WO2013137596A1 - Électrolyte non aqueux pour batterie secondaire au lithium et batterie secondaire au lithium le comprenant - Google Patents

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

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WO2013137596A1
WO2013137596A1 PCT/KR2013/001902 KR2013001902W WO2013137596A1 WO 2013137596 A1 WO2013137596 A1 WO 2013137596A1 KR 2013001902 W KR2013001902 W KR 2013001902W WO 2013137596 A1 WO2013137596 A1 WO 2013137596A1
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lithium secondary
carbonate
nonaqueous electrolyte
secondary battery
lithium
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PCT/KR2013/001902
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English (en)
Korean (ko)
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곽승엽
이범진
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서울대학교 산학협력단
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Publication of WO2013137596A1 publication Critical patent/WO2013137596A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • C07D233/56—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 only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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 for lithium secondary batteries and a lithium secondary battery comprising the same, and more particularly, to a nonaqueous electrolyte for lithium secondary batteries having improved ion conductivity, initial capacity, and cycle characteristics, and a lithium secondary battery comprising the same. .
  • lithium secondary batteries developed in the early 1990s, having excellent energy density, rapid charge / discharge characteristics, and cycle performance, are the most suitable electrochemical devices that can satisfy these requirements.
  • an anode containing graphite capable of inserting and desorption a cathode containing a lithium-containing oxide, and the like, a separator for preventing a short circuit between the two electrodes, and a nonaqueous electrolyte solution in which lithium salt is dissolved in an appropriate amount in an organic solvent.
  • the average discharge voltage of the lithium secondary battery is about 3.6V to 3.7V, and one of the advantages is that the discharge voltage is higher than that of an alkaline battery, a nickel-cadmium battery, or the like.
  • an electrochemically stable nonaqueous electrolyte is required in the charge and discharge voltage range of 0 to 4.2V.
  • the nonaqueous electrolyte is generally composed of an organic solvent and a lithium salt, but in some cases, an additive may be added to supplement the mechanical strength of the nonaqueous electrolyte and the interface with the electrode.
  • lithium ions in the nonaqueous electrolyte are reduced to be inserted between the graphite constituting the negative electrode, and the lithium metal oxide constituting the positive electrode is dissolved in the nonaqueous electrolyte to maintain the lithium ion concentration of the nonaqueous electrolyte.
  • lithium ions and anions of organic solvents or lithium salts are partially decomposed to form a thin solid electrolyte interface (SEI) on the electrode surface.
  • SEI acts as a barrier to prevent the breakdown of the electrode structure by inserting organic solvents having a high molecular weight into the graphite constituting the negative electrode, and also serves as a passage to help smooth movement of lithium ions. Therefore, the composition and structure of the SEI formed on the surface of the negative electrode during the initial charging of the battery has a great influence on the battery performance. Therefore, in order to realize a high performance secondary battery, development of a non-aqueous electrolyte capable of forming a stable SEI for minimizing degradation of battery performance due to reduction and decomposition of an organic solvent has been urgently required.
  • the ionic liquid due to the high price and high viscosity of the ionic liquid, it is used as an additive of a conventional non-aqueous electrolyte containing a lithium salt and an organic solvent, rather than using only the non-aqueous electrolyte itself.
  • the cations of the ionic liquid move with the lithium ions to the electrode according to the potential difference, thereby decreasing the mobility of the lithium ions, and the ions of the ionic liquid moved to the electrode are inserted into the electrodes with the lithium ions.
  • the problem to be solved by the present invention is to improve the ion conductivity, to form a stable SEI on the anode surface, a non-aqueous electrolyte that can reduce the irreversible capacity and improve the charge and discharge characteristics of the battery and a lithium secondary battery comprising the same To provide.
  • Another object of the present invention is to provide an electrochemical and thermally stable nonaqueous electrolyte and a lithium secondary battery comprising the same.
