WO2024253495A1 - Électrolyte utilisant un matériau zwitterionique à constante diélectrique élevée, et son procédé de préparation - Google Patents

Électrolyte utilisant un matériau zwitterionique à constante diélectrique élevée, et son procédé de préparation Download PDF

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WO2024253495A1
WO2024253495A1 PCT/KR2024/011019 KR2024011019W WO2024253495A1 WO 2024253495 A1 WO2024253495 A1 WO 2024253495A1 KR 2024011019 W KR2024011019 W KR 2024011019W WO 2024253495 A1 WO2024253495 A1 WO 2024253495A1
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electrolyte
zwitterionic
lithium
dielectric constant
metal
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Korean (ko)
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강용묵
서지훈
이수원
김빛가람
박상현
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Korea University Research and Business Foundation
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Korea University Research and Business Foundation
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    • 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

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  • Lithium-ion batteries are being used in various industrial fields, and their importance as a core technology for electric vehicles is increasing.
  • Lithium metal has a high theoretical capacity of 3860 mAh/g, which is more than 10 times the theoretical capacity of 372 mAh/g of graphite, which is used as a commercialized anode material for existing lithium-ion batteries, and a low reduction potential (-3.04 V (vs. SHE), making it an essential material for reducing the weight and increasing the capacity of batteries.
  • lithium metal As technological demands for advanced and lightweight batteries increase, the use of lithium metal as a next-generation anode material is essential. However, there is a limitation in that lithium ion deposition is concentrated in a specific area to thermodynamically stabilize the metal surface, which causes lithium dendrites to form.
  • the electrolyte uses a double-ion material as an electrolyte additive to suppress lithium dendrites that occur during charge and discharge, thereby imparting stability to the interface between the electrolyte and the negative electrode, thereby utilizing lithium metal as a negative electrode material of a battery and at the same time securing long-life and high-output characteristics of the battery.
  • an electrolyte using a high-k dielectric constant zwitterionic material for a secondary battery utilizing a metal anode material as a cathode can be provided, the electrolyte including an electrolyte mixture comprising an organic electrolyte including an organic solvent and a metal salt; and a zwitterionic compound having a weight-average molecular weight in a range of 100 to 60,000 g/mol and having a zwitterion.
  • the organic electrolyte may be provided using a high-dielectric constant zwitterionic material in which the metal salt is dissolved in the organic solvent at a concentration of 1 M to 4 M.
  • an electrolyte using a high-k zwitterionic material can be provided, wherein the zwitterionic compound is at least one compound selected from among a first zwitterionic compound including a zwitterionic monomer; a second zwitterionic compound derived from the zwitterionic monomer and polymerized via an initiator; a third zwitterionic compound derived from the zwitterionic monomer and polymerized via a crosslinking agent and an initiator; and a fourth zwitterionic compound derived from a combination of a cationic monomer and an anionic monomer and polymerized via an initiator.
  • the zwitterionic compound is at least one compound selected from among a first zwitterionic compound including a zwitterionic monomer; a second zwitterionic compound derived from the zwitterionic monomer and polymerized via an initiator; a third zwitterionic compound derived from the zwitterionic monomer and polymerized via
  • an electrolyte using a high-dielectric constant zwitterionic material can be provided, wherein the zwitterionic monomer is at least one material selected from the group consisting of 2-Methacryloyloxyethyl phosphorylcholine (MPC), 3-[[2-(Methacryloyloxy)ethyl]dimethylammonio] propoinate, and Sulfobetainemethacrylate.
  • MPC 2-Methacryloyloxyethyl phosphorylcholine
  • 3-[[2-(Methacryloyloxy)ethyl]dimethylammonio] propoinate and Sulfobetainemethacrylate.
  • an electrolyte using a high-k zwitterionic material can be provided, wherein the cationic monomer is at least one material selected from the group consisting of METAC, AETMA, and AMPTMA ((3-Acrylamidopropyl) trimethylammonium chloride), and the anionic monomer is at least one material selected from the group consisting of SPA, SPM (3-Sulfopropyl methacrylate), and AMPA.
  • the cationic monomer is at least one material selected from the group consisting of METAC, AETMA, and AMPTMA ((3-Acrylamidopropyl) trimethylammonium chloride)
  • the anionic monomer is at least one material selected from the group consisting of SPA, SPM (3-Sulfopropyl methacrylate), and AMPA.
