Compounds for electrolytes, compounds for electrolyte additives, electrolyte substances, electrolyte additives, electrolytes for secondary batteries and secondary batteries

Abstract

The present invention relates to compounds for electrolytes, compounds for electrolyte additives, electrolyte substances, electrolyte additives, electrolytes for secondary batteries, and secondary batteries, and provides an electrolyte for secondary batteries containing a novel compound or its isomer.

Description

[Technical Field]

[0001] The present invention relates to compounds for electrolytes, compounds for electrolyte additives, electrolyte substances, electrolyte additives, electrolytes for secondary batteries, and secondary batteries. [Background technology]

[0002] Lithium-ion batteries are used as power sources for portable electronic devices such as video cameras, mobile phones, and laptop computers. Rechargeable lithium-ion batteries have more than three times the energy density per unit weight compared to conventional lead-acid batteries, nickel-cadmium batteries, nickel-metal hydride batteries, and nickel-zinc batteries, and can be rapidly charged.

[0003] Because lithium secondary batteries operate at high drive voltages, highly reactive aqueous electrolytes cannot be used. Generally, organic electrolytes are used as electrolytes for lithium secondary batteries. Organic electrolytes are manufactured by dissolving lithium salts in an organic solvent. Organic solvents are preferably stable at high voltages, have high ionic conductivity and dielectric constant, and have low viscosity.

[0004] On the other hand, the voltage, lifespan, capacity, and stability of a battery can vary significantly depending on the materials used for the negative electrode, positive electrode, and electrolyte. Therefore, there is a need for lithium-ion battery electrolytes that can provide lithium-ion batteries with improved lifespan characteristics and high-temperature stability. [Overview of the project] [Problems that the invention aims to solve]

[0005] The object of the present invention is to provide an electrolyte for secondary batteries containing a novel compound or its isomer.

[0006] Another object of the present invention is to provide a secondary battery containing the electrolyte for secondary batteries. [Means for solving the problem]

[0007] To achieve the above object, one embodiment of the present invention provides an electrolyte for a secondary battery containing a compound of Chemical Formula 1 below or an isomer thereof.

[0008] An electrolyte for a secondary battery containing a compound represented by Chemical Formula 1 below or an isomer thereof: [Chemical Formula 1]

Chemical

[0009] In one embodiment of the present invention, the substituted alkyl, alkenyl, amine, acyl, alkynyl, cycloalkyl, silyl, alkoxy, heteroalkyl, and heterocycloalkyl groups may each be independently substituted with one or more substituents selected from the group consisting of alkoxy groups, alkynyloxy groups, heteroaryl groups, alkenyl groups, heterocycloalkyl groups, carbonyl groups, halogen groups, hydroxyl groups, alkenyloxy groups, carboxyl groups, carbonate groups, alkyl groups, alkynyl groups, amine groups, cycloalkyl groups, silyl groups, sulfonate groups, phosphate groups, thiophosphate groups, nitro groups, cyano groups, heteroalkyl groups, cycloalkyl groups, aryl groups, and ether groups.

[0010] In one embodiment of the present invention, the electrolyte may further comprise one or more additives selected from the group consisting of LiPO2F2, unsaturated cyclic carbonates, cyclic sultones, cyclic sulfetralactones, nitrile compounds, and mixtures thereof.

[0011] In one embodiment of the present invention, the unsaturated cyclic carbonate may be selected from the group consisting of vinylene carbonate, phenyl carbonate, vinyl carbonate, and allyl carbonate.

[0012] In one embodiment of the present invention, the electrolyte may further contain an organic solvent.

[0013] In another aspect of the present invention, a lithium-ion battery is provided that includes the non-aqueous electrolyte for secondary batteries.

[0014] In one embodiment of the present invention, a secondary battery can be provided which includes an electrode assembly comprising a positive electrode, a negative electrode, and a separator separating the positive electrode and the negative electrode, a case for housing the electrode assembly, and an electrolyte solution housed in the case and immersing the electrode assembly. [Effects of the Invention]

[0015] A secondary battery containing the electrolyte additive and electrolyte for secondary batteries according to the present invention can improve the lifespan performance at room temperature. [Brief explanation of the drawing]

[0016] [Figure 1] A cross-sectional view of a secondary battery including an electrolyte and an electrolyte additive according to one embodiment of the present invention is shown. [Figure 2] This figure shows the results of an analysis of the lifespan performance at room temperature for a secondary battery according to one embodiment of the present invention. [Figure 3] This figure shows the results of an analysis of the lifespan performance at room temperature for a secondary battery according to one embodiment of the present invention. [Figure 4] This figure shows the results of an analysis of the lifespan performance at room temperature for a secondary battery according to one embodiment of the present invention. [Figure 5] This figure shows the results of an analysis of the lifespan performance at room temperature for a secondary battery according to one embodiment of the present invention. [Modes for carrying out the invention]

[0017] One embodiment of the present invention is shown in the accompanying drawings. However, the spirit of the present invention can be embodied in many other forms and should not be construed as being limited to the embodiments described herein. Rather, these embodiments are provided so as to make the present disclosure thorough and complete and will fully convey the scope of the spirit of the invention to a person of ordinary skill in the art. The same reference numerals in the drawings refer to the same components.