  • the imidazolium-based zwitter ion represented by the following formula (1); Organic solvents; And a lithium salt; a nonaqueous electrolyte solution for a lithium secondary battery is provided.
  • R 1 is a linear or branched alkyl group having 1 to 6 carbon atoms, n is an integer of 3 or 4, and m is an integer of 2 or 3.
  • R 1 is methyl, ethyl or butyl, n is 3, m may be 2.
  • the imidazolium-based zwitter ions may be included in an amount of 0.5 wt% to 3.0 wt% based on the total weight of the nonaqueous electrolyte.
  • the anion of the lithium salt is F - , Cl - , Br - , I - , NO 3 - , N (CN) 2 - , BF 4 - , ClO 4 - , PF 6 - , (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 - , CF 3 CF 2 SO 3 - , (CF 3 SO 2 ) 2 N - , (FSO 2 ) 2 N - , CF 3 CF 2 (CF 3 ) 2 CO - , (CF 3 SO 2 ) 2 CH - , (SF 5 ) 3 C - , (CF 3 SO 2 ) 3 C - , CF 3 (CF 2 ) 7 SO 3 - , CF 3 CO 2 - , CH 3 CO 2
  • the lithium salt concentration of the electrolyte solution may be 0.8 M to 1.5 M.
  • the organic solvent is ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2 3-pentylene carbonate, vinylene carbonate, vinylethylene carbonate, fluoroethylene carbonate (FEC), dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, ethylmethyl carbonate (EMC), Methylpropyl carbonate, ethylpropyl carbonate, ethylpropyl carbonate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -valerolactone and It may be any one selected from the group consisting of ⁇ -caprolactone or a mixture of two or more thereof.
  • the nonaqueous electrolyte solution for lithium secondary batteries may further include an ionic liquid.
  • the ionic liquid may be any one selected from the group consisting of imidazolium, pyridinium, ammonium, morpholinium, and pyrrolidinium, or a mixture of two or more thereof.
  • a lithium secondary battery comprising an anode, a cathode, and a nonaqueous electrolyte, wherein the nonaqueous electrolyte is a nonaqueous electrolyte described above.
  • imidazolium-based zwitter ions are adsorbed on the electrode by nitrile groups and contribute to the formation of stable SEI, thereby causing electrochemical stability and thermal stability of the lithium secondary battery. And ionic conductivity, and in particular, reduction of irreversible capacity and improvement of charge / discharge characteristics of the battery.
  • Example 1 is a graph showing the measurement of the circulating voltage current of the three-electrode cell using the nonaqueous electrolyte prepared according to Example 1 and Comparative Example 2 of the present invention.
  • Figure 2 is a graph showing the initial discharge capacity, measured through a charge and discharge test for the lithium secondary battery prepared according to Examples 1 to 3 and Comparative Example 1 of the present invention.
  • Figure 4 is a graph showing the cycle characteristics measured by repeated charge and discharge tests for 100 times at 1 C lithium secondary batteries prepared according to Examples 1 to 3 and Comparative Example 1 of the present invention.
  • the nonaqueous electrolyte solution for lithium secondary batteries according to the present invention includes an imidazolium-based zwitter ion organic solvent and a lithium salt represented by the following general formula (1).
  • R 1 is a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms, n is an integer of 3 or 4, m is an integer of 2 or 3.
  • the imidazolium-based zwitter ion represented by Formula 1 may be prepared by reacting imidazolium substituted with a nitrile group with 1,4-butanesultone or 1,3-propanesultone as in Scheme 1 below. .
  • examples of the unsubstituted alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, isoamyl, hexyl and the like.
  • One or more hydrogen atoms included in the alkyl group may be a halogen atom, a hydroxy group, a hydrosulfide group, a nitro group, a cyano group, a substituted or unsubstituted amino group (-NH 2 , -NH (R), -N (R ')).