  • an electrolyte using a high-dielectric constant zwitterionic material can be provided, which has a dielectric constant value higher than that of the organic solvent and increases the dielectric constant of the electrolyte mixture, thereby stabilizing the interface between the electrolyte and the metal negative electrode material.
  • an electrolyte using a high-k zwitterionic material in which the zwitterionic compound forms a polarized field on the surface of the metal negative electrode material, thereby suppressing the formation of metal dendrites due to biased deposition of metal ions.
  • an electrolyte using a high-dielectric constant zwitterionic material can be provided, wherein the organic solvent includes at least one material selected from the group consisting of ethylene carbonate, diethyl carbonate, propylene carbonate, dimethyl carbonate, and ethyl methyl carbonate.
  • the metal salt is lithium perchlorate (LiClO 4 ), lithium bis(trifluoromethanesulfonyl)imide (Li(CF 3 SO 2 ) 2N, LiTFSI), lithium tetrafluoroborate (LiBF 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), lithium bis-perfluoroethylsulfonylimide (Li(C 2 F 5 SO 2 ) 2N), lithium thiocyanate (LiSCN), lithium triflate (LiCF 3 SO 3 ), lithium tetrafluoroaluminate (LiAlF 4 ), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LIODFB), lithium difluoro(oxalato)borate (LiDFOB), lithium bis(fluorosulfony
  • a method for manufacturing an electrolyte using a high-k dielectric constant zwitterionic material for a secondary battery utilizing a metal anode material as a cathode may be provided, the method including: a first step of preparing an organic electrolyte including an organic solvent and a metal salt; and a second step of preparing an electrolyte mixture by mixing a zwitterionic compound having a zwitterionic compound and a weight average molecular weight satisfying a range of 100 to 60,000 g/mol and having a zwitterion into the prepared organic electrolyte.
  • a secondary battery including: a cathode; an anode including a metal cathode material; an electrolyte disposed between the cathode and the anode, the electrolyte using a high-k zwitterionic material according to any one of claims 1 to 8; and a separator positioned on the electrolyte using the high-k zwitterionic material.
  • An electrolyte using a high-dielectric constant zwitterionic material according to one embodiment of the present invention and a method for manufacturing the same have the effect of providing stability to the interface between the electrolyte and the anode by suppressing lithium dendrites generated during charge and discharge by using the zwitterionic material as an electrolyte additive, thereby utilizing lithium metal as an anode material of a battery and securing long-life and high-output characteristics of the battery at the same time.
  • FIG. 1 is a drawing for explaining a high-dielectric constant binary ion material according to embodiments of the present invention.
  • Figure 2 is a flow chart for explaining a method for manufacturing an electrolyte using a high-dielectric constant binary ion material according to embodiments of the present invention.
  • Figure 3 is a diagram showing the dielectric constant values of electrolytes according to Example 1 and Comparative Example 1.
  • FIG. 4 is a drawing showing the shape of the lithium metal surface after charge and discharge in a secondary battery lithium metal symmetric cell according to Example 2 and Comparative Example 2.
  • Figure 5 is a diagram showing charge/discharge curves obtained from constant current measurements in a secondary battery lithium metal symmetric cell according to Example 2 and Comparative Example 2.
  • Figure 6 is a drawing showing the flatness of the charge/discharge curve obtained from a constant current measurement in a secondary battery lithium metal symmetric cell according to Example 2 and Comparative Example 2 by dividing the curve into sections.
  • Figure 8 is a drawing showing the results of analyzing the lithium metal surface composition using an X-ray photoelectron spectroscopy after charge and discharge of a secondary battery lithium metal symmetric cell according to Example 2 and Comparative Example 2.
  • Figure 9 shows the results of constant current charge/discharge evaluation of lithium secondary battery coin cells according to Example 3 and Comparative Example 3.
  • a layer When a layer is referred to herein as being "on" another layer, it may be formed directly on the upper surface of the other layer, or a third layer may be interposed therebetween.
  • first, second, etc. are used herein to describe various regions, layers, etc., these regions, layers, etc. should not be limited by these terms. These terms are only used to distinguish a given region or layer from another region or layer. Thus, a part referred to as a first part in one embodiment may be referred to as a second part in another embodiment.
  • the embodiments described and illustrated herein also include complementary embodiments thereof. Parts denoted by the same reference numerals throughout the specification represent like elements.
  • the electrolyte using the high-dielectric constant zwitterionic material of the present invention is designed to increase the dielectric constant of the electrolyte and stabilize the interface between the electrolyte and the metal negative electrode material.
