WO2023211103A1 - Composé d'alkylsulfone fluoré et électrolyte non aqueux pour batterie secondaire et batterie secondaire le comprenant - Google Patents

Composé d'alkylsulfone fluoré et électrolyte non aqueux pour batterie secondaire et batterie secondaire le comprenant Download PDF

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WO2023211103A1
WO2023211103A1 PCT/KR2023/005572 KR2023005572W WO2023211103A1 WO 2023211103 A1 WO2023211103 A1 WO 2023211103A1 KR 2023005572 W KR2023005572 W KR 2023005572W WO 2023211103 A1 WO2023211103 A1 WO 2023211103A1
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Prior art keywords
formula
aqueous electrolyte
secondary battery
compound represented
solvent
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English (en)
Korean (ko)
Inventor
최현진
신미라
김경철
박일성
이상율
이호춘
한철희
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Chun Bo ltd
Daegu Gyeongbuk Institute of Science and Technology
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Chun Bo ltd
Daegu Gyeongbuk Institute of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/14—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C317/18—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to acyclic carbon atoms of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/24—Sulfones; Sulfoxides having sulfone or sulfoxide groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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 fluorinated alkyl sulfone compound, a non-aqueous electrolyte for secondary batteries containing the same, and a secondary battery, and more specifically, to a fluorinated alkyl sulfone compound with low viscosity and excellent flame retardancy without insufficient solubility in lithium salts, and the same. It relates to non-aqueous electrolytes for secondary batteries and secondary batteries with excellent battery characteristics and flame retardancy.
  • Secondary batteries specifically lithium secondary batteries, have been adopted as a power source for many portable devices due to their high energy density and ease of design. Recently, they have also been used as a power source for electric vehicles and as a power storage power source that can store electricity produced through the development of alternative energy. Expectations are rising.
  • a lithium secondary battery consists of a cathode, an anode, an electrolyte, and a separator.
  • lithium ions are desorbed from the cathode, causing an oxidation reaction, and lithium ions are inserted into the anode, causing a reduction reaction.
  • lithium ions are desorbed from the positive electrode, causing an oxidation reaction, and lithium ions are inserted from the negative electrode, causing a reduction reaction.
  • the electrolyte does not conduct electrons but only exhibits ionic conductivity, and serves to transfer lithium ions between the anode and cathode.
  • the electrolyte solution is usually a non-aqueous electrolyte solution in which lithium salt and various additives are dissolved in a non-aqueous solvent.
  • non-aqueous solvents include cyclic carbonate-based solvents such as ethylene carbonate (EC), propylene carbonate (PC), vinylene carbonate, dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), and ethyl.
  • EC ethylene carbonate
  • PC propylene carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • DPC dipropyl carbonate
  • EMC methyl carbonate
  • fluorinated ethers have low viscosity and are advantageous in low resistance characteristics, but have the problem of insufficient solubility in lithium salts such as LiPF 6 .
  • One object of the present invention is to provide a fluoroalkyl sulfone compound with low viscosity and excellent flame retardancy while not lacking in solubility in lithium salts.
  • Another object of the present invention is to provide a non-aqueous electrolyte for secondary batteries containing the fluorinated alkyl sulfone compound and having excellent battery characteristics and flame retardancy.
  • Another object of the present invention is to provide a secondary battery containing the non-aqueous electrolyte for secondary batteries.
  • the present invention provides a compound represented by the following formula (1).
  • R 1 is an alkyl group or an aryl group of C 1 -C 4 ,
  • R 2 is a hydrogen atom or a fluorine atom
  • l and n are each independently integers from 1 to 2
  • n is an integer from 0 to 1
  • o is an integer from 1 to 10.
  • R 1 may be an alkyl group of C 1 -C 2 or a phenyl group.
  • the compound represented by Formula 1 may be selected from compounds represented by any one of Formulas 1-1 to 1-13 below.
  • the present invention provides a non-aqueous electrolyte solution for secondary batteries containing the above compound as a lithium salt and a solvent.
  • the non-aqueous electrolyte for secondary batteries according to an embodiment of the present invention may further include a carbonate-based solvent.