  • R "), R 'and R" are independently of each other an alkyl group having 1 to 10 carbon atoms), amidino group, hydrazine, or hydrazone group carboxyl group, sulfonic acid group, phosphoric acid group, C1-C20 alkyl group, C1-C20 halogenation Alkyl group, C1-C20 alkenyl group, C1-C20 alkynyl group, C1-C20 heteroalkyl group, C6-C20 aryl group, C6-C20 arylalkyl group, C6-C20 heteroaryl group, or C6-C20 It may be substituted with a heteroarylalkyl group.
  • Imidazolium-based zwitter ions represented by the formula (1) according to the invention is characterized in that it includes both nitrile group and sulfonate group.
  • imidazolium-based zwitter ions By including the imidazolium-based zwitter ions, during the initial aging of the lithium secondary battery, imidazolium-based zwitter ions are adsorbed to the electrode by the nitrile group to form a stable SEI.
  • the imidazolium-based zwitter ion may be selected according to the specific type of the organic solvent, lithium salt, electrode active material.
  • the composition may be included in an amount of 0.5 wt% to 3.0 wt%, more preferably 0.5 wt% to 1.5 wt% based on the total weight of the nonaqueous electrolyte.
  • the numerical range is satisfied, a stable SEI is formed and the electrochemical stability, thermal stability, and ion conductivity of the lithium secondary battery are further improved.
  • the said lithium salt contained in the nonaqueous electrolyte of this invention is an anion, F - , Cl - , Br - , I - , NO 3 - , N (CN) 2 - , BF 4 - , ClO 4 - , PF 6 - , (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 - , CF 3 CF 2 SO 3 - , (CF 3 SO 2 ) 2 N - , (FSO 2 ) 2 N - , CF 3 CF 2 (CF 3 ) 2 CO - , (CF 3 SO 2 ) 2 CH - , (SF 5 ) 3 C - , (CF 3 SO 2 ) 3 C - , CF 3 (CF 2 ) 7 SO 3 -
  • Non-limiting examples of the lithium salt herein include LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , CH 3 SO 3 Li, CF 3 SO 3 Li, (CF 3 SO 2 ) 2 NLi, chloroborane lithium, lower aliphatic lithium carbonate and lithium tetraphenyl borate may be used, but the present invention is not limited thereto.
  • the lithium salt concentration of the nonaqueous electrolyte may be 0.8 M to 1.5 M.
  • concentration of the lithium salt satisfies the numerical range, the performance of the lithium secondary battery is prevented from deteriorating.
  • organic solvent included in the nonaqueous electrolyte solution described above those conventionally used in the nonaqueous electrolyte solution for a lithium secondary battery may be used without limitation, and for example, ethers, esters, amides, linear carbonates, and cyclic carbonates may be used alone or in combination. It can mix and use the above.
  • carbonate compounds which are typically cyclic carbonates, linear carbonates, or mixtures thereof may be included.
  • 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, vinylethylene carbonate and any one selected from the group consisting of halides thereof or mixtures of two or more thereof.
  • halides include, for example, fluoroethylene carbonate (FEC), but are not limited thereto.
  • linear carbonate compound may be any one selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, ethylmethyl carbonate (EMC), methylpropyl carbonate and ethylpropyl carbonate. Mixtures of two or more of them may be representatively used, but are not limited thereto.
  • ethylene carbonate and propylene carbonate which are cyclic carbonates among the carbonate-based organic solvents, have high dielectric constants and can dissociate lithium salts in the non-aqueous electrolyte more efficiently.
  • These cyclic carbonates include dimethyl carbonate and diethyl carbonate.
  • 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.
  • esters in the organic solvent include methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -valerolactone, and One or a mixture of two or more selected from the group consisting of ⁇ -caprolactone may be used, but is not limited thereto.
  • the nonaqueous electrolyte solution for lithium secondary batteries of the present invention may further include an ionic liquid within a range not departing from the object of the present invention.
