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WO2018131954A1 - Électrolyte non aqueux et batterie secondaire au lithium le comprenant - Google Patents

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

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Publication number
WO2018131954A1
WO2018131954A1 PCT/KR2018/000648 KR2018000648W WO2018131954A1 WO 2018131954 A1 WO2018131954 A1 WO 2018131954A1 KR 2018000648 W KR2018000648 W KR 2018000648W WO 2018131954 A1 WO2018131954 A1 WO 2018131954A1
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Prior art keywords
formula
secondary battery
lithium
group
carbon atoms
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PCT/KR2018/000648
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English (en)
Korean (ko)
Inventor
유성훈
이경미
김슬기
이현영
강유선
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LG Chem Ltd
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LG Chem Ltd
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Priority to PL18738577T priority Critical patent/PL3407414T3/pl
Priority to CN201880001276.8A priority patent/CN108713272B/zh
Priority to US16/078,894 priority patent/US10862166B2/en
Priority to EP18738577.8A priority patent/EP3407414B1/fr
Priority claimed from KR1020180004666A external-priority patent/KR102108159B1/ko
Publication of WO2018131954A1 publication Critical patent/WO2018131954A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—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 non-aqueous electrolyte for lithium secondary battery and a lithium secondary battery including the same, in which a side reaction of an electrolyte is suppressed even in a high voltage environment, thereby improving electrical characteristics.
  • 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 has a structure in which an electrolyte including lithium salt is impregnated in an electrode assembly in which a cathode, a porous separator, and an anode are sequentially stacked.
  • lithium ions of the positive electrode active material are released and inserted into the active material layer of the negative electrode, and during discharge, lithium ions of the active material layer are released and inserted into the positive electrode active material, and the electrolyte serves as a medium for transferring lithium ions between the negative electrode and the positive electrode. Do it.
  • the electrolyte generally contains an organic solvent and an electrolyte salt.
  • an organic solvent for example, in a mixed solvent of a highly dielectric cyclic carbonate such as propylene carbonate and ethylene carbonate and a linear carbonate such as diethyl carbonate, ethyl methyl carbonate and dimethyl carbonate, Addition of salts is common.
  • LiPF 6 lithium salts are unstable at high temperatures, so the anions are thermally decomposed to produce acidic materials such as hydrofluoric acid (HF).
  • the first technical problem of the present invention is to provide a nonaqueous electrolyte solution for a lithium secondary battery including an additive capable of suppressing the generation of by-products generated by decomposition of lithium salts.
  • the second technical problem of the present invention is to provide a lithium secondary battery having improved cycle characteristics and stability even at high temperature and high voltage charging by including the nonaqueous electrolyte.
  • non-aqueous electrolyte comprising a compound represented by the formula (1):
  • R 1 to R 4 are each independently an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or — (CH 2 ) n —R 5 ;
  • R 5 is an aryl group having 6 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms substituted with an alkyl group having 1 to 2 carbon atoms,
  • n is an integer of 0-2.
  • R 1 is an alkyl group having 1 to 6 carbon atoms, or-(CH 2 ) n -R 5, wherein R 5 is an aryl group having 6 to 18 carbon atoms, or an alkyl group having 1 to 2 carbon atoms Substituted aryl group having 6 to 18 carbon atoms, n is an integer of 0 to 2, R 2 to R 4 may be each independently an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms.
  • the compound represented by Formula 1 may be at least one selected from the group consisting of compounds represented by Formulas 1a to 1f.
  • the compound represented by Formula 1 may be at least one selected from the group consisting of compounds represented by Formulas 1a to 1d and 1f.
  • the compound represented by Formula 1 may be included in about 0.5% to 40% by weight, specifically 1% to 30% by weight based on the total weight of the non-aqueous electrolyte.
  • a negative electrode, a positive electrode, a separator interposed between the negative electrode and the positive electrode, and a non-aqueous electrolyte the non-aqueous electrolyte provides a lithium secondary battery which is a non-aqueous electrolyte of the present invention.
  • Example 1 is a graph illustrating cycle life characteristics of a lithium secondary battery according to Experimental Example 1 of the present invention.
  • 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.
  • R 1 to R 4 are each independently an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or — (CH 2 ) n —R 5 ;
  • R 5 is an aryl group having 6 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms substituted with an alkyl group having 1 to 2 carbon atoms,
  • n is an integer of 0-2.
  • LiPF 6 is unstable at high temperatures in lithium salts, producing acidic materials such as hydrofluoric acid (HF) during thermal decomposition. When such an acidic substance is present in the battery, it causes side reactions and degrades the characteristics of the secondary battery.