[0018] The terms used herein are for the purpose of describing specific embodiments only and do not limit the ideas of the invention. The singular form used herein is intended to include multiple forms, including “at least one,” unless explicitly indicated otherwise in the text. “At least one” should not be construed as limiting to the singular. As used herein, the term “and / or” includes all any combination of one or more of the listed items. The terms “include” and / or “contain” as used in the detailed description identify the presence of the described features, regions, integers, steps, operations, components, and / or ingredients, and do not exclude the presence or addition of one or more other features, regions, integers, steps, operations, components, ingredients, and / or groups thereof.

[0019] Unless otherwise defined, all terms used herein (including technical and scientific terms) have the same meaning as they would be generally understood by a person of ordinary skill in the art to which this disclosure belongs. Furthermore, it will be understood that terms defined in commonly used dictionaries should be interpreted as having the meaning consistent with their meaning in the context of the relevant art and this disclosure, and not as idealized or overly formal.

[0020] While specific embodiments are described, alternatives, modifications, variations, improvements, and substantial equivalents not currently anticipated or foreseeable may occur to the applicant or those skilled in the art. Therefore, the attached claims, which may be filed and amended, are intended to include all such alternatives, modifications, variations, improvements, and substantial equivalents.

[0021] In this invention, the term "isomer" refers to a compound or salt thereof of the present invention that has the same chemical or molecular formula but is structurally or sterically different. Such 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. All of these isomers and mixtures thereof are also within the scope of this invention.

[0022] In this invention, the term "alkyl" may refer to a linear or branched chain unless otherwise specified, and the number of carbon atoms is not particularly limited but may range from 1 to 7. Specific examples of alkyl groups include, but are not limited to, 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, and n-heptyl.

[0023] In this specification, the term "alkenyl" may refer to an alkyl group containing one or more double bonds, whether linear or branched, unless otherwise specified. The number of carbon atoms is not particularly limited, but may range from 2 to 6. Specific examples include, but are not limited to, vinyl, 1-profenyl, isoprofenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1-butenyl, and 1,3-butadienyl.

[0024] In this specification, the term "alkynyl" may refer to an alkyl group containing one or more triple bonds, whether linear or branched, unless otherwise specified. The number of carbon atoms is not particularly limited, but may range from 2 to 6. Specific examples include, but are not limited to, ethynyl, propanyl, butynyl, and pentynyl groups.

[0025] The term "amine" as used herein may be selected from the group consisting of -NH2, alkylamine group, N-alkylarylamine group, arylamine group, N-arylheteroarylamine group, N-alkylheteroarylamine group, and heteroarylamine group, and the number of carbon atoms is not particularly limited, but may be 1 to 30. More specific examples of amine groups include, but are not limited to, methylamine group, dimethylamine group, ethylamine group, diethylamine group, phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, 9-methyl-anthracenylamine group, diphenylamine group, ditolylamine group, N-phenyltolylamine group, triphenylamine group, N-phenylbiphenylamine group, N-phenylnaphthylamine group, N-biphenylnaphthylamine group, N-naphthylfluorenylamine group, N-phenylphenantrenylamine group, N-biphenylphenantrenylamine group, N-phenylfluorenylamine group, N-phenylterphenylamine group, N-phenantrenylfluorenylamine group, and N-biphenylfluorenylamine group.

[0026] In this specification, the term "heteroalkyl" refers to an alkyl group containing one or more heteroatoms from O, N, Si, B, Se, P, and S, and the number of carbon atoms is not particularly limited, but can range from 1 to 6. Examples of heteroalkyl groups include, but are not limited to, -CH2-CH2-O-CH3, -CH2-CH2-NH-CH3, -CH2-CH2-N(CH3)-CH3, and -CH2-S-CH2-CH3.

[0027] In this specification, the term "cycloalkyl" refers to a non-aromatic carbon ring, and the number of carbon atoms is not particularly limited, but may range from 3 to 12. Examples of cycloalkyls include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl.

[0028] In this specification, the term "heterocycloalkyl" refers to a cycloalkyl compound containing one or more heterogeneous elements from O, N, Si, B, Se, P, and S, and is not particularly limited in terms of the number of carbon atoms, but can range from 3 to 12. Examples of heterocycloalkyl compounds include, but are not limited to, epoxy, tetrahydrofuranyl, tetrahydropyranyl, tetrahydrothiophenyl, and tetrahydropyrrolyl.

[0029] The term "aryl" as used herein is not particularly limited, but may have 6 to 20 or 6 to 12 carbon atoms. Examples of monocyclic aryl groups include, but are not limited to, phenyl, biphenyl, and terphenyl groups. Examples of polycyclic aryl groups include, but are not limited to, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, ferrylenyl, clysenyl, and fluorenyl groups.

