WO2024128672A1 - Composé pour électrolyte, composé pour additif d'électrolyte, matériau d'électrolyte, additif d'électrolyte, électrolyte pour batterie secondaire, et batterie secondaire - Google Patents

Composé pour électrolyte, composé pour additif d'électrolyte, matériau d'électrolyte, additif d'électrolyte, électrolyte pour batterie secondaire, et batterie secondaire Download PDF

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WO2024128672A1
WO2024128672A1 PCT/KR2023/019968 KR2023019968W WO2024128672A1 WO 2024128672 A1 WO2024128672 A1 WO 2024128672A1 KR 2023019968 W KR2023019968 W KR 2023019968W WO 2024128672 A1 WO2024128672 A1 WO 2024128672A1
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substituted
group
unsubstituted
secondary battery
electrolyte
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Korean (ko)
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제종태
김기석
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Rexcel Co Ltd
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Rexcel Co Ltd
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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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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 compounds for electrolyte solutions, compounds for electrolyte solution additives, electrolyte materials, electrolyte solution additives, electrolyte solutions for secondary batteries, and secondary batteries.
  • Lithium secondary batteries are used as a driving power source for portable electronic devices such as video cameras, mobile phones, and laptop computers.
  • Rechargeable lithium secondary batteries have more than three times the energy density per unit weight compared to existing lead storage batteries, nickel-cadmium batteries, nickel-hydrogen batteries, and nickel-zinc batteries, and can be charged at high speeds.
  • Organic electrolytes are generally used as electrolytes for lithium secondary batteries.
  • the organic electrolyte solution is prepared by dissolving lithium salt in an organic solvent.
  • the organic solvent is preferably stable at high voltage, has high ionic conductivity and dielectric constant, and has low viscosity.
  • One object of the present invention is to provide an electrolyte solution for secondary batteries containing a novel compound or an isomer thereof.
  • Another object of the present invention is to provide a secondary battery containing the electrolyte solution for secondary batteries.
  • an embodiment of the present invention provides an electrolyte solution for a secondary battery containing a compound of the following formula (1), or an isomer thereof.
  • X is oxygen or sulfur
  • Y is oxygen or sulfur
  • Q 1 , Q 2 , and Q 3 are each independently hydrogen, substituted or unsubstituted C 1-12 amine, substituted or unsubstituted C 2-12 heterocycloalkyl containing nitrogen, or substituted C 2-12 heterocycloalkyl containing nitrogen. or unsubstituted C 3-20 heteroaryl;
  • Another embodiment of the present invention is,
  • An electrode assembly including an anode, a cathode, and a separator separating the anode and the cathode;
  • a secondary battery containing the electrolyte solution accommodated in the case and immersing the electrode assembly.
  • a secondary battery containing an electrolyte for a secondary battery and an electrolyte solution additive according to the present invention may have improved lifespan performance.
  • Figure 1 shows a cross-sectional view of a secondary battery containing an electrolyte and an electrolyte additive according to an embodiment of the present invention.
  • Figure 2 shows the results of analyzing the room temperature lifespan performance of a secondary battery according to an embodiment of the present invention.
  • Figure 3 shows the results of analyzing high temperature lifespan performance for a secondary battery according to an embodiment of the present invention.
  • the term “isomer” refers to a compound of the present invention or a salt thereof that has the same chemical or molecular formula but is structurally or sterically different.
  • These isomers include structural isomers such as tautomers, stereoisomers such as R or S isomers with asymmetric carbon centers, geometric isomers (trans, cis), and optical isomers (enantiomers). All these isomers and mixtures thereof are also included within the scope of the present invention.
  • alkyl may be straight chain or branched unless otherwise specified, and the number of carbon atoms is not particularly limited, but may be 1 to 10. Specific examples of alkyl groups include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n.
  • -pentyl isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, etc., but are not limited to these.
  • alkenyl may be straight chain or branched and may mean alkyl containing one or more double bonds.
  • the number of carbon atoms is not particularly limited, but may be 2 to 10. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, etc., but are not limited to these.
  • alkynyl may be straight chain or branched, unless otherwise specified, and may mean alkyl containing one or more triple bonds.