  • the HX material may cause a rapid oxidation reaction in the battery to elute or degrade the metal from the positive electrode active material. If the metal is eluted from the positive electrode active material, these eluted metals are electrodeposited on the negative electrode to form an additional negative electrode film to further increase the negative electrode resistance. Furthermore, by-products such as lithium fluoride (LiF) produced during the formation of hydrofluoric acid (HF) are adsorbed on the surface of the anode to increase the anode interface resistance. Due to this effect, overall performance of the secondary battery, such as cycle life characteristics, may be reduced.
  • LiF lithium fluoride
  • HF hydrofluoric acid
  • a polar non-aqueous solvent of a carbonate system reacts with lithium ions in the electrolyte to form a solid electrolyte interface (SEI) film on the surface of the negative electrode.
  • SEI film serves as a protective film for stabilizing a battery by inhibiting decomposition of a carbonate-based electrolyte on a negative electrode surface.
  • the SEI membrane may be gradually disintegrated by increased electrochemical energy and thermal energy when charging and discharging of the battery is continuously performed, or particularly at high temperature storage in a fully charged state.
  • the battery thickness is expanded or a short circuit is caused to cause a decrease in stability.
  • the compound represented by the formula (1) as an additive or a solvent in the non-aqueous electrolyte, it is possible to suppress the side reaction of the electrolyte.
  • the compound represented by Chemical Formula 1 contains a Si—O structure in which a silicon (Si) atom is bonded to an oxygen atom of a carbonate group, hydrofluoric acid (HF) generated by thermal decomposition of lithium salt (LiPF 6 ) Forming a Si-F bond by the substitution reaction and consumes the hydrofluoric acid (HF) present in the electrolyte.
  • HF hydrofluoric acid
  • damage to the SEI film can be prevented, an increase in the amount of film of the cathode can be suppressed, a rapid oxidation reaction by the hydrofluoric acid can be prevented, and a stable ion conductive film can be formed on the surface of the positive electrode, and metal dissolution from the positive electrode active material is prevented. It can be suppressed.
  • the lithium secondary battery including the non-aqueous electrolyte containing the compound represented by Chemical Formula 1 as an additive or a solvent may improve cycle life characteristics and stability improvement under high temperature and high voltage.
  • R 1 is an alkyl group having 1 to 6 carbon atoms, or-(CH 2 ) n -R 5, wherein R 5 is aryl having 6 to 18 carbon atoms Or an aryl group having 6 to 18 carbon atoms substituted with an alkyl group having 1 to 2 carbon atoms, n is an integer of 0 to 2, and R 2 to R 4 are each independently an alkyl group having 1 to 6 carbon atoms or 2 to 6 carbon atoms. It may be an alkenyl group of.
  • the alkyl group is a methyl group, an ethyl group, or a propyl group
  • the alkenyl group is a propenyl group
  • the aryl group is a phenyl group, halophenyl group, benzyl group, halobenzyl group, tolyl group, naphthyl group, trihalophenyl group, trihal It may be any one selected from the group consisting of a romethyl phenyl group, a halogenonitrobenzyl group, an anthryl group and a phenanthryl group.
  • the compound represented by Formula 1 may be at least one selected from the group consisting of compounds represented by Formulas 1a to 1f.
  • the compound represented by Formula 1 may be at least one selected from the group consisting of compounds represented by Formulas 1a to 1d and 1f.
  • the compound represented by Formula 1e may include a double bond, thereby forming a film on the surface of the negative electrode.
  • the effect of suppressing metal elution on the anode side is reduced, so that the effect of improving cycle life characteristics may not be apparent.
  • the compound represented by Formula 1 is about 0.5 to 40% by weight, specifically 1 to 30% by weight based on the total weight of the non-aqueous electrolyte May be included. If the content of the compound is less than 0.5% by weight, the effect of inhibiting the side reaction of the electrolyte may be insignificant or the effect of inhibiting the metal dissolution may be insignificant. If the content of the compound represented by Formula 1 is more than 40% by weight, the resistance due to excessive film formation may occur. Increasing may degrade cycle life characteristics.