[0030] In this specification, the term "heteroaryl" refers to an aryl compound containing one or more of the following heteroatoms: O, N, Si, B, Se, P, and S. The number of carbon atoms is not particularly limited, but can range from 5 to 20. Examples of heteroaryl groups include, but are not limited to, 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, quinoline group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyradinyl group, pyrazinopyradinyl group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuran group, phenanthroline group, isoxazolyl group, thiadiazolyl group, phenothiazine group, and dibenzofuran group.

[0031] In this specification, the term "alkoxy" refers to an alkyl group bonded to oxygen, and oxygen can be bonded to the aforementioned alkyl group. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, and pentoxy groups.

[0032] In this specification, the term "acyl" refers to the residue remaining after removing the OH group from the carboxyl group (-COOH) of a carboxylic acid, and the number of carbon atoms is not particularly limited, but may range from 1 to 6. Examples of acyls include, but are not limited to, acetyl, propionyl, malonyl, and benzoyl groups.

[0033] The term "silyl" as used herein may be represented as -SiR3, and examples of silyls may be selected from, but are not limited to, alkylsilyl groups, arylsilyl groups, alkylarylsilyl groups, and heteroarylsilyl groups. More specific examples include, but are not limited to, trimethylsilyl groups, triethylsilyl groups, t-butyldimethylsilyl groups, vinyldimethylsilyl groups, propyldimethylsilyl groups, triphenylsilyl groups, diphenylsilyl groups, and phenylsilyl groups.

[0034] In this specification, the terms "substituted or unsubstituted" may mean substituted or unsubstituted with one or more groups selected from the group consisting of alkoxy groups, alkynyloxy groups, heteroaryl groups, alkenyl groups, heterocycloalkyl groups, carbonyl groups, halogen groups, hydroxyl groups, alkenyloxy groups, carboxyl groups, carbonate groups, alkyl groups, alkynyl groups, amine groups, cycloalkyl groups, silyl groups, sulfonate groups, phosphate groups, thiophosphate groups, nitro groups, cyano groups, heteroalkyl groups, cycloalkyl groups, aryl groups, and ether groups.

[0035] Furthermore, throughout this specification, the same symbol may have the same meaning unless otherwise specified.

[0036] The present invention relates to compounds for electrolytes, compounds for electrolyte additives, electrolyte substances, electrolyte additives, electrolytes for secondary batteries, and secondary batteries.

[0037] One aspect of the present invention provides an electrolyte for a secondary battery containing a novel compound or an isomer thereof. The aforementioned compound can be represented by the following chemical formula 1. [Chemical Formula 1] [ka]

[0038] In the above chemical formula 1, the carbon atoms in the ring are linked by single or double bonds, The aforementioned X is oxygen or sulfur, The aforementioned Y is oxygen or sulfur, Said Z 1 , Z 2 , and Z 3 These are, independently, hydrogen, substituted or unsubstituted C 1-10 Alkyl, substituted, or unsubstituted C 1-10 Alkenyl, substituted, or unsubstituted C 1-10 Amine, substituted or unsubstituted C 1-10 Acyl, substituted, or unsubstituted C 1-10 Alkynyl, substituted, or unsubstituted C 3-10 Cycloalkyl, substituted or unsubstituted silyl, substituted or unsubstituted C 1-10 alkoxy, substituted, or unsubstituted C 1-12 Heteroalkyl, substituted, or unsubstituted C 1-6 Heterocycloalkyl, -SO2R 1 , -P(=G)(OR 1 )2, -P(=G)(R 1 Selected from the group consisting of )2, Said Z 1 and Z 2 They may or may not be bonded to each other to form a ring. The aforementioned G is oxygen or sulfur, The aforementioned R 1 is a substitution or non-substitution C 1-6 Alkyl, C 2-6 Alkenil, C 2-6 Alkinyl or C 6-20It could be Ariel.

[0039] In one embodiment of the present invention, the compound represented by chemical formula 1 is a compound derived from a heterocyclic compound and can be added to the electrolyte as an additive for lithium secondary batteries. The additive of the present invention can form a stable SEI (Solid Electrolyte Interphase) film on the negative electrode surface while minimizing the increase in resistance of the lithium secondary battery. Therefore, it is possible to suppress the decrease in the passivation capacity of SEI at high temperatures, prevent deterioration of the negative electrode, and form a film that facilitates lithium movement, thereby improving the lifespan at room temperature. The compound represented by chemical formula 1 of the present invention is, specifically, the Z 1 Each of these independently consists of hydrogen, substituted or unsubstituted C 1-10 Alkyl, substituted, or unsubstituted C 1-10 Alkenyl, substituted, or unsubstituted C 1-10 Amine, substituted or unsubstituted C 1-10 Acyl, substituted, or unsubstituted C 1-10 Alkynyl, substituted, or unsubstituted C 3-10 Cycloalkyl, substituted or unsubstituted silyl, -SO2R 1 and -P(=G)(OR 1 Selected from the group consisting of )2, the Z 2 and Z 3 Each of these is 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 C 1-12 The group consisting of heteroalkyls may be selected.