  • the mixing ratio of the compound represented by Formula 1 and the carbonate-based solvent may be 5:95 to 80:20 by volume.
  • the present invention provides a secondary battery containing the non-aqueous electrolyte for secondary batteries.
  • the fluorinated ether or ester compound containing a sulfone group of a specific structure according to the present invention has low viscosity and is excellent in flame retardancy while not lacking in solubility in lithium salts. Therefore, the fluorinated ether or ester compound containing a sulfone group according to the present invention can be advantageously used as a solvent for a non-aqueous electrolyte solution for secondary batteries, and in particular can achieve excellent battery characteristics and flame retardancy.
  • One embodiment of the present invention relates to a compound represented by the following formula (1).
  • R 1 is an alkyl group or an aryl group of C 1 -C 4 ,
  • R 2 is a hydrogen atom or a fluorine atom
  • l and n are each independently integers from 1 to 2
  • n is an integer from 0 to 1
  • o is an integer from 1 to 10.
  • the C 1 -C 4 alkyl group used herein refers to a straight-chain or branched monovalent hydrocarbon having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, and n-butyl. , i-butyl, t-butyl, etc., but are not limited thereto.
  • Aryl groups used herein include both aromatic groups, heteroaromatic groups, and partially reduced derivatives thereof.
  • the aromatic group is a simple or fused ring of 5 to 15 members
  • the heteroaromatic group refers to an aromatic group containing one or more oxygen, sulfur, or nitrogen.
  • Representative examples of aryl groups include phenyl, naphthyl, pyridinyl, furanyl, thiophenyl, indolyl, quinolinyl, imidazolinyl, Examples include oxazolyl, thiazolyl, and tetrahydronaphthyl, but are not limited thereto.
  • R 1 may be preferably a C 1 -C 2 alkyl group or a phenyl group in terms of battery life characteristics.
  • the compound represented by Formula 1 may be selected from compounds represented by any one of the following Formulas 1-1 to 1-13 in terms of flame retardancy and/or battery life characteristics.
  • the compound represented by Formula 2 is reacted with methanesulfonyl chloride in the presence of a base such as triethylamine (TEA) as shown in Scheme 1 to obtain Formula 3.
  • a base such as triethylamine (TEA)
  • TAA triethylamine
  • the compound represented by Formula 3 was etherified with the compound represented by Formula 4 in the presence of a base such as potassium carbonate (K 2 CO 3 ) to obtain the compound represented by Formula 5. It can be manufactured through an oxidation reaction using an oxidizing agent such as hydrogen peroxide (H 2 O 2 ).
  • One embodiment of the present invention relates to a non-aqueous electrolyte solution for a secondary battery containing a lithium salt and a compound represented by Formula 1 above as a solvent.
  • the compound represented by Formula 1 is a fluorinated alkyl sulfone ether compound or a fluorinated alkyl sulfone ester compound that not only serves as a medium through which ions involved in the electrochemical reaction of the battery can move, but also has one end Since it is a sulfone group, it does not lack solubility in lithium salts, but has excellent flame retardancy due to the fluorinated alkyl portion, and the sulfone group acts as a fluorine-containing film former through a reduction effect at the cathode, resulting in excellent battery characteristics, especially lifespan characteristics.
  • the non-aqueous electrolyte for secondary batteries according to an embodiment of the present invention may further include a carbonate-based solvent.
  • carbonate-based solvent one or more of a cyclic carbonate-based solvent and a linear carbonate-based solvent may be used.
  • the cyclic carbonate-based solvents 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, fluoroethylene carbonate (FEC), etc.
  • linear carbonate-based solvent examples include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, ethylmethyl carbonate (EMC), methylpropyl carbonate, and ethylpropyl carbonate.
  • the mixing ratio of the compound represented by Formula 1 and the carbonate-based solvent may be 5:95 to 80:20, preferably 10:90 to 70:30, based on volume.
  • the viscosity may increase and the flame retardant effect may be reduced, and if it is more than the above range, a lithium salt with low solubility may precipitate. This may cause battery performance to deteriorate.
  • the lithium salt serves as a source of lithium ions in the battery to enable basic operation of the secondary battery.