  • the electrolyte salt may be used without limitation those conventionally used in the lithium secondary battery electrolyte, for example, includes Li + as the cation of the lithium salt anion include F -, Cl -, Br - , I -, NO 3 -, N (CN) 2 -, BF 4 -, ClO 4 -, AlO 4 -, AlCl 4 -, PF 6 -, SbF 6 - , AsF 6 -, BF 2 C 2 O 4 -, BC 4 O 8 -, PF 4 C 2 O 4 -, PF 2 C 4 O 8 -, (CF 3) 2 PF 4 -, (CF 3) 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3) 5 PF -, (CF 3) 6 P -, CF 3 SO 3 -, C 4 F 9 SO 3 -, CF 3 CF 2 SO 3
  • the lithium salt is LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCH 3 CO 2 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , LiAlO 4 , and LiCH 3 SO 3
  • It may include a single or a mixture of two or more selected from the group consisting of, in addition to these LiBTI (lithium bisperfluoroethanesulfonimide, LiN (SO 2 C 2 F) commonly used in the electrolyte of the lithium secondary battery 5 ) without limitation, electrolyte salts such as lithium imide salts represented by 2 ), LiFSI (lithium fluorosulfonyl imide, LiN (SO 2 F) 2 ), and LiTFSI (lithium (bis) trifluoromethanesulfonimide, LiN (SO 2 CF 3 ) 2 )
  • the electrolyte salt is a single or two or more selected from the group consisting of LiPF 6 , LiBF 4 , LiCH 3 CO 2 , LiCF 3 CO 2 , LiCH 3 SO 3 , LiFSI, LiTFSI and LiN (C 2 F 5 SO 2 ) 2 Mixtures may be included.
  • the electrolyte salt may be appropriately changed within a usable range, 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 an electrode. If the concentration of the electrolyte salt exceeds 1.5M, the film forming effect may be less.
  • the organic solvent is not limited as long as it can minimize decomposition by an oxidation reaction or the like in the charge and discharge process of the secondary battery, and can exhibit the desired characteristics with the additive.
  • an ether solvent, an ester solvent, an amide solvent, etc. can be used individually or in mixture of 2 or more types, respectively.
  • 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. It is not limited to this.
  • 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, and 1,2-pentylene carbonate. , 2,3-pentylene carbonate, vinylene carbonate, and fluoroethylene carbonate (FEC), or any one or a mixture of two or more thereof.
  • linear carbonate compound examples include dimethyl carbonate (dimethyl carbonate, DMC), diethyl carbonate (diethyl carbonate, DEC), dipropyl carbonate, ethyl methyl 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.
  • the linear ester compound is any one selected from the group consisting of methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, and butyl propionate.
  • the above mixture and the like can be used representatively, but is not limited thereto.
  • the cyclic ester compound is any one selected from the group consisting of ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -valerolactone, ⁇ -caprolactone, or two or more thereof Mixtures may be used, but are not limited thereto.
  • the cyclic carbonate-based compound is a high viscosity organic solvent and has a high dielectric constant, and thus may be preferably used because it dissociates lithium salts in the electrolyte.
  • the cyclic carbonate-based compound has low viscosity and low viscosity such as dimethyl carbonate and diethyl carbonate.
  • the nonaqueous electrolyte solution for a lithium secondary battery according to an embodiment of the present invention may further include an additive for forming an SEI film, as necessary.
  • an additive for forming the SEI film usable in the present invention vinylene carbonate, vinyl ethylene carbonate, fluoroethylene carbonate, vinyl ethylene carbonate, cyclic sulfite, saturated sultone, unsaturated sultone, acyclic sulfone, etc. may be used alone or in combination. It can mix and use the above.
  • the cyclic sulfites 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-diethyl propylene sulfite, 4,6-dimethyl propylene sulfite, 4,6-diethyl propylene sulfite, 1,3-butylene glycol sulfite, and the like. Examples thereof include 1,3-propane sultone and 1,4-butane sultone.
  • unsaturated sultone examples include ethene sultone, 1,3-propene sultone, 1,4-butene sultone, 1-methyl-1,3 -Propene sulfone, and the like, and acyclic sulfones include divinyl sulfone, dimethyl sulfone, diethyl sulfone, methylethyl sulfone, and methyl vinyl sulfone.
  • a lithium secondary battery comprising a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode and a nonaqueous electrolyte, the nonaqueous electrolyte of the present invention as the nonaqueous electrolyte.
  • the lithium secondary battery of the present invention includes a non-aqueous electrolyte containing the compound represented by Chemical Formula 1, so that the negative electrode smoothly occludes and releases lithium even at high temperatures, thereby improving overall performance such as room temperature and high temperature lifetime characteristics of the secondary battery. Can be significantly improved.