[0040] The compound represented by chemical formula 1 of the present invention is, more specifically, the Z 1 Each of these independently consists of hydrogen, substituted or unsubstituted C 1-10 Alkenyl, substituted, or unsubstituted C 1-10 Acyl, substituted, or unsubstituted C 1-10 Alkinyl, -SO2R 1 Selected from the group consisting of the above Z 2 and Z3 Each of these is independently hydrogen, substituted or unsubstituted C 1-10 The group consisting of alkyl groups may be selected.

[0041] The substituted alkyl, alkenyl, amine, acyl, alkynyl, cycloalkyl, silyl, alkoxy, heteroalkyl, and heterocycloalkyl groups of the present invention may each be independently substituted with one or more substituents selected from the group consisting of alkoxy groups, alkynyloxy groups, heteroaryl groups, alkenyl groups, heterocycloalkyl groups, carbonyl groups, halogen groups, hydroxyl groups, alkenyloxy groups, carboxyl groups, carbonate groups, alkyl groups, alkynyl groups, amine groups, cycloalkyl groups, silyl groups, sulfonate groups, phosphate groups, thiophosphate groups, nitro groups, cyano groups, heteroalkyl groups, cycloalkyl groups, aryl groups, and ether groups. For example, the substituted alkoxy group may be substituted with an alkenyl group, an alkynyl group, an amine group, a cycloalkyl group, a carbonyl group, or a silyl group; the substituted heterocycloalkyl group may be substituted with a carbonyl group; the substituted carboxyl group may be substituted with a heteroaryl group, an alkenyl group, a heterocycloalkyl group, a carbonyl group substituted with a heterocycloalkyl group, or a halogen group; and the substituted carbonate group may be substituted with an alkyl group or an alkynyl group. Furthermore, the substituted sulfonate group may be substituted with an alkyl group, an alkenyl group, or a halogen-substituted alkyl group; and the substituted sulfonate group and the thiophosphate group may each be independently substituted with an alkyl group.

[0042] The electrolyte for the secondary battery of the present invention contains the compound represented by the chemical formula 1 as an additive, and may further contain additional additives. For example, it may further contain one or more additives selected from the group consisting of LiPO2F2, unsaturated cyclic carbonates, cyclic sultones, cyclic sulfetralactones, nitrile compounds, and mixtures thereof, but is not limited to these.

[0043] The unsaturated cyclic carbonate of the present invention is a cyclic carbonate having carbon-carbon unsaturated bonds, such as carbon-carbon double bonds or carbon-carbon triple bonds, and is not particularly limited; any unsaturated cyclic carbonate can be used.

[0044] As the additional additive of the present invention, the unsaturated cyclic carbonate can be one or more selected from the group consisting of vinylene carbonate, phenyl carbonate, vinyl carbonate, and allyl carbonate. As the vinylene carbonates, one or more can be selected from vinylene carbonate, methyl vinylene carbonate, 4,5-dimethyl vinylene carbonate, phenyl vinylene carbonate, 4,5-diphenyl vinylene carbonate, vinyl vinylene carbonate, 4,5-vinyl vinylene carbonate, allyl vinylene carbonate, and 4,5-diallyl vinylene carbonate.

[0045] As an additional additive to the present invention, cyclic sultones can be added. In one embodiment, 1,3-propanesultone, 1-fluoro-1,3-propanesultone, 2-fluoro-1,3-propanesultone, 3-fluoro-1,3-propanesultone, 1,4-butanesultone, methylenemethanedisulfonate, and ethylenemethanedisulfonate are preferred in terms of improving storage properties, and at least one selected from the group consisting of 1,3-propanesultone, 1-fluoro-1,3-propanesultone, 2-fluoro-1,3-propanesultone, and 3-fluoro-1,3-propanesultone can be added.

[0046] As a specific example of the present invention, the compound represented by chemical formula 1 may include at least one compound or isomer selected from the group represented by the following chemical formula:

[0047] [ka]

[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059] Furthermore, the compounds of the present invention may have a chiral carbon center and therefore may exist in the form of R or S isomers, racemic compounds, individual enantiomers or mixtures, individual diastereoisomers or mixtures, and all such stereoisomers and mixtures thereof may fall within the scope of the present invention.

[0060] The compound of the present invention may be present in an amount of about 0.1% by weight or more based on the total weight of the total electrolyte, but is not limited to this, and an appropriate amount can be used as needed within the above content range.

[0061] If the content of the compound in the total electrolyte is too high, the excess gas may cause the battery to swell, which could reduce its lifespan.