  • lithium salt those commonly used in non-aqueous electrolytes for secondary batteries can be used without limitation, for example, LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiClO 4 , LiCF 3 SO 3 , Li(CF 3 SO 2 ) 2 N, LiN(SO 2 CF 3 ) 2 , LiN(SO 2 C 2 F 5 ) 2 , LiC(SO 2 CF 3 ) 3 , LiN(SO 3 CF 3 ) 2 , LiC 4 F 9 SO 3 , LiAlO 4 , LiAlCl 4 , LiCl, LiI, LiB(C 2 O 4 ) 2 , Li(FSO 2 ) 2 N, etc. These can be used alone or in combination of two or more.
  • the concentration of the lithium salt is preferably in the range of 0.1 to 2M, and more preferably in the range of 0.7 to 1.6M. If the concentration of the lithium salt is less than 0.1M, the conductivity of the electrolyte may decrease and electrolyte performance may deteriorate, and if it exceeds 2M, the viscosity of the electrolyte may increase and the mobility of lithium ions may decrease.
  • One embodiment of the present invention relates to a secondary battery containing the above-described non-aqueous electrolyte solution.
  • the secondary battery may be a lithium secondary battery, for example, a lithium ion secondary battery.
  • the lithium secondary battery includes a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and the non-aqueous electrolyte solution described above.
  • the positive electrode may include a positive electrode active material layer containing a positive electrode active material, and if necessary, the positive electrode active material layer may further include a conductive material and/or a binder.
  • the positive electrode active material is a compound capable of reversible intercalation and deintercalation of lithium, and may include a lithium transition metal oxide containing lithium and one or more metals selected from cobalt, manganese, nickel, or aluminum.
  • the positive electrode active material includes lithium-manganese-based oxide (e.g., LiMnO 2 , LiMn 2 O 4 , etc.), lithium-cobalt-based oxide (e.g., LiCoO 2 , etc.), and lithium-nickel-based oxide (e.g., LiNiO 2 etc.), lithium-nickel-manganese oxide (for example, LiNi 1-Y Mn Y O 2 (0 ⁇ Y ⁇ 1), LiMn 2-z Ni z O 4 (0 ⁇ Z ⁇ 2), lithium-nickel-cobalt-based oxide (for example, LiNi 1-Y1 Co Y1 O 2 (0 ⁇ Y1 ⁇ 1), lithium-manganese-cobalt-based oxide (for example, LiCo 1-Y2 Mn Y2 O 2 (0 ⁇ Y2 ⁇ 1), LiMn 2-z1 Co z1 O 4 (0 ⁇ Z1 ⁇ 2), lithium-nickel-manganese-cobalt oxide (for example, Li(Ni p Co
  • the positive electrode active material may be included in an amount of 80 to 98% by weight, more specifically, 85 to 98% by weight, based on the total weight of the positive electrode active material layer.
  • the conductive material is used to provide conductivity to the electrode, and can be used without particular limitation as long as it does not cause chemical change and has electronic conductivity in the battery being constructed.
  • the conductive material includes carbon powder such as carbon black, acetylene black (or Denka black), Ketjen black, channel black, furnace black, and thermal black; Graphite powder such as natural graphite, artificial graphite, or graphite with a highly developed crystal structure; Conductive fibers such as carbon fiber and metal fiber; Metal powders such as carbon fluoride, aluminum, and nickel powder; Conductive whiskers such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives may be used.
  • carbon powder such as carbon black, acetylene black (or Denka black), Ketjen black, channel black, furnace black, and thermal black
  • Graphite powder such as natural graphite, artificial graphite, or graphite with a highly developed crystal structure
  • Conductive fibers such as carbon fiber and metal fiber
  • Metal powders such as carbon fluoride, aluminum, and nickel powder
  • Conductive whiskers such as zinc oxide and potassium titanate
  • Conductive metal oxides such as
  • the conductive material may be included in an amount of 0.1 to 10% by weight, preferably 0.1 to 5% by weight, based on the total weight of the positive electrode active material layer.
  • the binder serves to improve adhesion between positive electrode active material particles and adhesion between the positive active material and the current collector.
  • the binder includes polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, and tetrafluoroethylene.
