the electrolyte was measured using an inductively coupled plasma optical emission spectrometer ( ICP- OES). The amount of metal measured by ICP analysis 2 is shown in FIG.

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Abstract

La présente invention concerne un additif de solution d'électrolyte non aqueux, une solution d'électrolyte non aqueux destinée à une batterie au lithium-ion, et une batterie au lithium-ion comprenant l'additif de solution d'électrolyte non aqueux. Plus particulièrement, l'invention porte sur une solution d'électrolyte non aqueux dans laquelle un composé à base d'une base nucléophile comprenant un groupe propargyle est appliqué en tant qu'additif de solution d'électrolyte non aqueux destiné à une batterie au lithium-ion, et qui permet de supprimer l'élution d'impuretés métalliques qui engendrent des défauts dans une batterie et d'éliminer l'acide généré par la décomposition de sels de lithium, et une batterie secondaire au lithium dans laquelle une élution de métal de transition dans une anode et des phénomènes de basse tension sont améliorés à l'aide de l'additif de solution d'électrolyte non aqueux destiné à la batterie au lithium-ion.
PCT/KR2018/007729 2017-07-14 2018-07-06 Additif de solution d'électrolyte non aqueux, solution d'électrolyte non aqueux destiné à une batterie secondaire au lithium, et batterie secondaire au lithium comprenant un additif de solution d'électrolyte non aqueux WO2019013501A1 (fr)

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Application Number Priority Date Filing Date Title
US16/340,269 US11081729B2 (en) 2017-07-14 2018-07-06 Non-aqueous electrolyte solution additive, and non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery which include the same
PL18832898T PL3518334T3 (pl) 2017-07-14 2018-07-06 Dodatek do niewodnego roztworu elektrolitu, niewodny roztwór elektrolitu dla akumulatora litowego i akumulator litowy zawierający wspomniany dodatek
CN201880024734.XA CN110574210B (zh) 2017-07-14 2018-07-06 非水电解质溶液添加剂和包括该添加剂的用于锂二次电池的非水电解质溶液及锂二次电池
EP18832898.3A EP3518334B1 (fr) 2017-07-14 2018-07-06 Additif pour solution d'électrolyte non-aqueux, solution d'électrolyte non-aqueux destiné à une batterie secondaire au lithium, et batterie secondaire au lithium comprenant cet additif

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KR20170089773 2017-07-14
KR10-2017-0089773 2017-07-14
KR10-2018-0077576 2018-07-04
KR1020180077576A KR102270869B1 (ko) 2017-07-14 2018-07-04 비수전해액 첨가제, 이를 포함하는 리튬 이차전지용 비수전해액 및 리튬 이차전지

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WO2020153791A1 (fr) * 2019-01-25 2020-07-30 주식회사 엘지화학 Électrolyte pour batterie secondaire au lithium et batterie secondaire au lithium le comprenant
CN113711415A (zh) * 2019-08-21 2021-11-26 株式会社Lg新能源 锂二次电池用非水性电解液和包含它的锂二次电池
CN113728484A (zh) * 2019-01-25 2021-11-30 株式会社Lg新能源 锂二次电池用电解质和包含该电解质的锂二次电池
EP3913719A4 (fr) * 2019-02-28 2022-03-23 Lg Energy Solution, Ltd. Électrolyte pour accumulateur au lithium et accumulateur au lithium le comprenant
CN114976241A (zh) * 2022-05-18 2022-08-30 湖南大学 一种七氟丁酰咪唑作为添加剂的电解液及其锂离子电池
US20230098167A1 (en) * 2020-10-27 2023-03-30 Lg Energy Solution, Ltd. Non-Aqueous Electrolyte Solution for Lithium Secondary Battery and Lithium Secondary Battery Including the Same
KR20230127728A (ko) 2022-02-25 2023-09-01 주식회사 켐얼라이언스 이차전지용 전해질 및 이를 포함하는 이차전지

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US20140308564A1 (en) * 2013-04-10 2014-10-16 Samsung Sdi Co., Ltd. Rechargeable lithium battery and method of fabricating the same
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WO2020153791A1 (fr) * 2019-01-25 2020-07-30 주식회사 엘지화학 Électrolyte pour batterie secondaire au lithium et batterie secondaire au lithium le comprenant
CN113728484A (zh) * 2019-01-25 2021-11-30 株式会社Lg新能源 锂二次电池用电解质和包含该电解质的锂二次电池
JP2022517684A (ja) * 2019-01-25 2022-03-09 エルジー エナジー ソリューション リミテッド リチウム二次電池用電解質およびこれを含むリチウム二次電池
JP7154677B2 (ja) 2019-01-25 2022-10-18 エルジー エナジー ソリューション リミテッド リチウム二次電池用電解質およびこれを含むリチウム二次電池
EP3913719A4 (fr) * 2019-02-28 2022-03-23 Lg Energy Solution, Ltd. Électrolyte pour accumulateur au lithium et accumulateur au lithium le comprenant
JP2022521585A (ja) * 2019-02-28 2022-04-11 エルジー エナジー ソリューション リミテッド リチウム二次電池用電解質及びこれを含むリチウム二次電池
JP7233801B2 (ja) 2019-02-28 2023-03-07 エルジー エナジー ソリューション リミテッド リチウム二次電池用電解質及びこれを含むリチウム二次電池
CN113711415A (zh) * 2019-08-21 2021-11-26 株式会社Lg新能源 锂二次电池用非水性电解液和包含它的锂二次电池
EP3944392A4 (fr) * 2019-08-21 2022-07-20 LG Energy Solution, Ltd. Électrolyte non aqueux pour batterie rechargeable au lithium et batterie rechargeable au lithium comprenant celui-ci
US20230098167A1 (en) * 2020-10-27 2023-03-30 Lg Energy Solution, Ltd. Non-Aqueous Electrolyte Solution for Lithium Secondary Battery and Lithium Secondary Battery Including the Same
KR20230127728A (ko) 2022-02-25 2023-09-01 주식회사 켐얼라이언스 이차전지용 전해질 및 이를 포함하는 이차전지
CN114976241A (zh) * 2022-05-18 2022-08-30 湖南大学 一种七氟丁酰咪唑作为添加剂的电解液及其锂离子电池

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