  • a zwitterionic material to the electrolyte as an electrolyte additive, an electrolyte using a high-k zwitterionic material capable of effectively suppressing dendrite growth on the surface of a metal anode material through polarization formation was secured.
  • FIG. 1 is a drawing for explaining a high-dielectric constant binary ion material according to embodiments of the present invention.
  • Figure 1a is a drawing for explaining a manufacturing process of a high-dielectric constant zwitterionic material
  • Figure 1b) is a drawing for explaining a coin cell including a high-dielectric constant zwitterionic material.
  • an electrolyte using a high-k dielectric constant zwitterionic material for a secondary battery utilizing a metal anode material as a cathode includes an electrolyte mixture comprising an organic electrolyte including an organic solvent and a metal salt, and a zwitterionic compound having a zwitterionic compound and a weight-average molecular weight satisfying a range of 100 to 60,000 g/mol.
  • the present invention may be an electrolyte using a high-dielectric constant zwitterionic material that can be used in lithium secondary batteries, sodium secondary batteries, potassium secondary batteries, zinc secondary batteries, aluminum secondary batteries and magnesium secondary batteries, each of which utilizes lithium metal, sodium metal, potassium metal, zinc metal, aluminum metal and magnesium metal as an anode, and more specifically, it is preferable that the electrolyte use a high-dielectric constant zwitterionic material for a lithium secondary battery that utilizes lithium metal as an anode.
  • it may be composed of 90 to 99.5 wt% of the organic electrolyte and 0.5 to 10 wt% of the zwitterionic compound.
  • the organic electrolyte may be a metal salt dissolved in the organic solvent at a concentration of 1 M to 4 M.
  • an electrolyte using a high-dielectric constant zwitterionic material may be an electrolyte containing a zwitterionic compound, i.e., a liquid electrolyte having a high dielectric constant value, and the zwitterionic compound may be a monomer or polymer having a zwitterionic compound.
  • the zwitterionic compound may be a zwitterionic polymer derived from a monomer having the zwitterion or derived from a cationic monomer and an anionic monomer.
  • the metal anode material may include lithium metal, sodium metal, potassium metal, zinc metal, aluminum metal, magnesium metal, etc., and may be utilized as an anode of a lithium secondary battery and a next-generation secondary battery, such as a sodium secondary battery, a potassium secondary battery, a zinc secondary battery, an aluminum secondary battery, and a magnesium secondary battery.
  • Such an electrolyte containing a zwitterionic compound can suppress the growth of metal dendrites on the surface of a metal anode material and side reactions with the electrolyte.
  • the metal anode material is preferably lithium metal, and more specifically, the electrolyte including a zwitterionic compound suppresses lithium dendrite growth on the surface of the lithium metal and side reactions with the electrolyte.
  • the organic solvent according to one embodiment of the present invention is not particularly limited as long as it dissolves the component materials well and has low reactivity with the metal negative electrode material.
  • the organic solvent according to the present invention may include one or more substances selected from the group consisting of common organic solvents, specifically, ethylene carbonate, diethyl carbonate, propylene carbonate, dimethyl carbonate, and ethyl methyl carbonate.
  • the metal salt according to one embodiment of the present invention is not particularly limited as long as it helps improve ion conductivity, and may vary depending on the type of the metal negative electrode material.
  • the metal salt according to a preferred embodiment of the present invention is a conventional lithium salt, specifically, lithium perchlorate (LiClO 4 ), lithium bis(trifluoromethanesulfonyl)imide (Li(CF 3 SO 2 ) 2N, LiTFSI), lithium tetrafluoroborate (LiBF 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), lithium bis-perfluoroethylsulfonylimide (Li(C 2 F 5 SO 2 ) 2N), lithium thiocyanate (LiSCN), lithium triflate (LiCF 3 SO 3 ), lithium tetrafluoroaluminate (LiAlF 4 ), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LIODFB), lithium difluoro(oxalato)borate
  • the zwitterionic compound according to one embodiment of the present invention is not particularly limited as long as it is a compound that can include both a cationic functional group and an anionic functional group.
  • the zwitterionic compound according to the present invention comprises a conventional monomer or polymer, and specifically, is at least one compound selected from a first zwitterionic compound comprising a zwitterionic monomer, a second zwitterionic compound derived from the zwitterionic monomer and polymerized via an initiator, a third zwitterionic compound derived from the zwitterionic monomer and polymerized via a crosslinking agent and an initiator, and a fourth zwitterionic compound derived from a combination of a cationic monomer and an anionic monomer and polymerized via an initiator.