  • the number of carbon atoms is not particularly limited, but may be 2 to 10. Specific examples include, but are not limited to, ethynyl group, propynyl group, butynyl group, and fentainyl group.
  • heteroalkyl refers to alkyl containing one or more of O, N, Si, B, Se, P, and S as heterogeneous elements, and the number of carbon atoms is not particularly limited, but may be 1 to 10.
  • heteroalkyl include -CH 2 -CH 2 -O-CH 3 , -CH 2 -CH 2 -NH-CH 3 , -CH 2 -CH 2 -N(CH 3 )-CH 3 , -CH 2 -S -CH 2 -CH 3 , etc., but are not limited to these.
  • heterocycloalkyl refers to cycloalkyl containing one or more of O, N, Si, B, Se, P and S as heterogeneous elements, and the number of carbon atoms is not particularly limited, but may be 2 to 12. there is.
  • heterocycloalkyl include, but are not limited to, epoxy, tetrahydrofuranyl, tetrahydropyranyl, tetrahydrothiophenyl, and tetrahydropyrrolyl.
  • aryl is not particularly limited, but has 6 to 20 carbon atoms; Or it may be 6 to 10.
  • the aryl group may be a monocyclic aryl group, such as a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto.
  • the polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, etc., but is not limited thereto.
  • heteroaryl refers to an aryl containing one or more of O, N, Si, B, Se, P, and S as heterogeneous elements, and the number of carbon atoms is not particularly limited, but may be 3 to 20.
  • heteroaryl examples include xanthene, thioxanthen, thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, Pyrimidyl group, triazine group, acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino Pyrazinyl group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, be
  • acyl refers to the residue obtained by removing OH from the carboxyl group -COOH of a carboxylic acid, and the number of carbon atoms is not particularly limited, but may be 1 to 10.
  • examples of acyl include, but are not limited to, acetyl group, propionyl group, malonyl group, and benzoyl group.
  • One aspect of the present invention provides an electrolyte solution for secondary batteries containing a novel compound or an isomer thereof.
  • the compound may have the following formula (1).
  • X is oxygen or sulfur
  • Y is oxygen or sulfur
  • Q 1 , Q 2 , and Q 3 are each independently hydrogen, substituted or unsubstituted C 1-12 amine, substituted or unsubstituted C 2-12 heterocycloalkyl containing nitrogen, or substituted C 2-12 heterocycloalkyl containing nitrogen. or unsubstituted C 3-20 heteroaryl;
  • the formula (1) may be the formula (2) or formula (3) below.
  • X is oxygen or sulfur
  • Y is oxygen or sulfur
  • Z 1 and Z 2 may be combined with each other to form a substituted or unsubstituted alicyclic ring containing one or more nitrogens, or a substituted or unsubstituted aromatic ring containing one or more nitrogens;
  • Each W 2 is independently hydrogen or substituted or unsubstituted C 1-10 alkyl
  • W 3 is substituted or unsubstituted C 2-12 heterocycloalkyl, substituted or unsubstituted C 3-10 cycloalkyl, substituted or unsubstituted C 1-10 alkyl, substituted or unsubstituted C 1-10 acyl. , or substituted or unsubstituted C 1-10 sulfonyl;
  • G is oxygen or sulfur
  • R 1 and R 2 are each independently hydrogen, substituted or unsubstituted C 1-10 alkyl, substituted or unsubstituted C 1-10 alkenyl, substituted or unsubstituted C 1-10 alkoxy, substituted or unsubstituted Substituted C 1-10 alkynyl, substituted or unsubstituted C 3-10 amine, substituted or unsubstituted C 3-10 cycloalkyl, substituted or unsubstituted C 2-12 heterocycloalkyl, substituted or unsubstituted C It may be 1-10 acyl, substituted or unsubstituted C 3-10 silyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 3-20 heteroaryl.
  • the substituted alkyl, alkenyl, alkynyl, amine, cycloalkyl, acyl, silyl, heteroalkyl, heterocycloalkyl, alkoxy, aryl, heteroaryl, cycloaliphatic ring, aromatic ring, or sulfonyl is a halogen group, an alkyl group, Alkenyl group, alkynyl group, heterocycloalkyl group, ketone group, thioketone group, alkoxy group, alkenyloxy group, alkynyloxy group, heteroaryl group, cycloalkyl group, hydroxy group, carboxyl group, carbonate group, amine group, silyl group, sulfo group.