  • PVDF polyvinylidene fluoride
  • CMC carboxymethylcellulose
  • starch hydroxypropylcellulose
  • regenerated cellulose polyvinylpyrrolidone
  • tetrafluoroethylene polyethylene, polypropylene, styrene-butadiene rubber, fluorine rubber, etc. can be used.
  • the binder may be included in an amount of 0.1 to 15% by weight, preferably 0.1 to 10% by weight, based on the total weight of the positive electrode active material layer.
  • the positive electrode can be manufactured according to a manufacturing method commonly known in the art.
  • the positive electrode may be prepared by applying a positive electrode slurry prepared by dissolving or dispersing the positive electrode active material, binder, and/or conductive material in a solvent onto the positive electrode current collector, followed by drying and rolling, or the positive electrode slurry is manufactured separately. It can be manufactured by casting on a support, then peeling off the support, and laminating the film obtained on the positive electrode current collector.
  • the positive electrode current collector is not particularly limited as long as it is conductive without causing chemical changes in the battery.
  • stainless steel, aluminum, nickel, titanium, calcined carbon, or carbon on the surface of aluminum or stainless steel. , surface treated with nickel, titanium, silver, etc. can be used.
  • the positive electrode current collector may have various forms such as foil, net, or porous material, and may form fine irregularities on the surface to strengthen the bonding force of the positive electrode active material.
  • the solvent may be a solvent commonly used in the art, such as dimethyl sulfoxide (DMSO), isopropyl alcohol, N-methylpyrrolidone (NMP), acetone, or water. and the like, and one type of these may be used alone or a mixture of two or more types may be used.
  • DMSO dimethyl sulfoxide
  • NMP N-methylpyrrolidone
  • acetone or water. and the like, and one type of these may be used alone or a mixture of two or more types may be used.
  • the negative electrode includes a negative electrode active material layer containing a negative electrode active material, and the negative electrode active material layer may further include a conductive material and/or a binder, if necessary.
  • the negative electrode active material may include a carbon-based negative electrode active material and/or a silicon-based negative electrode active material.
  • Examples of the carbon-based negative electrode active material include graphite-based materials such as natural graphite, artificial graphite, and Kish graphite; Pyrolytic carbon, mesophase pitch based carbon fiber, meso-carbon microbeads, mesophase pitches and petroleum or coal tar pitch derived cokes. High-temperature calcined carbon, soft carbon, hard carbon, etc. may be used.
  • silicon-based anode active material examples include silicon (Si), silicon oxide (SiOx, where 0 ⁇ x ⁇ 2), silicon carbide (SiC), and Si-Y alloy (where Y is an alkali metal, alkaline earth metal, group 13). It is an element selected from the group consisting of elements, group 14 elements, transition metals, rare earth elements, and combinations thereof, but may include one or more types selected from the group consisting of Si.
  • the element Y includes Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Bi, S, It may be selected from the group consisting of Se, Te, Po, and combinations thereof.
  • the negative electrode active material may be included in an amount of 80 to 99% by weight based on the total weight of the negative electrode active material layer.
  • the conductive material is a component to further improve the conductivity of the negative electrode active material, and is not particularly limited as long as it has conductivity without causing chemical changes in the battery.
  • the conductive material includes graphite such as natural graphite or artificial graphite; Carbon black such as acetylene black, Ketjen black, channel black, furnace black, and thermal black; Conductive fibers such as carbon fiber and metal fiber; Metal powders such as carbon fluoride, aluminum, 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.
  • the conductive material may be added in an amount of 10% by weight or less, preferably 5% by weight or less, based on the total weight of the negative electrode active material layer.
  • the binder serves to assist bonding between the conductive material, the active material, and the current collector.
  • the binder includes polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, and polypropylene.
  • PVDF polyvinylidene fluoride
  • CMC carboxymethyl cellulose
  • starch hydroxypropyl cellulose
  • polyvinylpyrrolidone polyvinylpyrrolidone
  • tetrafluoroethylene polyethylene
  • polypropylene ethylene-propylene-diene polymer
  • sulfonated-ethylene-propylene-diene polymer styrene-butadiene rubber
  • nitrile-butadiene rubber fluorine rubber, etc.
  • the binder may be added in an amount of 0.1% to 10% by weight based on the total weight of the negative electrode active material layer.