  • the first zwitterionic compound may have a weight average molecular weight in a range of 100 to 400 g/mol
  • the second zwitterionic compound may have a weight average molecular weight in a range of 5000 to 15000 g/mol
  • the third zwitterionic compound may have a weight average molecular weight in a range of 30000 to 60000 g/mol
  • the fourth zwitterionic compound may have a weight average molecular weight in a range of 5000 to 15000 g/mol.
  • the above-mentioned zwitterionic monomer may be at least one material selected from the group consisting of 2-Methacryloyloxyethyl phosphorylcholine (MPC), 3-[[2-(Methacryloyloxy)ethyl]dimethylammonio] propoinate, and Sulfobetainemethacrylate, and may have a higher dielectric constant value than a conventional material having a zwitterionic monomer, and thus may be used as an electrolyte additive to increase the dielectric constant of the electrolyte.
  • MPC 2-Methacryloyloxyethyl phosphorylcholine
  • 3-[[2-(Methacryloyloxy)ethyl]dimethylammonio] propoinate and Sulfobetainemethacrylate
  • the cationic monomer may be at least one material selected from the group consisting of METAC, AETMA, and AMPTMA ((3-Acrylamidopropyl) trimethylammonium chloride), and the anionic monomer may be at least one material selected from the group consisting of SPA, SPM (3-Sulfopropyl methacrylate), and AMPA.
  • the zwitterionic compound has a higher dielectric constant than the organic solvent and can increase the dielectric constant of the electrolyte mixture to stabilize the interface between the electrolyte and the metal negative electrode material.
  • the above-described zwitterionic compound forms a polarized field on the surface of the metal anode material, thereby suppressing the formation of metal dendrites due to biased deposition of metal ions, thereby imparting interface stability to a secondary battery utilizing the metal anode material as the anode.
  • the polarization field can be formed on the surface of a metal cathode material having a relatively (-) polarity, with cations included in the zwitterionic compound being arranged in the direction of the metal cathode material and anions being arranged in the direction of the electrolyte, and the formation of such a polarization field can ensure uniform movement of metal ions.
  • the zwitterionic compound can increase the dielectric constant of the electrolyte mixture to stabilize the interface between the electrolyte and the lithium metal, and form a polarized field on the surface of the lithium metal to suppress the formation of lithium dendrites due to biased deposition of lithium ions, thereby imparting interface stability to a lithium secondary battery utilizing lithium metal as an anode.
  • the zwitterionic compound may be at least one compound selected from the first zwitterionic compound, the second zwitterionic compound, the third zwitterionic compound, and the fourth zwitterionic compound, wherein the second zwitterionic compound may be formed by heat-treating or UV-treating a first monomer mixture solution composed of a mixture of the zwitterionic monomer and the initiator and a solvent, depending on the type of the initiator.
  • the third zwitterionic compound can be formed by heat-treating or UV-treating a second monomer mixture consisting of a mixture of the zwitterionic monomer, a crosslinking agent, and an initiator and a solvent, depending on the type of initiator.
  • the fourth zwitterionic compound can be formed by heat-treating or UV-treating a third monomer mixture consisting of a mixture of a cationic monomer, an anionic monomer, and an initiator and a solvent, depending on the type of initiator.
  • the solvent is water.
  • a crosslinking agent according to one embodiment of the present invention may include any one material selected from the group consisting of conventional crosslinking agents, for example, poly(ethyleneglycol) diacrylate and trimethylolpropane triacrylate, and is not limited to a specific crosslinking agent, but is preferably poly(ethyleneglycol) diacrylate, which has excellent mechanical properties of a crosslinked structure obtained through a crosslinking reaction and excellent chemical resistance and electrochemical stability.
  • conventional crosslinking agents for example, poly(ethyleneglycol) diacrylate and trimethylolpropane triacrylate
  • the initiator according to one embodiment of the present invention is not particularly limited as long as it can initiate a polymerization reaction or a crosslinking reaction.
  • the initiator according to the present invention may include any one material selected from the group consisting of conventional initiators, for example, ammonium persulfate, 2.2'-Azobisisobutylonitrile, Photoinitiator 184, and Photoinitiator 2959, and is not limited to a specific initiator, but preferably, ammonium persulfate that can excellently initiate a crosslinking reaction.
  • conventional initiators for example, ammonium persulfate, 2.2'-Azobisisobutylonitrile, Photoinitiator 184, and Photoinitiator 2959
  • a secondary battery coin cell includes a cathode, an anode including a metal cathode material, an electrolyte using a high-k zwitterionic material of the present invention disposed between the cathode and the anode, and a separator positioned on the electrolyte using the high-k zwitterionic material.