  • nate group phosphate group, thiophosphate group, nitro group, cyano group, heteroalkyl group, aryl group, ether group, and acyl group.
  • the heterocycloalkyl group may be substituted with one or more substituents selected from the group consisting of a ketone group, a thioketone group, a halogen group, a nitro group, a cyano group, an alkyl group, an alkenyl group, or an alkynyl group.
  • Examples of cyclic ketones substituted with a ketone group include cyclohexanone, cyclophentanone, dihydro-2-furanone, and dihydro-2-thiophenone. 2-thiophenone), etc., but are not limited to these.
  • Examples of cyclic thioketones substituted with thioketone groups include cyclopentanethione, dihydro-2-furanthione, dihydro-2-thiophenethione, 3-methylthiazolidin-2-thione, etc., but is not limited to these.
  • the electrolyte solution for a secondary battery may further include one or more additives selected from the group consisting of LiPO 2 F 2 , unsaturated cyclic carbonate, cyclic sultone, nitrile compound, and mixtures thereof, but is not limited thereto.
  • the unsaturated cyclic carbonate includes, but is not limited to, vinylene carbonate (VC), vinylethylene carbonate (VEC), phenyl carbonate, allyl carbonate, catechol carbonate, ethynyl carbonate, and propargyl carbonate.
  • the cyclic sultone includes, but is not limited to, ethane sulton, propane sulton (PS), butane sulton, ethene sulton, butene sulton, and propene sulton (PS).
  • the nitrile compounds include succinonitrile, adiponitrile, glutaronitrile, acrylonitrile, methacrylonitrile, chloracrylonitrile, ethyl acrylonitrile, butyronitrile, propionitrile, and acetonitrile. It is not limited to
  • the electrolyte solution for a secondary battery may include at least one compound or isomer thereof selected from the group represented by the following formula:
  • the compounds of the present invention may have a chiral carbon center and therefore may exist as R or S isomers, racemic compounds, individual enantiomers or mixtures, individual diastereomers or mixtures, all of which are stereoisomers. and mixtures thereof may fall within the scope of the present invention.
  • the electrolyte compound may be included in an amount of about 0.1% by weight or more based on the total weight of the entire electrolyte solution, but is not limited thereto and an appropriate amount may be used within the above content range as needed.
  • the battery may expand due to excess gas, which may reduce lifespan characteristics.
  • the content of the electrolyte compound is 0.01 to 10% by weight, based on the total weight of the entire electrolyte solution; 0.01 to 9% by weight; 0.01 to 8% by weight; 0.01 to 7% by weight; 0.01 to 6% by weight; 0.01 to 5% by weight; 0.01 to 4% by weight; 0.01 to 3% by weight; 0.01 to 2% by weight; 0.01 to 1% by weight; 0.1 to 10% by weight; 0.1 to 9% by weight; 0.1 to 8% by weight; 0.1 to 7% by weight; 0.1 to 6% by weight; 0.1 to 5% by weight; 0.1 to 4% by weight; 0.1 to 3% by weight; 0.1 to 2% by weight; 0.1 to 1% by weight; 1 to 10% by weight; 1 to 9% by weight; 1 to 8% by weight; 1 to 7% by weight; 1 to 6% by weight; 1 to 5% by weight; 1 to 4% by weight; 0.1 to 3% by weight; 0.1 to 2% by weight; 0.1 to 1% by weight
  • the electrolyte solution for a secondary battery may further include a lithium salt or an organic solvent.
  • the concentration of the lithium salt in the electrolyte solution may be about 0.01 to 2.0M, but is not necessarily limited to this range and an appropriate concentration may be used as needed. Further improved battery characteristics can be obtained within the above concentration range.
  • the lithium salt used in the electrolyte is not particularly limited, and any lithium salt that can be used in the art can be used.
  • the organic solvent may include one or more selected from the group consisting of dialkyl carbonates, cyclic carbonates, linear or cyclic esters, linear or cyclic amides, aliphatic nitriles, linear or cyclic ethers, and derivatives thereof.
  • the organic solvent is dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), methylpropyl carbonate, ethylpropyl carbonate, diethyl carbonate (DEC), dipropyl carbonate, propylene carbonate (PC), and ethylene carbonate (EC).