  • the cathode can be manufactured according to a cathode manufacturing method commonly known in the art.
  • the negative electrode may be prepared by applying a negative electrode slurry prepared by dissolving or dispersing the negative electrode active material and optionally a binder and a conductive material in a solvent onto the negative electrode current collector, followed by rolling and drying, or by applying the negative electrode slurry onto a separate support. It can be manufactured by casting and then peeling off the support and laminating the film obtained on the negative electrode current collector.
  • the negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical changes in the battery.
  • it can be used on the surface of copper, stainless steel, aluminum, nickel, titanium, fired carbon, copper or stainless steel. Surface treatment with carbon, nickel, titanium, silver, etc., aluminum-cadmium alloy, etc. can be used.
  • the negative electrode current collector may be used in various forms such as films, sheets, foils, nets, porous materials, foams, and non-woven fabrics, and may form fine irregularities on the surface to strengthen the bonding force of the negative electrode active material.
  • the solvent may be a solvent commonly used in the art, such as dimethyl sulfoxide (DMSO), isopropyl alcohol, N-methylpyrrolidone (NMP), acetone, or water. etc. can be mentioned.
  • DMSO dimethyl sulfoxide
  • NMP N-methylpyrrolidone
  • acetone or water. etc. can be mentioned.
  • the separator serves to separate the cathode and the anode and provide a passage for lithium ions to move.
  • the separator may be used without particular limitation as long as it is commonly used in the field.
  • the separator has low resistance to ion movement in the electrolyte and has excellent electrolyte moisturizing ability.
  • the separator includes commonly used porous polymer films, such as polyolefin-based polymers such as ethylene homopolymer, propylene homopolymer, ethylene/butene copolymer, ethylene/hexene copolymer, and ethylene/methacrylate copolymer.
  • the porous polymer film prepared can be used alone or by stacking them.
  • the separator may be a conventional porous nonwoven fabric, for example, a nonwoven fabric made of high melting point glass fiber, polyethylene terephthalate fiber, etc.
  • the pore diameter of the separator is generally 0.01 to 50 ⁇ m, and the porosity may be 5 to 95%.
  • the thickness of the separator may generally range from 5 to 300 ⁇ m.
  • the external shape of the secondary battery may be cylindrical, prismatic, pouch-shaped, or coin-shaped.
  • the secondary battery can be manufactured by injecting the non-aqueous electrolyte solution of the present invention into an electrode assembly composed of sequentially stacking a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode.
  • the secondary battery can be usefully used in portable devices such as mobile phones, laptop computers, and digital cameras, and electric vehicles such as hybrid electric vehicles (HEV).
  • portable devices such as mobile phones, laptop computers, and digital cameras
  • electric vehicles such as hybrid electric vehicles (HEV).
  • HEV hybrid electric vehicles
  • solution A 2-(Methylthio)ethan-1-ol (9.2g, 0.1mol) and triethylamine (20.2g, 0.2mol) were added to 100mL of methylene chloride and stirred at room temperature for 30 minutes to prepare solution A.
  • Solution B was prepared by adding methanesulfonyl chloride (12.6 g, 0.11 mol) into 50 mL of methylene chloride and stirring for 30 minutes at room temperature. The prepared solution B was added dropwise at room temperature for 1 hour using a dropping funnel.
  • solution A 2-(Methylthio)ethan-1-ol (9.2g, 0.1mol) and triethylamine (20.2g, 0.2mol) were added to 100mL of methylene chloride and stirred at room temperature for 30 minutes to prepare solution A.
  • Solution B was prepared by adding methanesulfonyl chloride (12.6 g, 0.11 mol) into 50 mL of methylene chloride and stirring for 30 minutes at room temperature. The prepared solution B was added dropwise at room temperature for 1 hour using a dropping funnel.