  • the positive and negative electrodes according to the present invention may be conventionally known positive and negative electrodes and are not limited to specific negative and positive electrodes, but preferably, the negative electrode may include lithium metal, which is a metal negative electrode material.
  • the negative electrode may include lithium metal, which is a metal negative electrode material.
  • a symmetrical cell using metal for both the positive and negative electrodes can be manufactured, and when lithium metal is used, it corresponds to a secondary battery lithium symmetrical cell.
  • the above positive and negative electrodes can be arranged on an electrolyte using the high-k zwitterionic material of the present invention, that is, the electrolyte using the high-k zwitterionic material according to the present invention contains a zwitterionic compound as an electrolyte additive, thereby forming a polarization field on the surface of lithium metal to uniformly move lithium ions, thereby preventing the conventional biased deposition of lithium ions, thereby effectively suppressing the growth of lithium dendrites.
  • Figure 2 is a flow chart for explaining a method for manufacturing an electrolyte using a high-dielectric constant binary ion material according to embodiments of the present invention.
  • an electrolyte using a high-k material includes a first step (S100) of preparing an organic electrolyte including an organic solvent and a lithium salt, and a second step (S200) of preparing an electrolyte mixture by mixing a zwitterion compound having a zwitterion and a weight average molecular weight satisfying a range of 100 to 60,000 g/mol into the prepared organic electrolyte.
  • the above step S100 relates to an organic electrolyte preparation process, and refers to a process of preparing an organic electrolyte by mixing an organic solvent and a lithium salt prior to manufacturing an electrolyte using the high-dielectric constant binary ion material of the present invention.
  • the organic electrolyte may be prepared by dissolving the lithium salt in the organic solvent at a concentration of 1 M to 4 M. That is, the lithium salt may be added to 1 L of the organic solvent at a concentration of 1 M to 4 M.
  • the S200 step is a process for preparing a zwitterionic compound and additionally mixing the prepared zwitterionic compound into the organic electrolyte prepared in the S100 step to increase the overall permittivity of the electrolyte.
  • the S200 step may include a preparation step of preparing a zwitterionic compound; and a stirring step of mixing and stirring the prepared organic electrolyte and the prepared zwitterionic compound.
  • the above preparation step may vary depending on the type of the zwitterionic compound, and specifically, when the zwitterionic compound is a first zwitterionic compound including a zwitterionic monomer, a first zwitterionic compound is prepared that is at least one substance selected from the group consisting of 2-Methacryloyloxyethyl phosphorylcholine (MPC), 3-[[2-(Methacryloyloxy)ethyl]dimethylammonio] propoinate, and Sulfobetainemethacrylate.
  • MPC 2-Methacryloyloxyethyl phosphorylcholine
  • 3-[[2-(Methacryloyloxy)ethyl]dimethylammonio] propoinate and Sulfobetainemethacrylate.
  • a first monomer mixture solution comprising a mixture of the zwitterionic monomer and the initiator and a solvent is prepared, and the prepared first monomer mixture solution is cast on a substrate, and then cured through heat treatment or UV treatment depending on the type of the initiator to prepare a second zwitterionic compound.
  • the zwitterionic compound is a third zwitterionic compound
  • a second monomer mixture solution comprising a mixture of the zwitterionic monomer, a crosslinking agent, and an initiator and a solvent is prepared, and the prepared second monomer mixture solution is cast on a substrate, and then cured through heat treatment or UV treatment depending on the type of the initiator to prepare the third zwitterionic compound.
  • the zwitterionic compound is a fourth zwitterionic compound
  • a third monomer mixture solution consisting of a mixture of a cationic monomer, an anionic monomer, and an initiator and a solvent is prepared, and the prepared third monomer mixture solution is cast on a substrate, and then cured through heat treatment or UV treatment depending on the type of the initiator to prepare the fourth zwitterionic compound.
  • the stirring process may be a process of mixing the organic electrolyte prepared in step S100 and the prepared zwitterionic compound, which is at least one compound selected from the first zwitterionic compound, the second zwitterionic compound, the third zwitterionic compound, and the fourth zwitterionic compound, and stirring at a speed of 300 rpm for 1 to 3 hours in a room temperature atmosphere to prepare an electrolyte mixture.