  • DMC dimethyl carbonate
  • EMC ethylmethyl carbonate
  • DEC diethyl carbonate
  • PC propylene carbonate
  • EC ethylene carbonate
  • FEC fluoroethylene carbonate
  • butylene carbonate butylene carbonate
  • EP ethyl propionate
  • AN acetonitrile
  • SN succinonitrile
  • valerolactone may include one or more selected from the group consisting of valerolactone, gamma-butyrolactone, and tetrahydrofuran, but is not necessarily limited to these, and any organic solvent that can be used in organic electrolytes in the art is possible.
  • the compound of Formula 1 may be provided as an electrolyte solution additive.
  • Another aspect of the present invention provides a secondary battery including the electrolyte solution for secondary batteries.
  • the secondary battery includes an electrode assembly including a positive electrode, a negative electrode, and a separator separating the positive electrode and the negative electrode;
  • It may include an electrolyte solution for a secondary battery that is accommodated in the case and immerses the electrode assembly.
  • the form of the secondary battery is not particularly limited, and includes, but is not limited to, lithium ion batteries, lithium ion polymer batteries, lithium sulfur batteries, and lithium air batteries.
  • the secondary battery is a lithium ion battery, it can be manufactured by the following method.
  • the anode is prepared.
  • a positive electrode active material composition is prepared by mixing a positive electrode active material, a conductive material, a binder, and a solvent.
  • a positive electrode plate is manufactured by coating the positive electrode active material composition directly on a metal current collector.
  • the positive electrode active material composition may be cast on a separate support, and then the film peeled from the support may be laminated on a metal current collector to produce a positive electrode plate.
  • the positive electrode is not limited to the forms listed above and may have forms other than those listed above.
  • the positive electrode active material is a lithium-containing metal oxide, and any material commonly used in the industry can be used without limitation.
  • any material commonly used in the industry can be used without limitation.
  • one or more types of complex oxides of lithium and a metal selected from cobalt, manganese, nickel, and combinations thereof can be used, and specific examples thereof include Li a A 1-b B b D 2 (above where 0.90 ⁇ a ⁇ 1.8, and 0 ⁇ b ⁇ 0.5); Li a E 1-b B b O 2-c D c (in the above formula, 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05); LiE 2-b B b O 4-c D c (wherein 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05); Li a Ni 1-bc Co b B c D ⁇ (wherein 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5,
  • A is Ni, Co, Mn, or a combination thereof
  • B is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element, or a combination thereof
  • D is O, F, S, P, or a combination thereof
  • E is Co, Mn, or a combination thereof
  • F is F, S, P, or a combination thereof
  • G is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or a combination thereof
  • Q is Ti, Mo, Mn, or a combination thereof
  • I is Cr, V, Fe, Sc, Y, or a combination thereof
  • J is V, Cr, Mn, Co, Ni, Cu, or a combination thereof.
  • the compound having a coating layer on the surface may be used, or a mixture of the above compound and a compound having a coating layer may be used.
  • This coating layer may include a coating element compound of an oxide, hydroxide, oxyhydroxide of the coating element, oxycarbonate of the coating element, or hydroxycarbonate of the coating element.
  • the compounds that make up these coating layers may be amorphous or crystalline.
  • Coating elements included in the coating layer may include Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, or mixtures thereof.
  • any coating method may be used as long as the above compounds can be coated with these elements in a manner that does not adversely affect the physical properties of the positive electrode active material (e.g., spray coating, dipping method, etc.). Since this is well-understood by people working in the field, detailed explanation will be omitted.
  • Carbon black, graphite particles, etc. may be used as the conductive material, but are not limited to these, and any material that can be used as a conductive material in the relevant technical field can be used.
  • the binder includes vinylidene fluoride/hexafluoropropylene copolymer, polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethyl methacrylate, polytetrafluoroethylene and mixtures thereof, or styrene butadiene rubber-based polymer, etc. may be used, but is not limited to these and any binder that can be used as a binder in the art may be used.
  • the solvent may be N-methylpyrrolidone, acetone, or water, but is not limited to these and any solvent that can be used in the art can be used.