  • the lithium secondary battery may be prepared by injecting the nonaqueous electrolyte of the present invention into an electrode structure including 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 slurry including a positive electrode active material, a binder, a conductive material, and a solvent on a positive electrode current collector, followed by drying and rolling.
  • the positive electrode current collector is not particularly limited as long as it has conductivity without causing chemical changes in the battery.
  • the positive electrode current collector may be formed of stainless steel, aluminum, nickel, titanium, calcined carbon, or carbon on the surface of aluminum or stainless steel. Surface treated with nickel, titanium, silver, or the like may be used.
  • the 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 is a lithium-manganese oxide (eg, LiMnO 2 , LiMn 2 O 4, etc.), lithium-cobalt oxide (eg, LiCoO 2, etc.), lithium-nickel oxide (for example, LiNiO 2 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-cobal
  • the lithium composite metal oxide may be LiCoO 2 , LiMnO 2 , LiNiO 2 , or lithium nickel manganese cobalt oxide (eg, Li (Ni 0.6 Mn 0.2 Co 0.2 ) O 2 in that the capacity characteristics and stability of the battery may be improved. , Li (Ni 0.5 Mn 0.3 Co 0.2 ) O 2 , or Li (Ni 0.8 Mn 0.1 Co 0.1 ) O 2 , or the like, or lithium nickel cobalt aluminum oxide (for example, Li (Ni 0.8 Co 0.15 Al 0.05 ) O 2, etc.
  • the lithium composite metal oxide may be Li (Ni 0.6 Mn 0.2 Co 0.2 ) O 2 , in view of the remarkable improvement effect according to the type and content ratio of the member forming the lithium composite metal oxide.
  • the cathode active material may be included in an amount of 80 wt% to 99 wt%, specifically 90 wt% to 99 wt%, based on the total weight of solids in the cathode slurry.
  • the energy density may be lowered, thereby lowering the capacity.
  • the binder is a component that assists the bonding of the active material, the conductive material, and the like to the current collector, and is generally added in an amount of 1 to 30% by weight based on the total weight of solids in the positive electrode slurry.
  • binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, Polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene-butadiene rubber, fluorine rubber, various copolymers, and the like.
  • the conductive material is a material that imparts conductivity without causing chemical change to the battery, and may be added in an amount of 1 to 20 wt% based on the total weight of solids in the cathode slurry.
  • Such conductive materials include carbon powders such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, or thermal black; Graphite powders such as natural graphite, artificial graphite, or graphite with very advanced crystal structure; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials, such as polyphenylene derivatives, may be used.
  • carbon powders such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, or thermal black
  • Graphite powders such as natural graphite, artificial graphite, or graphite with very advanced crystal structure
  • Conductive fibers such as carbon fibers and metal fibers
  • Metal powders such as carbon fluoride powder, aluminum powder and nickel powder
  • Conductive whiskeys such as zinc oxide and potassium titanate
  • Ketjenblack EC What is marketed by names, such as the series (made by Armak Company), Vulcan XC-72 (made by Cabot Company), and Super (P made by Timcal), can also be used.
  • the solvent may include an organic solvent such as N-methyl-2-pyrrolidone (NMP), and may be used in an amount that becomes a desirable viscosity when including the positive electrode active material and optionally a binder and a conductive material.
  • NMP N-methyl-2-pyrrolidone
  • the concentration of the solids in the slurry including the positive electrode active material and optionally the binder and the conductive material may be 10 wt% to 60 wt%, preferably 20 wt% to 50 wt%.
  • the negative electrode may be prepared by, for example, coating a negative electrode slurry including a negative electrode active material, a binder, a conductive material, a solvent, and the like on a negative electrode current collector, followed by drying and rolling.
  • the negative electrode current collector generally has a thickness of 3 to 500 ⁇ m.
  • a negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery.
  • copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel Surface-treated with carbon, nickel, titanium, silver, and the like on the surface, aluminum-cadmium alloy and the like can be used.
  • fine concavities and convexities may be formed on the surface to enhance the bonding strength of the negative electrode active material, and may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
  • the negative electrode active material may be lithium metal, a carbon material capable of reversibly intercalating / deintercalating lithium ions, a metal or an alloy of these metals and lithium, a metal complex oxide, and may dope and undo lithium. At least one selected from the group consisting of materials, and transition metal oxide transition metal oxides.
  • any carbon-based negative electrode active material generally used in a lithium ion secondary battery may be used without particular limitation.
  • Examples thereof include crystalline carbon, Amorphous carbons or these may be used together.