  • the ionic liquid is any one or two or more selected from the group consisting of imidazolium, pyridinium, ammonium, morpholinium, and pyrrolidinium, which are ionic liquids commonly used in lithium secondary batteries. It may be a mixture, but is not limited thereto.
  • the content of the ionic liquid may be 10 wt% to 50 wt%, more preferably 10 wt% to 30 wt%, based on the total weight of the nonaqueous electrolyte, but is not limited thereto.
  • nonaqueous electrolyte of the present invention may further include various additives such as an adhesion improving agent, a filler, and the like in order to improve the mechanical strength of the nonaqueous electrolyte and the interface performance with the electrode.
  • various additives such as an adhesion improving agent, a filler, and the like in order to improve the mechanical strength of the nonaqueous electrolyte and the interface performance with the electrode.
  • the lithium secondary battery according to the present invention is a lithium secondary battery including an anode, a cathode, and a nonaqueous electrolyte, wherein the nonaqueous electrolyte is a nonaqueous electrolyte according to the present invention.
  • the lithium secondary battery of the present invention can be prepared according to conventional methods known in the art. For example, a porous separator may be placed between the cathode and the anode, and then the nonaqueous electrolyte solution according to the present invention may be added.
  • any porous substrate commonly used in an electrochemical device may be used.
  • a polyolefin-based porous membrane or a nonwoven fabric may be used. It is not limited.
  • polyolefin-based porous membrane examples include polyethylene, polypropylene, polybutylene, polypentene, such as high density polyethylene, linear low density polyethylene, low density polyethylene, ultra high molecular weight polyethylene, respectively, or a mixture thereof
  • polyolefin-based polymers such as polyethylene, polypropylene, polybutylene, polypentene, such as high density polyethylene, linear low density polyethylene, low density polyethylene, ultra high molecular weight polyethylene, respectively, or a mixture thereof
  • polyethylene such as polyethylene, polypropylene, polybutylene, polypentene, such as high density polyethylene, linear low density polyethylene, low density polyethylene, ultra high molecular weight polyethylene, respectively, or a mixture thereof
  • polypentene such as high density polyethylene, linear low density polyethylene, low density polyethylene, ultra high molecular weight polyethylene, respectively, or a mixture thereof
  • the nonwoven fabric may be, for example, polyethylene terephthalate, polybutyleneterephthalate, polyester, polyacetal, polyamide, polycarbonate, or polycarbonate. ), Polyimide, polyetheretherketone, polyethersulfone, polyphenyleneoxide, polyphenylenesulfidro, polyethylenenaphthalene, etc. Or the nonwoven fabric formed from the polymer which mixed these is mentioned.
  • the structure of the nonwoven can be a spunbond nonwoven or melt blown nonwoven composed of long fibers.
  • the anode has a structure in which an anode layer including an anode active material and a binder is supported on one side or both sides of a current collector.
  • the anode layer may further include a cellulose thickener such as carboxy methyl cellulose (CMC) in order to further increase the viscosity of the anode active material slurry.
  • CMC carboxy methyl cellulose
  • anode active material a lithium metal, a carbon material, a metal compound, or a mixture thereof, which may normally occlude and release lithium ions, may be used.
  • both low crystalline carbon and high crystalline carbon may be used as the carbon material.
  • Soft crystalline carbon and hard carbon are typical low crystalline carbon
  • high crystalline carbon is natural graphite, Kish graphite, pyrolytic carbon, liquid crystal pitch-based carbon fiber.
  • High temperature calcined carbon such as (mesophase pitch based carbon fiber), meso-carbon microbeads, Mesophase pitches and petroleum or coal tar pitch derived cokes.
  • the cathode has a structure in which a cathode layer including a cathode active material, a conductive material, and a binder is supported on one or both surfaces of a current collector.
  • the cathode active material may include a lithium-containing oxide, and the lithium-containing oxide may be a lithium-containing transition metal oxide.