  • the contents of the positive electrode active material, conductive material, binder, and solvent are levels commonly used in lithium ion batteries. Depending on the use and configuration of the lithium ion battery, one or more of the conductive material, binder, and solvent may be omitted.
  • a negative electrode active material composition is prepared by mixing a negative electrode active material, a conductive material, a binder, and a solvent.
  • the negative electrode active material composition is directly coated and dried on a metal current collector to produce a negative electrode plate.
  • the negative electrode active material composition may be cast on a separate support, and then the film peeled from the support may be laminated on a metal current collector to produce a negative electrode plate.
  • the negative electrode active material can be any material that can be used as a negative electrode active material for a lithium ion battery in the art.
  • it may include one or more selected from the group consisting of lithium metal, metal alloyable with lithium, transition metal oxide, non-transition metal oxide, and carbon-based material.
  • the metal alloyable with lithium is Si, Sn, Al, Ge, Pb, Bi, Sb Si-Y alloy (Y is an alkali metal, alkaline earth metal, Group 13 element, Group 14 element, transition metal, rare earth element or a combination thereof, but not Si), Sn-Y alloy (where Y is an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, a transition metal, a rare earth element, or a combination thereof, but not Sn. ), etc.
  • 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 Se, Te, Po, or a combination thereof.
  • the transition metal oxide may be lithium titanium oxide, vanadium oxide, lithium vanadium oxide, etc.
  • the non-transition metal oxide may be SnO 2 , SiO x (0 ⁇ x ⁇ 3), etc.
  • the carbon-based material may be crystalline carbon, amorphous carbon, or a mixture thereof.
  • the crystalline carbon may be amorphous, plate-shaped, flake-shaped, spherical or fibrous, such as natural graphite or artificial graphite, and the amorphous carbon may be soft carbon (low-temperature sintered carbon) or hard carbon. carbon), mesophase pitch carbide, calcined coke, etc.
  • the same conductive material and binder as those in the positive electrode active material composition may be used.
  • the contents of the negative electrode active material, conductive material, binder, and solvent are levels commonly used in lithium ion batteries. Depending on the use and configuration of the lithium ion battery, one or more of the conductive material, binder, and solvent may be omitted.
  • a separator is prepared to separate the anode and cathode.
  • any separator commonly used in lithium ion batteries can be used.
  • An electrolyte that has low resistance to ion movement and has excellent electrolyte moisturizing ability can be used.
  • it is selected from glass fiber, polyester, Teflon, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), or combinations thereof, and may be in the form of non-woven or woven fabric.
  • PTFE polytetrafluoroethylene
  • a rollable separator such as polyethylene or polypropylene may be used in a lithium ion battery, and a separator with excellent organic electrolyte impregnation ability may be used in a lithium ion polymer battery.
  • the separator may be manufactured according to the following method.
  • a separator composition is prepared by mixing polymer resin, filler, and solvent.
  • the separator composition may be directly coated and dried on the top of the electrode to form a separator.
  • the separator film peeled from the support is laminated on the top of the electrode to form a separator.
  • the polymer resin used to manufacture the separator is not particularly limited, and any materials used in the binder of the electrode plate can be used.
  • any materials used in the binder of the electrode plate can be used.
  • vinylidene fluoride/hexafluoropropylene copolymer polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethyl methacrylate, or mixtures thereof may be used.
  • the secondary battery 1 includes an anode 40, a cathode 60, and a separator 50.
  • the above-described anode 40, cathode 60, and separator 50 are wound or folded and accommodated in the cases 10 and 80.
  • electrolyte is injected into the cases 10 and 80 to complete the secondary battery 1.
  • the case may have various shapes depending on the purpose and design standard of the secondary battery, and may be formed to have various sizes and shapes, such as square, thin film, or coin shape.
  • the secondary battery may be a coin-type battery.
  • the secondary battery may be a lithium ion battery.
  • An electrode assembly may be formed by placing a separator between the anode and the cathode.
  • the electrode assembly is stacked in a bi-cell structure and then impregnated with an electrolyte solution. When the resulting product is placed in a pouch and sealed, a lithium ion polymer battery is completed.
  • a plurality of electrode assemblies are stacked to form a battery pack, and this battery pack can be used in all devices that require high capacity and high output. For example, it can be used in laptops, smartphones, electric vehicles, etc.