  • Examples of the crystalline carbon include graphite such as amorphous, plate, flake, spherical or fibrous natural graphite or artificial graphite, and examples of the amorphous carbon include soft carbon (soft carbon) Or hard carbon, mesophase pitch carbide, calcined coke, or the like.
  • the metals or alloys of these metals with lithium include Cu, Ni, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al And a metal selected from the group consisting of Sn or an alloy of these metals with lithium may be used.
  • the metal complex oxide may include PbO, PbO 2 , Pb 2 O 3 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , GeO, GeO 2 , Bi 2 O 3 , Bi 2 O 4 , Bi 2 O 5 , Li x Fe 2 O 3 (0 ⁇ x ⁇ 1), Li x WO 2 (0 ⁇ x ⁇ 1), and Sn x Me 1- x Me ' y O z (Me: Mn, Fe Me ': Al, B, P, Si, Group 1, Group 2, Group 3 elements of the periodic table, halogen; 0 ⁇ x ⁇ 1;1 ⁇ y ⁇ 3; 1 ⁇ z ⁇ 8 Any one selected from the group can be used.
  • Examples of the material capable of doping and undoping lithium include Si, SiO x (0 ⁇ x ⁇ 2), Si-Y alloys (wherein Y is an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, a transition metal, Is an element selected from the group consisting of rare earth elements and combinations thereof, not Si), Sn, SnO 2 , Sn-Y (Y is an alkali metal, alkaline earth metal, group 13 element, group 14 element, transition metal, rare earth) An element selected from the group consisting of elements and combinations thereof, and not Sn; and at least one of these and SiO 2 may be mixed and used.
  • transition metal oxide examples include lithium-containing titanium composite oxide (LTO), vanadium oxide, lithium vanadium oxide, and the like.
  • the negative active material may be included in an amount of 80 wt% to 99 wt% based on the total weight of solids in the negative electrode slurry.
  • the binder is a component that assists in bonding between the conductive material, the active material and the current collector, and is typically added in an amount of 1 to 30 wt% based on the total weight of solids in the negative electrode slurry.
  • binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, Polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene-butadiene rubber, fluorine rubber, various copolymers thereof, and the like.
  • the conductive material is a component for further improving the conductivity of the negative electrode active material, and may be added in an amount of 1 to 20 wt% based on the total weight of solids in the negative electrode slurry.
  • 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, alcohol, etc., and may be used in an amount that becomes a desirable viscosity when including the negative electrode active material and optionally a binder and a conductive material.
  • concentration of the solids in the slurry including the negative electrode active material and, optionally, the binder and the conductive material may be 50 wt% to 75 wt%, preferably 50 wt% to 65 wt%.
  • porous polymer films conventionally used as separators for example, polyolefins such as ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymer and ethylene / methacrylate copolymer, etc.
  • the porous polymer film made of the polymer may be used alone or by laminating them, or a conventional porous nonwoven fabric, for example, a non-woven fabric made of high melting point glass fiber, polyethylene terephthalate fiber, or the like may be used. It is not.
  • the external shape of the lithium secondary battery of the present invention is not particularly limited, but may be cylindrical, square, pouch type, or coin type using a can.
  • non-aqueous organic solvent fluoroethylene carbonate (FEC): propylene carbonate (PC): ethylene carbonate (EMC) 30:10: 60 volume ratio
  • FEC fluoroethylene carbonate
  • PC propylene carbonate
  • EMC ethylene carbonate
  • the positive electrode active material slurry 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
  • a lithium secondary battery (battery capacity 5.5 mAh) was prepared by pouring the prepared non-aqueous electrolyte.
  • an electrolyte solution and a secondary battery including the same were prepared in the same manner as in Example 1 except for including the compound of Formula 1b instead of the compound of Formula 1a.
  • an electrolyte solution and a secondary battery including the same were prepared in the same manner as in Example 1 except for including the compound of Formula 1c instead of the compound of Formula 1a.
  • an electrolyte solution and a secondary battery including the same were prepared in the same manner as in Example 1 except for including the compound of Formula 1d instead of the compound of Formula 1a.
  • an electrolyte solution and a secondary battery including the same were prepared in the same manner as in Example 1 except for including the compound of Formula 1e instead of the compound of Formula 1a.
  • an electrolyte solution and a secondary battery including the same were prepared in the same manner as in Example 1 except for including the compound of Formula 1f instead of the compound of Formula 1a.
  • an electrolyte solution and a secondary battery including the same were prepared in the same manner as in Example 1, except that 40 g of the compound of Formula 1a was included in 60 g of the non-aqueous organic solvent.