  • the prepared zwitterionic compound which is at least one compound selected from the first zwitterionic compound, the second zwitterionic compound, the third zwitterionic compound, and the fourth zwitterionic compound
  • the electrolyte mixture can be prepared to be composed of 90 to 99.5 wt% of the organic electrolyte and 0.5 to 10 wt% of the zwitterionic compound.
  • Example 1 Preparation of electrolyte using high-k zwitterionic material
  • an organic solvent was prepared by mixing ethylene carbonate and diethyl carbonate in a volume ratio of 1:1, and lithium hexafluorophosphate, a lithium salt, was dissolved in the prepared organic solvent at a concentration of 1 M to prepare an organic electrolyte.
  • Example 2 Manufacturing of a secondary battery lithium metal symmetric cell containing an electrolyte using a high-k zwitterionic material
  • a secondary battery lithium metal symmetrical cell was manufactured using an electrolyte using the high-k double-ion material of Example 1, lithium metal as both the anode and cathode, and a polyethylene separator as the separator (Example 2).
  • Example 3 Manufacturing of lithium secondary battery coin cell including electrolyte using high-k zwitterionic material
  • a lithium secondary battery coin cell was manufactured using an electrolyte using the high-k double-ion material of Example 1, lithium metal as an anode, a cathode including a cathode active material, and a polyethylene separator as a separator (Example 3).
  • An organic solvent was prepared by mixing ethylene carbonate and diethyl carbonate in a volume ratio of 1:1, and lithium hexafluorophosphate, a lithium salt, was dissolved in the prepared organic solvent at a concentration of 1 M to prepare an organic electrolyte (Comparative Example 1).
  • Comparative Example 2 Manufacturing of a secondary battery lithium metal symmetrical cell containing an organic electrolyte
  • a secondary battery lithium metal symmetrical cell was manufactured using the organic electrolyte of Comparative Example 1, lithium metal as both the anode and the cathode, and a polyethylene separator as the separator (Comparative Example 2).
  • a lithium secondary battery coin cell was manufactured using the organic electrolyte of Comparative Example 1, lithium metal as an anode, a cathode including a cathode active material, and a polyethylene separator as a separator (Comparative Example 3).
  • Figure 3 is a diagram showing the dielectric constant values of electrolytes according to Example 1 and Comparative Example 1.
  • Figure 3a shows the results of measuring the dielectric constant of the electrolyte according to Comparative Example 1
  • Figure 3b shows the results of measuring the dielectric constant of the electrolyte according to Example 1.
  • the dielectric constant value of the electrolyte according to Example 1 was measured to be much higher than the dielectric constant value of the electrolyte according to Comparative Example 1, which means that the distribution of interfacial charges is higher in the electrolyte with the added zwitterionic material than in the general organic electrolyte, and this seems to indicate that the zwitterionic material present in the electrolyte according to Example 1 forms a strong polarization field at the interface.
  • FIG. 4 is a drawing showing the shape of the lithium metal surface after charge and discharge in a secondary battery lithium metal symmetric cell according to Example 2 and Comparative Example 2.
  • FIG. 4a is a drawing showing the movement of lithium ions at the electrolyte/lithium metal interface of the lithium metal symmetric cell of the secondary battery according to Comparative Example 2
  • FIG. 4b is a drawing showing the surface shape of the lithium metal of the secondary battery lithium metal symmetric cell according to Comparative Example 2
  • FIG. 4c) is a drawing showing the movement of lithium ions at the electrolyte/lithium metal interface of the lithium metal symmetric cell of the secondary battery according to Example 2
  • FIG. 4d) is a drawing showing the surface shape of the lithium metal of the lithium metal symmetric cell of the secondary battery according to Example 2.
  • the surface shape of the lithium metal of the secondary battery lithium metal symmetric cell according to Comparative Example 2 is uneven and lithium dendrites like a tree trunk are formed due to biased deposition caused by uneven movement of lithium ions.
  • Figure 5 is a diagram showing charge/discharge curves obtained from constant current measurements in a secondary battery lithium metal symmetric cell according to Example 2 and Comparative Example 2.
  • FIG. 5a is a charge/discharge curve of a secondary battery lithium metal symmetric cell according to Comparative Example 2
  • FIG. 5b) is a charge/discharge curve of a secondary battery lithium metal symmetric cell according to Example 2.
  • Figure 6 is a drawing showing the flatness of the charge/discharge curve obtained from a constant current measurement in a secondary battery lithium metal symmetric cell according to Example 2 and Comparative Example 2 by dividing the curve into sections.