  • Methyl (2-(3,3,4,4,5,5,6,6,6-nonafluorohexyl)oxy)ethyl)sulfan (25.7 g, 0.076 mol) was dissolved in 100 g of acetic acid, then dissolved in 1N aqueous sulfuric acid solution. 10 mL was added, hydrogen peroxide (30% aqueous solution, 20 g) was added, and the mixture was stirred at room temperature for 12 hours. After confirming that all the reactants had disappeared using gas chromatography, 100 g of water and 100 g of methylene chloride were added for extraction, and the obtained organic layer was washed twice with a saturated aqueous NaHCO 3 solution. The organic solvent in the obtained organic layer was distilled off to obtain the title compound (22.2 g, 0.06 mol).
  • solution A 2-(Methylthio)ethan-1-ol (9.2g, 0.1mol) and triethylamine (20.2g, 0.2mol) were added to 100mL of methylene chloride and stirred at room temperature for 30 minutes to prepare solution A.
  • Solution B was prepared by adding methanesulfonyl chloride (12.6 g, 0.11 mol) into 50 mL of methylene chloride and stirring for 30 minutes at room temperature. The prepared solution B was added dropwise at room temperature for 1 hour using a dropping funnel.
  • solution A 2-(Methylthio)ethan-1-ol (9.2g, 0.1mol) and triethylamine (20.2g, 0.2mol) were added to 100mL of methylene chloride and stirred at room temperature for 30 minutes to prepare solution A.
  • Solution B was prepared by adding methanesulfonyl chloride (12.6 g, 0.11 mol) into 50 mL of methylene chloride and stirring for 30 minutes at room temperature. The prepared solution B was added dropwise at room temperature for 1 hour using a dropping funnel.
  • Methyl (2-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)oxy)sulfan (33.3, 0.076 mol) was added to 100 g of acetic acid. After dissolving, 10 mL of 1N sulfuric acid aqueous solution was added, hydrogen peroxide (30% aqueous solution, 20 g) was added, and the mixture was stirred at room temperature for 12 hours. After confirming that all the reactants had disappeared using gas chromatography, 100 g of water and 100 g of methylene chloride were added for extraction, and the obtained organic layer was washed twice with a saturated aqueous NaHCO 3 solution. The organic solvent in the obtained organic layer was distilled off to obtain the title compound (28.2 g, 0.06 mol).
  • solution A 2-(Methylthio)ethan-1-ol (9.2g, 0.1mol) and triethylamine (20.2g, 0.2mol) were added to 100mL of methylene chloride and stirred at room temperature for 30 minutes to prepare solution A.
  • Solution B was prepared by adding methanesulfonyl chloride (12.6 g, 0.11 mol) into 50 mL of methylene chloride and stirring for 30 minutes at room temperature. The prepared solution B was added dropwise at room temperature for 1 hour using a dropping funnel.
  • Methyl 2-(methylsulfonyl)acetate (15.2g, 0.1mol), 3,3,3-trifluoropropan-1-ol (12.5g, 0.11mol) and K 2 CO 3 (13.8g, 0.1mol) was added to 100 mL of acetonitrile and stirred at 40°C for 24 hours. After confirming that all of the raw material methyl 2-(methylsulfonyl)acetate had disappeared by gas chromatography, the mixture was cooled to room temperature, filtered to remove solids, and the solvent was distilled off. Next, the residue was extracted using 100 g of methylene chloride and 100 g of distilled water, and the organic solvent was distilled off to obtain the title compound (21.7 g, 0.093 mol, yield 93%).
  • Methyl 2-(methylsulfonyl)acetate (15.2g, 0.1mol), 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10 -Heptadecafluorodecan-1-ol (51.1 g, 0.11 mol) and K 2 CO 3 (13.8 g, 0.1 mol) were added to 100 mL of acetonitrile and stirred at 40°C for 24 hours. After confirming that all of the raw material methyl 2-(methylsulfonyl)acetate had disappeared by gas chromatography, the mixture was cooled to room temperature, filtered to remove solids, and the solvent was distilled off. Next, the residue was extracted using 100 g of methylene chloride and 100 g of distilled water, and the organic solvent was distilled off to obtain the title compound (54.3 g, 0.093 mol, yield 93%).
  • Ethylene carbonate (EC) and a compound represented by the following formula 1-1 were mixed at a volume ratio of 3:7.
  • LiPF 6 as a lithium salt was mixed with the mixed solution at a concentration of 1.0 mol/L to prepare 1M LiPF 6 /EC: non-aqueous electrolyte solution of Chemical Formula 1-1.