  • the lithium-containing transition metal oxide may be coated with a metal or metal oxide such as aluminum (Al).
  • Al aluminum
  • sulfides, selenides, and halides may also be used.
  • the conductive material is not particularly limited as long as it is an electron conductive material that does not cause chemical change in the electrochemical device.
  • carbon black, graphite, carbon fiber, carbon nanotubes, metal powder, conductive metal oxide, organic conductive materials, and the like can be used, and currently commercially available products as acetylene black series (Chevron Chemical) Chevron Chemical Company or Gulf Oil Company, etc., Ketjen Black EC series (Armak Company), Vulcan XC-72 (Cabot Company) (Cabot Company) and Super P (MMM).
  • acetylene black, carbon black, graphite, etc. are mentioned.
  • the binder used for the cathode and the anode has a function of retaining the cathode active material and the anode active material in the current collector and connecting the active materials, and a binder commonly used may be used without limitation.
  • PVDF-co-HFP vinylidene fluoride-hexafluoropropylene copolymer
  • PVDF-co-HFP vinylidene fluoride-hexafluoropropylene copolymer
  • polyacrylonitrile polyacrylonitrile
  • polymethylmethacrylate polymethylmethacrylate
  • SBR butadiene rubber
  • CMC carboxymethyl cellulose
  • the current collectors used for the cathode and the anode are metals of high conductivity, and metals to which the slurry of the active material can easily adhere can be used as long as they are not reactive in the voltage range of the battery.
  • a non-limiting example of a cathode current collector is a foil prepared by aluminum, nickel or a combination thereof
  • a non-limiting example of an anode current collector is copper, gold, nickel or a copper alloy or a combination thereof.
  • the current collector may be used by stacking substrates made of the materials.
  • the cathode and the anode were kneaded using an active material, a conductive material, a binder, a thickener, and a high boiling point solvent to form an electrode mixture, and then the mixture was applied to a copper foil of a current collector, dried, and press-molded. It may be produced by heat treatment under vacuum at about 2 hours to a temperature of about °C to 250 °C.
  • the external shape of the lithium secondary battery according to the present invention is not particularly limited, but may be cylindrical, square, pouch type or coin type using a can.
  • LiCoO 2 was used as the cathode active material
  • graphite was used as the anode active material
  • polypropylene was used as the separator
  • 0.5 g of the prepared nonaqueous electrolyte was injected as the electrolyte, followed by A lithium secondary battery was prepared by aging for 2 hours under conditions.
  • a non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1 except that 0.78 mmol of 1-propanenitrile-2-methylimidazolium-3-propanesulfonate was added.
  • a nonaqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1 except that 1.18 mmol of 1-propanenitrile-2-methylimidazolium-3-propanesulfonate was added.
  • a nonaqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1 except that 1-propanenitrile-2-methylimidazolium-3-propanesulfonate was not added.
  • LiCoO 2 was used as the cathode active material
  • graphite was used as the anode active material
  • polypropylene was used as the separator
  • 0.5 g of the prepared nonaqueous electrolyte was injected as the electrolyte, followed by A lithium secondary battery was prepared by aging for 2 hours under conditions.
  • a nonaqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Comparative Example 2, except that 0.78 mmol of 1,2-dimethylimidazolium-3-propanesulfonate was added.
  • a nonaqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Comparative Example 2 except that 1.18 mmol of 1,2-dimethylimidazolium-3-propanesulfonate was added.
  • a non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Comparative Example 2, except that 1.58 mmol of 1,2-dimethylimidazolium-3-propanesulfonate was added.
  • the resistance values of the nonaqueous electrolytes prepared in Examples 1 to 3 and Comparative Examples 1 to 5 were measured using an electrochemical impedance analyzer (Solartron 1255) at 20 ° C. And a lithium secondary battery using a stainless electrode, 0.5g of each non-aqueous electrolyte was injected.