  • FIG. 6a is a diagram showing a charge/discharge curve and the flatness of the curve between 10 and 20 hours of a secondary battery lithium metal symmetrical cell according to Comparative Example 2
  • FIG. 6b is a diagram showing a charge/discharge curve and the flatness of the curve between 10 and 20 hours of a secondary battery lithium metal symmetrical cell according to Example 2
  • FIG. 6c is a diagram showing a charge/discharge curve and the flatness of the curve between 60 and 70 hours of a secondary battery lithium metal symmetrical cell according to Comparative Example 2
  • FIG. 6d) is a diagram showing a charge/discharge curve and the flatness of the curve between 60 and 70 hours of a secondary battery lithium metal symmetrical cell according to Example 2
  • FIG. 6d is a diagram showing a charge/discharge curve and the flatness of the curve between 60 and 70 hours of a secondary battery lithium metal symmetrical cell according to Example 2
  • FIG. 6b is a diagram showing a charge/discharge curve and the
  • FIG. 6e is a diagram showing a charge/discharge curve and the flatness of the curve between 120 and 130 hours of a secondary battery lithium metal symmetrical cell according to Comparative Example 2
  • FIG. 6f is a diagram showing a charge/discharge curve and the flatness of the curve between 120 and 130 hours of a secondary battery lithium metal symmetrical cell according to Example 2
  • This is a drawing showing a charge/discharge curve and the flatness of the curve between 120 and 130 hours
  • FIG. 6g) is a drawing showing a charge/discharge curve and the flatness of the curve between 190 and 200 hours of a lithium metal symmetrical cell of a secondary battery according to Example 2.
  • the secondary battery lithium metal symmetric cell according to Comparative Example 2 showed a rapid increase in voltage polarization after about 80 hours, which is a phenomenon resulting from dead lithium formed due to dendrite growth on the surface of the lithium metal, and a section where the voltage polarization suddenly dropped also appeared, which indicates that the lithium metals of the positive and negative electrodes were directly connected due to extreme dendrite growth.
  • the secondary battery lithium metal symmetric cell according to Example 2 did not show a sharp rise or fall in voltage polarization during 300 hours of charge and discharge, indicating that dendrite growth on the lithium metal surface was significantly suppressed.
  • the flatness represents the difference between the maximum voltage value within a charge or discharge curve and the minimum voltage value in the pit portion.
  • the flatness calculated from the curve within the charge/discharge section between 10 and 20 hours of the lithium metal symmetrical cell of the secondary battery according to Example 2 is 14.8 mV, which is much lower than 60.7 mV of the lithium metal symmetrical cell of the secondary battery according to Comparative Example 2. It is judged that this is because the strong polarization field of the interface formed from the zwitterion material in the electrolyte uniformly distributed the lithium ion flux.
  • the calculated flatness in the curve within the charge/discharge section between 60 and 70 hours was reduced by approximately 8.8% based on the flatness calculated in FIG. 6b)
  • the calculated flatness in the curve within the charge/discharge section between 120 and 130 hours was reduced by approximately 2.8%
  • the calculated flatness in the charge/discharge section between 190 and 200 hours was reduced by approximately 10.9%, which indicates that the strong polarization field at the interface formed from the zwitterionic material in the electrolyte significantly improved the cycle life characteristics of the lithium metal symmetric cell by uniformly dispersing the lithium ion flux.
  • Figure 7 is a drawing showing the results of analyzing the lithium metal surface composition using an energy dispersive spectrometer after charge and discharge of a secondary battery lithium metal symmetric cell according to Example 2 and Comparative Example 2.
  • FIG. 7a) is a drawing showing the location of elemental analysis of a lithium metal surface according to Comparative Example 2
  • FIG. 7b) is a drawing showing the location of elemental analysis of a lithium metal surface according to Example 2
  • FIG. 7c is a drawing showing the lithium metal surface composition value according to Comparative Example 2
  • FIG. 7d is a drawing showing the lithium metal surface composition value according to Example 2.
  • Figure 8 is a drawing showing the results of analyzing the lithium metal surface composition using an X-ray photoelectron spectroscopy after charge and discharge of a secondary battery lithium metal symmetric cell according to Example 2 and Comparative Example 2.
  • FIG. 8a) is a drawing showing the lithium metal surface composition according to Comparative Example 2
  • FIG. 8b) is a drawing showing the lithium metal surface composition according to Example 2.