  • DL-homocysteine thiolactone hydrochloride (20.0 g, 0.130 mol) and dichloromethane (144 mL) were added to a 500 mL three-neck reactor, and triethylamine (31.6 g, 0.312 mol) was added dropwise at room temperature - Cooled to 20 degrees. When cooling was completed, methanesulfonyl chloride (17.9 g, 0.156 mol) was slowly added dropwise to the reaction solution and stirred for 1 hour.
  • DL-homocysteine thiolactone hydrochloride (20.0 g, 0.130 mol) and dichloromethane (250 mL) were added to a 500 mL three-neck reactor, and triethylamine (29.0 g, 0.286 mol) was added dropwise at room temperature - Cooled to 20 degrees.
  • a solution of triphosgene (13.5 g, 0.046 mol) dissolved in dichloromethane (50 mL) was slowly added dropwise and stirred for 1 hour.
  • the reaction solution and water 400 mL were added to a 1L Erlenmeyer flask, stirred strongly, and then filtered. After the filtrate was separated into layers, the organic layer was concentrated.
  • the concentrated solid, ethyl acetate (160 mL), and acetone (80 mL) were added to a 500 mL one-neck reactor and refluxed for 10 minutes.
  • the solution was cooled to room temperature and filtered.
  • the filtered solid, ethyl acetate (100 mL), and acetone (50 mL) were added to a 500 mL one-neck reactor and refluxed for 10 minutes.
  • the solution was cooled to room temperature and filtered.
  • the filtered solid was dried.
  • DL-homocysteine thiolactone hydrochloride (8.0 g, 0.052 mol) and dichloromethane (86 mL) were added to a 500 mL three-neck reactor, and triethylamine (12.7 g, 0.125 mol) was added dropwise at room temperature - Cooled to 20 degrees. When cooling was completed, diethyl chlorophosphate (10.8 g, 0.062 mol) was slowly added dropwise to the reaction solution and stirred for 1 hour.
  • LiPF 6 1.0M LiPF 6 was dissolved in a solvent mixed with ethylene carbonate (EC):ethylmethyl carbonate (EMC):dimethyl carbonate (DMC) in a volume ratio of 20:40:40.
  • EC ethylene carbonate
  • EMC ethylmethyl carbonate
  • DMC dimethyl carbonate
  • LiNi 0.6 Mn 0.2 Co 0.2 O 2 96% by weight, 2% by weight superP (TIMCAL) as a conductive material, 2% by weight polyvinylidene fluoride (PVdF, Sigma-Aldrich) were mixed and added to N-methyl-2-pyrrolidone solvent.
  • a cathode active material slurry was prepared by stirring for 30 minutes using a mechanical stirrer. The slurry was applied to a thickness of 60 ⁇ m on a 20 ⁇ m thick aluminum current collector using a doctor blade, dried in a hot air dryer at 100°C for 1 hour, dried again in vacuum for 8 hours, and rolled to form a positive electrode plate. was manufactured.
  • a lithium battery was manufactured using polypropylene with a thickness of 14 ⁇ m as a separator and the organic electrolyte solutions prepared in Comparative Example 1, Example 1, and Example 2 as the electrolyte solution.
  • lithium secondary batteries charge at 1.0 C-rate up to 4.2V under constant current/constant voltage (CC/CV) conditions at 25°C, then cut-off at 0.05 C-rate while maintaining 4.2V in constant voltage mode. Next, it was discharged at 1.0 C-rate until 2.7 V. The above charging and discharging conditions were repeated for 1 cycle and up to 100 cycles.
  • CC/CV constant current/constant voltage
  • the lithium batteries of Examples 1 and 2 containing the additive of the present invention had a capacity retention rate of 3.8% and 3.8% at room temperature, respectively, compared to the lithium battery of Comparative Example 1 containing vinyl carbonate. It improved by 1.6%.
  • Comparative Example 1 contained the additive at a concentration of 1.0% by weight, and Examples 1 and 2 contained a lower concentration of 0.5% by weight. Despite containing a lower concentration of the additive, it had a better shelf life at room temperature. Confirmed. Additionally, in Example 3, it can be seen that the capacity retention rate increases by 4.3% when combined with vinyl carbonate.