  • Formula 1-2 non-aqueous electrolyte was prepared in the same manner as in Example 1, except that a compound represented by Formula 1-2 was used instead of the compound represented by Formula 1-1. did.
  • Formula 1-3 non-aqueous electrolyte was prepared in the same manner as in Example 1, except that a compound represented by Formula 1-3 was used instead of the compound represented by Formula 1-1. did.
  • Formula 1-6 non-aqueous electrolyte was prepared in the same manner as in Example 1, except that a compound represented by Formula 1-6 was used instead of the compound represented by Formula 1-1. did.
  • Formula 1-7 non-aqueous electrolyte was prepared in the same manner as in Example 1, except that a compound represented by Formula 1-7 was used instead of the compound represented by Formula 1-1. did.
  • Formula 1-8 non-aqueous electrolyte was prepared in the same manner as in Example 1, except that a compound represented by Formula 1-8 was used instead of the compound represented by Formula 1-1. did.
  • Formula 1-9 non-aqueous electrolyte was prepared in the same manner as in Example 1, except that a compound represented by Formula 1-9 was used instead of the compound represented by Formula 1-1. did.
  • Formula 1-10 non-aqueous electrolyte was prepared in the same manner as in Example 1, except that a compound represented by Formula 1-10 was used instead of the compound represented by Formula 1-1. did.
  • Ethylene carbonate (EC) and ethylmethyl carbonate (EMC) were mixed in a volume ratio of 3:7.
  • LiPF 6 as a lithium salt was mixed in the mixed solution at a concentration of 1.0 mol/L, and 1 wt% fluoroethylene carbonate (FEC) was mixed as an additive to prepare a 1M LiPF 6 /EC:EMC + 1 wt% FEC non-aqueous electrolyte.
  • a 1M LiPF 6 /EC:Formula a non-aqueous electrolyte solution was prepared in the same manner as in Example 1, except that a compound represented by Formula a below was used instead of the compound represented by Formula 1-1.
  • Li 1.13 Mn 0.463 Ni 0.203 Co 0.203 O 2 (0.3Li 2 MnO 3 ⁇ 0.7LiMn 1/3 Ni 1/3 Co 1/3 O 2 ) as the positive electrode active material, graphite as the negative electrode active material, and the above examples.
  • the chemical conversion process was performed by charging and discharging in the 3.0-4.5V voltage range with a charging voltage of 4.5V at 0.2C. .
  • the non-aqueous electrolyte solution prepared in the above Examples and Comparative Examples was left at room temperature (25°C) for 24 hours, then visually observed for the presence or absence of undissolved precipitates, and solubility was evaluated according to the following evaluation criteria.
  • the secondary battery was discharged to SOC 50% at a constant current of 0.2C in a fully charged state, and after a 1-hour rest period, it was discharged at a constant current of 1.5C for 10 seconds. In the next process, after a pause of 40 seconds, it was charged with a constant current of 1.125C.
  • the initial direct current resistance (DC-IR, R dis ) was calculated from the discharge data using Equation 1 below.
  • ⁇ V represents OCV dis (voltage just before 10 second discharge starts) - V dis (10 second discharge end voltage), and I is the current value during discharge.
  • the secondary battery was charged at 1C to 4.5V at room temperature (25°C), discharged at 1C at 2.75V, then charged at 1C to 4.2V and discharged at 1C at 2.75V for 500 cycles to obtain the discharge capacity in the first cycle and discharge in the 500th cycle.
  • the capacity maintenance rate (%) was evaluated according to Equation 2 below.
  • Capacity maintenance rate [%] [Discharge capacity in the 500th cycle / Discharge capacity in the 1st cycle] ⁇ 100
  • the time from removing the torch until extinguishment was measured to determine the self-extinguishing time (SET) in seconds per weight of the non-aqueous electrolyte. , sg -1) was measured, and the same test was repeated more than 4 times to obtain the average SET value.
  • the ignition characteristics of the non-aqueous electrolyte were evaluated according to the following evaluation criteria.