  • the lithium metal surface composition information of the lithium metal symmetric cell of the secondary battery according to Example 2 and the lithium metal surface composition information of the lithium metal symmetric cell of the secondary battery according to Comparative Example 2 do not show a significant difference, and in particular, the ratio of nitrogen element is about 6% in the lithium metal according to Example 2 and about 3% in the lithium metal according to Comparative Example 2, which is lower than the nitrogen element value of 7% in the lithium metal before charging and discharging.
  • the low nitrogen element ratio of the lithium metal according to Example 2 indicates that the zwitterion MPC containing nitrogen atoms in the electrolyte was not decomposed during the charge/discharge process.
  • Figure 9 shows the results of constant current charge/discharge evaluation of lithium secondary battery coin cells according to Example 3 and Comparative Example 3.
  • Fig. 9a shows the results of a constant current charge/discharge evaluation of a lithium secondary battery coin cell according to Comparative Example 3
  • Fig. 9b shows the results of a constant current charge/discharge evaluation of a lithium secondary battery coin cell according to Example 3.
  • MPC a zwitterionic material present in the electrolyte on the lithium metal surface of the coin cell according to Example 3, forms a polarization field at the lithium metal/electrolyte interface, thereby inducing a uniform lithium ion flux, thereby significantly suppressing lithium dendrites.

Landscapes

  • Secondary Cells (AREA)

Abstract

La présente invention concerne un électrolyte utilisant un matériau zwitterionique à constante diélectrique élevée, et son procédé de préparation. Selon un mode de réalisation, l'électrolyte fourni à l'aide d'un matériau zwitterionique à constante diélectrique élevée, qui est destiné à une batterie secondaire utilisant un matériau d'anode métallique en tant qu'anode, contient un mélange d'électrolyte composé : d'un électrolyte organique comprenant un solvant organique et un sel métallique; et d'un composé zwitterionique ayant un poids moléculaire moyen en poids qui satisfait une plage comprise entre 100 et 60 000 g/mol et ayant un zwitterion.
PCT/KR2024/011019 2023-06-09 2024-07-29 Électrolyte utilisant un matériau zwitterionique à constante diélectrique élevée, et son procédé de préparation Pending WO2024253495A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN120690928A (zh) * 2025-06-17 2025-09-23 安徽鑫钠新材料科技有限公司 一种长循环适用的钠离子电解液的制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150050412A (ko) * 2013-10-29 2015-05-08 주식회사 엘지화학 겔 폴리머 전해질 및 이를 포함하는 리튬 이차전지
KR20170044136A (ko) * 2014-08-22 2017-04-24 린텍 가부시키가이샤 전해질 조성물, 이차 전지 및 이차 전지의 사용 방법
KR102254908B1 (ko) * 2019-11-21 2021-05-24 연세대학교 산학협력단 그래프트 공중합체, 이의 제조방법, 및 상기 공중합체를 포함하는 고분자 전해질막
KR20210074479A (ko) * 2019-12-12 2021-06-22 현대자동차주식회사 양쪽성 이온염을 포함하는 리튬-공기전지용 겔 고분자 전해질 및 이를 포함하는 리튬-공기전지

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150050412A (ko) * 2013-10-29 2015-05-08 주식회사 엘지화학 겔 폴리머 전해질 및 이를 포함하는 리튬 이차전지
KR20170044136A (ko) * 2014-08-22 2017-04-24 린텍 가부시키가이샤 전해질 조성물, 이차 전지 및 이차 전지의 사용 방법
KR102254908B1 (ko) * 2019-11-21 2021-05-24 연세대학교 산학협력단 그래프트 공중합체, 이의 제조방법, 및 상기 공중합체를 포함하는 고분자 전해질막
KR20210074479A (ko) * 2019-12-12 2021-06-22 현대자동차주식회사 양쪽성 이온염을 포함하는 리튬-공기전지용 겔 고분자 전해질 및 이를 포함하는 리튬-공기전지

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
GAN HUIHUI, ZHANG YONG, LI SHAOQIAO, YU LIPING, WANG JIRONG, XUE ZHIGANG: "Self-Healing Single-Ion Conducting Polymer Electrolyte Formed via Supramolecular Networks for Lithium Metal Batteries", ACS APPLIED ENERGY MATERIALS, AMERICAN CHEMICAL SOCIETY, vol. 4, no. 1, 25 January 2021 (2021-01-25), pages 482 - 491, XP093245670, ISSN: 2574-0962, DOI: 10.1021/acsaem.0c02384 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN120690928A (zh) * 2025-06-17 2025-09-23 安徽鑫钠新材料科技有限公司 一种长循环适用的钠离子电解液的制备方法

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