  • lithium secondary batteries charge at 1.0 C-rate up to 4.2V under constant current/constant voltage (CC/CV) conditions at 45°C, then cut-off at 0.05 C-rate while maintaining 4.2V in constant voltage mode. Next, it was discharged at 1.0 C-rate until 2.7 V. The above charging and discharging conditions were repeated for 1 cycle and up to 100 cycles.
  • CC/CV constant current/constant voltage
  • the lithium batteries of Examples 4, 5, and 6 containing the additive of the present invention had a capacity retention rate of 1.6% at high temperature compared to the lithium battery of Comparative Example 2 containing vinyl carbonate. ,0.4% and 1.1% improved.
  • Comparative Example 1 contained additives at a concentration of 1.0% by weight, and Examples 4, 5, and 6 contained a lower concentration of 0.1% by weight. Despite containing a lower concentration of additives, they showed better high-temperature lifespan. Confirmed to have it.
  • DC-IR Resistance measurement
  • the additive of the present invention has an excellent resistance increase rate even at room temperature and high temperature, and through this, it was confirmed that the additive of the present invention plays a role in increasing the lifespan of secondary battery operation.

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Abstract

La présente invention concerne un composé pour un électrolyte, un composé pour un additif d'électrolyte, un matériau d'électrolyte, un additif d'électrolyte, un électrolyte pour une batterie secondaire, et une batterie secondaire, et concerne en particulier un électrolyte pour une batterie secondaire, l'électrolyte comprenant un nouveau composé ou un isomère de celui-ci.
PCT/KR2023/019968 2022-12-15 2023-12-06 Composé pour électrolyte, composé pour additif d'électrolyte, matériau d'électrolyte, additif d'électrolyte, électrolyte pour batterie secondaire, et batterie secondaire Ceased WO2024128672A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20220176335 2022-12-15
KR10-2022-0176335 2022-12-15
KR10-2023-0172627 2023-12-01
KR1020230172627A KR102962502B1 (ko) 2022-12-15 2023-12-01 전해액용 화합물, 전해액 첨가제용 화합물, 전해액 물질, 전해액 첨가제, 이차 전지용 전해액 및 이차 전지

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WO2024128672A1 true WO2024128672A1 (fr) 2024-06-20

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PCT/KR2023/019968 Ceased WO2024128672A1 (fr) 2022-12-15 2023-12-06 Composé pour électrolyte, composé pour additif d'électrolyte, matériau d'électrolyte, additif d'électrolyte, électrolyte pour batterie secondaire, et batterie secondaire

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07282846A (ja) * 1994-04-07 1995-10-27 Matsushita Electric Ind Co Ltd 非水電解質電池
JP2004014351A (ja) * 2002-06-07 2004-01-15 Matsushita Electric Ind Co Ltd 非水電解質二次電池
KR101137747B1 (ko) * 2005-06-10 2012-04-25 미쓰비시 가가꾸 가부시키가이샤 비수계 전해액 및 비수계 전해액 이차 전지, 그리고 카보네이트 화합물
JP2017174543A (ja) * 2016-03-22 2017-09-28 三菱ケミカル株式会社 非水系電解液、及びそれを用いた非水系電解液二次電池
KR20180119345A (ko) * 2017-04-25 2018-11-02 삼성에스디아이 주식회사 리튬 이차 전지용 전해질 및 이를 포함하는 리튬 이차 전지

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07282846A (ja) * 1994-04-07 1995-10-27 Matsushita Electric Ind Co Ltd 非水電解質電池
JP2004014351A (ja) * 2002-06-07 2004-01-15 Matsushita Electric Ind Co Ltd 非水電解質二次電池
KR101137747B1 (ko) * 2005-06-10 2012-04-25 미쓰비시 가가꾸 가부시키가이샤 비수계 전해액 및 비수계 전해액 이차 전지, 그리고 카보네이트 화합물
JP2017174543A (ja) * 2016-03-22 2017-09-28 三菱ケミカル株式会社 非水系電解液、及びそれを用いた非水系電解液二次電池
KR20180119345A (ko) * 2017-04-25 2018-11-02 삼성에스디아이 주식회사 리튬 이차 전지용 전해질 및 이를 포함하는 리튬 이차 전지

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