[0062] From this perspective, the content of the compound is based on the total weight of the total electrolyte and is 0.01-10% by weight, 0.01-9% by weight, 0.01-8% by weight, 0.01-7% by weight, 0.01-6% by weight, 0.01-5% by weight, 0.01-4% by weight, 0.01-3% by weight, 0.01-2% by weight, 0.01-1% by weight, 0.1-10% by weight, 0.1-9% by weight, 0.1-8% by weight, 0.1-7% by weight, 0.1-6% by weight, 0.1-5% by weight, and 0.1 The concentration can be ~4% by weight, 0.1~3% by weight, 0.1~2% by weight, 0.1~1% by weight, 1~10% by weight, 1~9% by weight, 1~8% by weight, 1~7% by weight, 1~6% by weight, 1~5% by weight, 1~4% by weight, 1~3% by weight, 1~2% by weight, 5~10% by weight, 5~9% by weight, 5~8% by weight, 5~7% by weight, or 5~6% by weight, as long as it functions as an overcharge protection agent without degrading the lifespan characteristics.

[0063] On the other hand, in one embodiment, the electrolyte for the secondary battery may further contain a lithium salt and an organic solvent.

[0064] The concentration of the lithium salt in the electrolyte may be approximately 0.01 to 2.0 M, but is not necessarily limited to this range, and an appropriate concentration can be used as needed. Further improved battery characteristics can be obtained within the aforementioned concentration range.

[0065] The lithium salt used in the electrolyte is not particularly limited, and any lithium salt that can be used in the art is acceptable. For example, LiPF6, LiBF4, LiSbF6, LiAsF6, LiClO4, LiCF3SO3, Li(CF3SO2)2N, LiC4F9SO3, LiAlO2, LiAlCl4, LiC2F6NO4S2, LiB(C2O4)2, LiN(C x F 2x+1 SO2)(C y F 2y+1 You may use one or more selected from the group consisting of SO2) (where x and y are one or more independent integers), LiCl, and LiI.

[0066] 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.

[0067] Specifically, the organic solvent may include, but is not limited to, one or more selected from the group consisting of dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), methyl propyl carbonate, ethyl propyl carbonate, diethyl carbonate (DEC), dipropyl carbonate, propylene carbonate (PC), ethylene carbonate (EC), fluoroethylene carbonate (FEC), butylene carbonate, ethyl propionate (EP), ethyl butyrate, acetonitrile (AN), succinone nitrile (SN), dimethyl sulfoxide, dimethylformamide, dimethylacetamide, γ-valerolactone, γ-butyrolactone, and tetrahydrofuran. Any organic solvent that can be used as an organic electrolyte in the art is acceptable.

[0068] Another aspect of the present invention provides a secondary battery comprising the electrolyte for the secondary battery.

[0069] The secondary battery includes an electrode assembly comprising a positive electrode, a negative electrode, and a separator that separates the positive electrode and the negative electrode. A case for housing the electrode assembly, and The case may contain the electrolyte for the secondary battery, which is housed within the case and immersed in the electrode assembly.

[0070] The aforementioned secondary battery is not particularly limited in form and includes, but is not limited to, lithium-ion batteries, lithium-ion polymer batteries, lithium-sulfur batteries, lithium-air batteries, etc.

[0071] For example, if the secondary battery is a lithium-ion battery, it can be manufactured by the following method.

[0072] First, the positive electrode is prepared.

[0073] For example, 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 directly coating the positive electrode active material composition onto a metal current collector. Alternatively, the positive electrode active material composition can be cast onto a separate support, and then the film peeled off the support is laminated onto the metal current collector to manufacture a positive electrode plate. The positive electrode is not limited to the forms listed above, and may be in forms other than those listed above.

[0074] The positive electrode active material is a lithium-containing metal oxide, and any of those commonly used in the art can be used without limitation. For example, one or more composite oxides of lithium with metals selected from cobalt, manganese, nickel, and combinations thereof can be used, and a specific example is Li a A 1-b B b D2 (wherein the above formula, 0.90 ≤ a ≤ 1.8 and 0 ≤ b ≤ 0.5), Lia 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 (In the above formula, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05), Li a Ni 1-b-c Co b B c D α (In the above formula, 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05, 0 < α ≤ 2), Li a Ni 1-b-c Co b B c O 2-α F α (In the above formula, 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05, 0 < α < 2), Li a Ni 1-b-c Co b B c O 2-α F2(In the above formula, 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05, 0 < α < 2), Li a Ni 1-b-c Mn b B c D α (In the above formula, 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05, 0 < α ≤ 2), Li a Ni 1-b-c Mn b B c O 2-α F α (In the above formula, 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05, 0 < α < 2), Li a Ni 1-b-c Mn b B c O 2-α F2(In the above formula, 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05, 0 < α < 2), Li a Ni b E c Gd O2 (in the above formula, 0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.9, 0 ≤ c ≤ 0.5, 0.001 ≤ d ≤ 0.1), Li a Ni b Co c Mn d G e O2 (In the above formula, 0.90≦a≦1.8, 0≦b≦0.9, 0≦c≦0.5, 0≦d≦0.5, 0.001≦e≦0.1), Li a NiG b O2 (In the above formula, 0.90 ≤ a ≤ 1.8 and 0.001 ≤ b ≤ 0.1), Li a CoG b O2 (In the above formula, 0.90 ≤ a ≤ 1.8 and 0.001 ≤ b ≤ 0.1), Li a MnG b O2 (In the above formula, 0.90 ≤ a ≤ 1.8 and 0.001 ≤ b ≤ 0.1), Li a Mn2G b O4 (where 0.90 ≤ a ≤ 1.8 and 0.001 ≤ b ≤ 0.1 in the above formula), QO2, QS2, LiQS2, V2O5, LiV2O5, LiIO2, LiNiVO4, Li (3-F) J2(PO4)3(0≦f≦2), Li (3ーF) Compounds represented by either the chemical formula Fe2(PO4)3 (0≦f≦2) or LiFePO4 can be used.