  • Non-flammable SET value less than 6 sg -1
  • Flammability SET value > 20 sg -1
  • the non-aqueous electrolyte solutions of Examples 1 to 8 containing the compound represented by Formula 1 as a solvent according to the present invention have excellent flame retardancy and excellent battery characteristics without insufficient solubility in lithium salts. You can check it.

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Abstract

La présente invention concerne : un solvant fluoré ayant une structure spécifique ; un électrolyte non aqueux pour une batterie secondaire, comprenant un sel de lithium et le solvant fluoré ; et une batterie secondaire comprenant l'électrolyte non aqueux. Un éther fluoré contenant un groupe sulfone ou un composé ester ayant une structure spécifique, selon la présente invention, a une faible viscosité et une excellente ininflammabilité sans solubilité déficiente d'un sel de lithium. Par conséquent, le composé éther ou ester fluoré contenant un groupe sulfone selon la présente invention peut être utilisé de manière avantageuse en tant que solvant d'un électrolyte non aqueux pour une batterie secondaire et, en particulier, permet d'obtenir d'excellentes caractéristiques de batterie et une excellente ininflammabilité.
PCT/KR2023/005572 2022-04-25 2023-04-24 Composé d'alkylsulfone fluoré et électrolyte non aqueux pour batterie secondaire et batterie secondaire le comprenant Ceased WO2023211103A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025102763A1 (fr) * 2023-11-17 2025-05-22 宁德时代新能源科技股份有限公司 Électrolyte pour batterie secondaire au lithium-métal, batterie secondaire et dispositif électrique

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120141870A1 (en) * 2010-12-07 2012-06-07 E. I. Du Pont De Nemours And Company Multifunctional sulfone/fluorinated ester solvents
CN103755604A (zh) * 2014-01-20 2014-04-30 湖南有色郴州氟化学有限公司 氢氟醚砜类化合物及其制备方法、锂离子电池电解液
JP2019169305A (ja) * 2018-03-22 2019-10-03 富山薬品工業株式会社 蓄電デバイス用非水電解液

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150088913A (ko) 2011-03-24 2015-08-03 닛본 덴끼 가부시끼가이샤 2차 전지
WO2019039763A1 (fr) 2017-08-22 2019-02-28 리켐주식회사 Électrolyte pour batterie secondaire au lithium et batterie secondaire au lithium le comprenant
EP3706227A4 (fr) 2017-10-31 2021-09-08 Kanto Denka Kogyo Co., Ltd. Solution électrolytique non aqueuse et batterie à électrolyte non aqueux

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120141870A1 (en) * 2010-12-07 2012-06-07 E. I. Du Pont De Nemours And Company Multifunctional sulfone/fluorinated ester solvents
CN103755604A (zh) * 2014-01-20 2014-04-30 湖南有色郴州氟化学有限公司 氢氟醚砜类化合物及其制备方法、锂离子电池电解液
JP2019169305A (ja) * 2018-03-22 2019-10-03 富山薬品工業株式会社 蓄電デバイス用非水電解液

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE Registry 11 February 2016 (2016-02-11), ANONYMOUS: "Propanoic acid, 3-(methylsulfonyl)-, 2,2-difluoroethyl ester (CA INDEX NAME)", XP093103185, retrieved from STNext Database accession no. 1864391-36-5 *
DATABASE Registry 2 March 2016 (2016-03-02), ANONYMOUS: "Acetic acid, 2-(methylsulfonyl)-, 2,2,2-trifluoroethyl ester (CA INDEX NAME)", XP093103183, retrieved from STNext Database accession no. 1878044-76-8 *
YUE ZHENG; MEI XINYI; DUNYA HAMZA; MA QIANG; MCGARRY CHRISTOPHER; MANDAL BRAJA K.: "Synthesis and physical properties of new fluoroether sulfones", JOURNAL OF FLUORINE CHEMISTRY, ELSEVIER, NL, vol. 216, 28 October 2018 (2018-10-28), NL , pages 118 - 123, XP085533191, ISSN: 0022-1139, DOI: 10.1016/j.jfluchem.2018.10.014 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025102763A1 (fr) * 2023-11-17 2025-05-22 宁德时代新能源科技股份有限公司 Électrolyte pour batterie secondaire au lithium-métal, batterie secondaire et dispositif électrique

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