  • an electrolyte solution and a secondary battery including the same were prepared in the same manner as in Example 1, except that 99.5 g of the non-aqueous organic solvent contained 0.5 g of the compound of Formula 1a.
  • an electrolyte solution and a secondary battery including the same were prepared in the same manner as in Example 1, except that 45 g of the compound of Formula 1a was included in 55 g of the non-aqueous organic solvent.
  • An electrolyte and a secondary battery including the same were prepared in the same manner as in Example 1, except that the compound of Formula 1a was not added when preparing the nonaqueous electrolyte.
  • an electrolyte solution and a secondary battery including the same were prepared in the same manner as in Example 1, except that the compound of Formula 2 was added instead of the compound of Formula 1a.
  • the secondary batteries prepared in Examples 1 to 9 and the secondary batteries prepared in Comparative Examples 1 and 2 were charged at 60 ° C. with 0.7C constant current until 4.35V, and then charged with 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 and discharge current rate
  • C-rate of the battery represented by ampere (A)
  • A ampere
  • 1C means 5.5mA current
  • the secondary battery of Comparative Example 1 is 375 ppm, and the secondary battery of Comparative Example 2 is high as 318 ppm. That is, in the case of the secondary battery including the nonaqueous electrolyte of the present invention, the amount of HF present or generated in the electrolyte is reduced, so that a stable film can be formed on the surface of the anode, thereby suppressing metal elution from the electrode (anode). You can see that.

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Abstract

La présente invention concerne un électrolyte non aqueux destiné à une batterie secondaire au lithium, qui comprend un composé capable d'inhiber une réaction parallèle d'un électrolyte dans un environnement à haute température et à haute tension, et une batterie secondaire au lithium qui comprend l'électrolyte non aqueux destiné à une batterie secondaire au lithium et présente ainsi des caractéristiques de cycle et une stabilité améliorées même dans une charge à haute température et à haute tension.
PCT/KR2018/000648 2017-01-12 2018-01-12 Électrolyte non aqueux et batterie secondaire au lithium le comprenant Ceased WO2018131954A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
PL18738577T PL3407414T3 (pl) 2017-01-12 2018-01-12 Niewodny elektrolit i zawierający go akumulator litowy
CN201880001276.8A CN108713272B (zh) 2017-01-12 2018-01-12 非水电解质溶液以及包括所述非水电解质溶液的锂二次电池
US16/078,894 US10862166B2 (en) 2017-01-12 2018-01-12 Non-aqueous electrolyte solution and lithium secondary battery including the same
EP18738577.8A EP3407414B1 (fr) 2017-01-12 2018-01-12 Électrolyte non aqueux et batterie secondaire au lithium le comprenant

Applications Claiming Priority (4)

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KR20170005600 2017-01-12
KR10-2017-0005600 2017-01-12
KR1020180004666A KR102108159B1 (ko) 2017-01-12 2018-01-12 비수전해액 및 이를 포함하는 리튬 이차전지
KR10-2018-0004666 2018-01-12

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03236169A (ja) * 1990-02-13 1991-10-22 Nippon Telegr & Teleph Corp <Ntt> 化学電池
JP2007123097A (ja) * 2005-10-28 2007-05-17 Sony Corp 電池
WO2011034067A1 (fr) * 2009-09-15 2011-03-24 宇部興産株式会社 Solution d'électrolyte non aqueux et élément électrochimique utilisant celle-ci
JP2013145702A (ja) * 2012-01-16 2013-07-25 Adeka Corp 非水電解液二次電池及び二次電池用非水電解液
KR20140020328A (ko) * 2011-06-09 2014-02-18 아사히 가세이 가부시키가이샤 배터리 전해질용 물질 및 사용 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03236169A (ja) * 1990-02-13 1991-10-22 Nippon Telegr & Teleph Corp <Ntt> 化学電池
JP2007123097A (ja) * 2005-10-28 2007-05-17 Sony Corp 電池
WO2011034067A1 (fr) * 2009-09-15 2011-03-24 宇部興産株式会社 Solution d'électrolyte non aqueux et élément électrochimique utilisant celle-ci
KR20140020328A (ko) * 2011-06-09 2014-02-18 아사히 가세이 가부시키가이샤 배터리 전해질용 물질 및 사용 방법
JP2013145702A (ja) * 2012-01-16 2013-07-25 Adeka Corp 非水電解液二次電池及び二次電池用非水電解液

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3407414A4 *

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