[0075] In the above chemical formula, A is Ni, Co, Mn, or a combination thereof; B is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, rare earth elements, 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; and J is V, Cr, Mn, Co, Ni, Cu, or a combination thereof. For example, LiCoO2, LiMn xO 2x (x=1, 2), LiNi 1-x Mn x O 2x (0 <x<1)、LiNi 1-x-y Co x Mn y Examples include O2 (0 ≤ x ≤ 0.5, 0 ≤ y ≤ 0.5) and LiFePO4.

[0076] Of course, compounds having a coating layer on their surface can also be used, or the compound and a compound having a coating layer can be mixed and used. This coating layer may include coating element compounds of oxide, hydroxide, oxyhydroxy, oxycarbonate, or hydroxycarbonate of the coating element. The compounds constituting these coating layers may be amorphous or crystalline. As coating elements included in the coating layer, Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, or mixtures thereof can be used. Any coating method can be used for the coating layer formation step, as long as the compound is coated with these elements in a way that does not adversely affect the physical properties of the positive electrode active material (e.g., spray coating, immersion method, etc.). Since this is something that people engaged in this field will understand well, a detailed explanation will be omitted.

[0077] The conductive material can be carbon black, graphite fine particles, etc., but is not limited to these; any conductive material that can be used in the relevant technical field can be used.

[0078] As the binder, vinylidene fluoride / hexafluoropropylene copolymer, polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethyl methacrylate, polytetrafluoroethylene and mixtures thereof, or styrene-butadiene rubber polymers can be used, but are not limited to these; any binder that can be used in the art can be used.

[0079] As the aforementioned solvent, N-methylpyrrolidone, acetone, water, etc., can be used, but the solvent is not limited to these, and any solvent that can be used in the art can be used.

[0080] The content of the positive electrode active material, conductive material, binder, and solvent is at levels typically used in lithium-ion batteries. Depending on the application and configuration of the lithium-ion battery, one or more of the conductive material, binder, and solvent may be omitted.

[0081] Next, the negative electrode is prepared.

[0082] For example, 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 plate is manufactured by directly coating and drying the negative electrode active material composition onto a metal current collector. Alternatively, the negative electrode active material composition can be cast onto a separate support, and then the film peeled off the support is laminated onto a metal current collector to manufacture the negative electrode plate.

[0083] The negative electrode active material can be any material that can be used as a negative electrode active material for lithium-ion batteries in the art. For example, it may include one or more selected from the group consisting of lithium metal, metals alloyable with lithium, transition metal oxides, non-transition metal oxides, and carbon-based materials.

[0084] For example, the metals that can form an alloy with lithium may be Si, Sn, Al, Ge, Pb, Bi, Sb, Si-Y alloy (where Y is an alkali metal, alkaline earth metal, Group 13 element, Group 14 element, transition metal, rare earth element, or a combination of these elements and is not Si), Sn-Y alloy (where Y is an alkali metal, alkaline earth metal, Group 13 element, Group 14 element, transition metal, rare earth element, or a combination of these elements and is not Sn), etc. The element Y may be 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, Tl, Ge, P, As, Sb, Bi, S, Se, Te, Po, or a combination thereof.

[0085] For example, the transition metal oxide may be lithium titanate, vanadium oxide, lithium vanadate, etc.

[0086] For example, the non-transition metal oxide may be SnO2, SiO x (0 < x < 3), etc.

[0087] The carbon-based material may be crystalline carbon, amorphous carbon, or a mixture thereof. The crystalline carbon may be graphite such as amorphous, plate-like, flaky, spherical or fibrous natural graphite or artificial graphite, and the amorphous carbon may be soft carbon (low-temperature calcined carbon) or hard carbon, mesophase pitch carbide, calcined coke, etc. <s

[0088] In the negative electrode active material composition, the conductive material and the binder can be the same as those in the case of the positive electrode active material composition.