  • the cross-sectional area of the electrode was 0.283 cm 2 , the distance between the two electrodes was measured to be 0.022 cm, the calculated ion conductivity value based on this is shown in Table 1 below.
  • Example 1 After the three-electrode cells were prepared using the nonaqueous electrolytes prepared in Example 1 and Comparative Example 2, cyclic voltammetry was measured for each cell.
  • a measuring instrument CHI900B SECM manufactured by CH Instruments was used. At this time, a graphite electrode was used as an electrode, and lithium metal was used as a counter electrode and a reference electrode, respectively. The measurement speed was 0.5 mVS -1 .
  • Example 1 including imidazolium-based zwitter ions substituted with a nitrile group, as shown in FIG. 1, SEI was well formed at the interface of the graphite electrode so that insertion and desorption of lithium ions occurred smoothly.
  • Comparative Example 2 containing an imidazolium-based zwitter ion unsubstituted nitrile group, it was confirmed that the stable SEI was not formed, the insertion and desorption of lithium ions did not occur smoothly.
  • Test Example 3 Measurement of charge and discharge performance
  • the charge and discharge characteristics of the lithium secondary batteries prepared in Examples 1 to 3 and Comparative Example 1 were measured by using a charger (WBCS 3000: Wonatech).
  • Charging and discharging up to three times was performed at 0.2 C, and performance measurement for each charging and discharging rate was performed at 0.5 C up to 4.2 V, and discharge was performed at 0.5 C, 1.0 C, 1.5 C and 2.0 C, respectively. It was. In addition, repeated charge / discharge performance measurements were performed 100 times at 1C.
  • Examples 1 to 3 which are lithium secondary batteries containing imidazolium-based zwitter ions substituted with nitrile groups, it was confirmed that the initial discharge capacity was improved compared to Comparative Example 1. .
  • the lithium secondary battery including the imidazolium-based zwitter ion in which the nitrile group is substituted has higher charge / discharge rate and higher repetitive charge / discharge performance than not included.

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Abstract

L'invention concerne un électrolyte non aqueux pour une batterie secondaire au lithium et la batterie secondaire au lithium comprenant celui-ci. L'électrolyte non aqueux pour une batterie secondaire au lithium selon la présente invention comporte un zwitterion à base d'imidazolium dont la structure est particulière, un solvant organique et un sel de lithium. La présente invention améliore la stabilité électrochimique, la stabilité thermique et la conductivité ionique de la batterie secondaire au lithium en permettant au zwitterion à base d'imidazolium de contribuer à la formation d'une interface d'électrolyte stable (SEI) par absorption sur une électrode en utilisant un groupe nitrile, pendant le vieillissement initial de la batterie secondaire au lithium et, plus particulièrement, l'invention peut réduire une capacité irréversible et améliorer des propriétés de charge et de décharge de la batterie.
PCT/KR2013/001902 2012-03-12 2013-03-08 Électrolyte non aqueux pour batterie secondaire au lithium et batterie secondaire au lithium le comprenant WO2013137596A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015151977A1 (fr) * 2014-03-31 2015-10-08 リンテック株式会社 Composé zwitterionique et conducteur d'ions
CN112216871A (zh) * 2019-07-10 2021-01-12 比亚迪股份有限公司 一种锂离子电池电解液及其制备方法、锂离子电池和电池模组
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KR101979897B1 (ko) * 2018-10-29 2019-05-17 한밭대학교 산학협력단 쯔비터이온성 리튬-실리카 설포베타인 실란 및 이의 제조방법과 이를 포함하는 전해질 조성물.
JP7408223B2 (ja) 2021-03-31 2024-01-05 エルジー エナジー ソリューション リミテッド 二次電池用電解液添加剤、それを含むリチウム二次電池用非水電解液およびリチウム二次電池
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CN112216871A (zh) * 2019-07-10 2021-01-12 比亚迪股份有限公司 一种锂离子电池电解液及其制备方法、锂离子电池和电池模组
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