[0089] The content of the negative electrode active material, conductive material, binder, and solvent is at levels typically used in lithium-ion batteries. Depending on the application and configuration of the lithium-ion battery, one or more of the conductive material, binder, and solvent may be omitted.

[0090] Next, a separator is prepared to separate the positive and negative electrodes.

[0091] Any separator commonly used in lithium-ion batteries can be used. A separator with low resistance to electrolyte ion movement while possessing excellent electrolyte moisture absorption capacity can be used. For example, it may be a nonwoven or woven fabric selected from glass fiber, polyester, Teflon®, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), or a combination thereof. For example, a rollable separator such as polyethylene or polypropylene can be used in lithium-ion batteries, while a separator with excellent organic electrolyte impregnation capacity can be used in lithium-ion polymer batteries. For example, the separator can be manufactured according to the following method.

[0092] A separator composition is prepared by mixing a polymer resin, a filler, and a solvent. The separator composition can be directly coated onto the electrode and dried to form a separator. Alternatively, the separator composition may be cast onto a support and dried, and then the separator film peeled off the support may be laminated onto the electrode to form a separator.

[0093] The polymer resin used in the manufacture of the separator is not particularly limited, and all substances used as binders for electrode plates can be used. For example, vinylidene fluoride / hexafluoropropylene copolymer, polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethyl methacrylate, or mixtures thereof can be used.

[0094] Next, prepare the electrolyte solution for the secondary battery as described above.

[0095] As shown in Figure 1, the secondary battery 1 includes a positive electrode 40, a negative electrode 60, and a separator 50. The positive electrode 40, negative electrode 60, and separator 50 are wound up or folded and housed in cases 10 and 80. Subsequently, electrolyte is injected into cases 10 and 80 to complete the secondary battery 1.

[0096] The aforementioned case can have various forms depending on the application and design standards of the secondary battery, and can be formed to have various sizes and shapes, such as rectangular, thin-film, and button-shaped.

[0097] For example, the secondary battery may be a button-type battery. Specifically, the secondary battery may be a lithium-ion battery.

[0098] An electrode assembly can be formed by placing a separator between the positive electrode and the negative electrode. After stacking the electrode assembly in a bicell structure, it is impregnated with an electrolyte, and the resulting product is placed in a pouch and sealed to complete a lithium-ion polymer battery.

[0099] Furthermore, multiple electrode assemblies can be stacked to form a battery pack, which can then be used in all devices requiring high capacity and high output. For example, it can be used in laptop computers, smartphones, electric vehicles, and the like. [Examples]

[0100] The present invention will be described in detail below using manufacturing examples, embodiments, and experimental examples.

[0101] However, the manufacturing examples, embodiments, and experimental examples described later are merely illustrative of one aspect of the present invention, and the present invention is not limited thereto.

[0102] <Manufacturing Example 1> Manufacturing of Compound 1 [ka] <Compound 1> In a 250 mL three-neck reactor, 4-hydroxymethyl-2-oxazolidinone (5 g, 0.04 mol) and triethylamine (6.5 g, 0.06 mol) were dissolved in dimethylformamide (20 ml), then ethyl acetate (80 ml) was added and the mixture was cooled to 0°C. Methanesulfonyl chloride (14.9 g, 0.05 mol) was added dropwise, and the mixture was stirred for 1 hour.

[0103] 50 ml of ethyl acetate and 50 ml of water were added to a reactor and stirred vigorously. After standing, the layers were separated. The aqueous layer was extracted with ethyl acetate (50 ml x 2). Anhydrous magnesium sulfate was added to the organic layer and stirred for 5 minutes, after which the solid was filtered. The filtrate was concentrated and purified by column chromatography.

[0104] 5.6 g of compound 1 (yield: 70%) was obtained, and this 1 H-NMR and 13 Confirmed by 13C-NMR.

[0105] 1 H-NMR (400MHz, DMSO-d6)d7.95(s, 1H), 4.25-4.37(m, 1H), 4.23-4.15(m, 2H), 4.14-4.08(m, 2H), 3.23(s, 3H), 13 C-NMR (400MHz, DMSO-d6)d159.1, 71.0, 65.9, 50.9, 37.1

[0106] <Manufacturing Example 2> Manufacturing of Compound 2 [ka] <Compound 2> 2-oxazolidinone (8 g, 0.09 mol) and triethylamine (18.6 g, 0.18 mol) were dissolved in methylene chloride (80 ml) in a 250 mL three-neck reactor, and then cooled to 0°C. Propargyl chloroformate (12.5 g, 0.1 mol) was added dropwise, and the mixture was stirred for 2 hours.

[0107] Water (80 mL) was added to the reactor and stirred vigorously, then allowed to stand and separate the layers. The aqueous layer was extracted with methylene chloride (100 mL x 2). Anhydrous magnesium sulfate was added to the organic layer and stirred for 5 minutes, after which the solid was filtered. The filtrate was concentrated and purified by column chromatography. 13 g of compound 2 (yield: 84%) was obtained, and this 1 H-NMR and 13 Confirmed by 13C-NMR.

[0108] 1 H-NMR (400MHz, CDCl3)d4.86(d, 2H, J=0.006Hz), 4.42-4.38(m, 2H), 4.08-4.04(m, 2H), 2.55-2.54(m, 1H), 13 C-NMR (400MHz, CDCl3)d151.7, 150.3, 76.7, 76.1, 61.8, 54.4, 43.4

[0109] <Manufacturing Example 3> Manufacturing of Compound 3 [ka] <Compound 3> 2-thiazolidinone (8 g, 0.08 mol) and triethylamine (15.7 g, 0.16 mol) were dissolved in methylene chloride (80 ml) in a 250 mL three-neck reactor, and then cooled to 0°C. Propargyl chloroformate (10.5 g, 0.09 mol) was added dropwise, and the mixture was stirred for 2 hours.

[0110] Water (80 mL) was added to the reactor and stirred vigorously, then allowed to stand and separate the layers. The aqueous layer was extracted with methylene chloride (100 mL x 2). Anhydrous magnesium sulfate was added to the organic layer and stirred for 5 minutes, after which the solid was filtered. The filtrate was concentrated and purified by column chromatography. 12 g of compound 3 (yield: 84%) was obtained, and this 1 H-NMR and 13 Confirmed by 13C-NMR.

[0111] 1H-NMR (400MHz, CDCl3)d4.84(d, 2H, J=0.006Hz), 4.18-4.14(m, 2H), 3.32-3.28(m, 2H), 2.54-2.53(m, 1H), 13 C-NMR (400MHz, CDCl3)d170.2, 149.9, 76.8, 76.0, 54.3, 47.6, 25.2

[0112] <Manufacturing Example 4> Manufacturing of Compound 4 [ka] <Compound 4> 4-hydroxymethyl-2-oxazolidinone (5 g, 0.04 mol) and triethylamine (6.5 g, 0.06 mol) were dissolved in dimethylformamide (20 ml) in a 250 mL three-neck reactor, and then cooled to 0°C. Methanesulfonyl chloride (19.7 g, 0.17 mol) was added dropwise, and the mixture was stirred for 1 hour.

[0113] 50 ml of ethyl acetate and 50 ml of water were added to a reactor and stirred vigorously. After standing, the layers were separated. The aqueous layer was extracted with ethyl acetate (50 ml x 2). Anhydrous magnesium sulfate was added to the organic layer and stirred for 5 minutes, after which the solid was filtered. The filtrate was concentrated and purified by column chromatography.

[0114] 7.2 g of compound 4 was obtained (yield: 75.9%), and this 1 Confirmed by 1H-NMR. 1 H-NMR (400MHz, CDCl3)d4.517-4.478(t, 1H), 4.122-4.083(t, 1H), 3.347(s, 3H)

[0115] <Manufacturing Example 5> Manufacturing of Compound 5 [ka] <Compound 5> Oxazolidinone (5g, 0.048mol) was added to dimethylformamide (60ml) in a 100mL three-neck reactor, stirred at room temperature for 10 minutes, and then cooled to 0°C. After cooling was complete, 60% sodium hydride (2.3g, 0.058mol) was added in portions and stirred for 30 minutes. Then, 80% propargyl bromide (10.1g, 0.068mol) was added dropwise, and the mixture was heated to room temperature and stirred for 1 hour.

[0116] A saturated ammonium chloride aqueous solution (40 mL) was added to the reactor and stirred vigorously, then allowed to stand and separate the layers. The aqueous layer was extracted with ethyl acetate (50 mL x 2). Anhydrous magnesium sulfate was added to the organic layer and stirred for 5 minutes, after which the solid was filtered. The filtrate was then concentrated and purified by column chromatography. 6.8 g of compound 5 (yield: 80%) was obtained, and this 1 H-NMR and 13 Confirmed by 13C-NMR.

[0117] 1 H-NMR (400MHz, CDCl3-d)d4.38-4.34(m, 2H), 4.09-4.08(m, 2H), 3.68-3.64(m, 2H), 2.31-2.30(m, 1H), 13 C-NMR (400MHz, CDCl3-d)d158.0, 76.9, 73.4, 62.1, 43.9, 34.1

[0118] <Manufacturing Example 6> Manufacturing of Compound 6 [ka] <Compound 6> In a 250 mL three-neck reactor, 4-hydroxymethyl-2-oxazolidinone (5 g, 0.04 mol) and triethylamine (6.5 g, 0.06 mol) were dissolved in dimethylformamide (20 ml), then ethyl acetate (80 ml) was added and the mixture was cooled to 0°C. Vinyl sulfonyl chloride (6.7 g, 0.05 mol) was added dropwise, and the mixture was stirred for 1 hour.

[0119] 50 ml of ethyl acetate and 50 ml of water were added to a reactor and stirred vigorously. After standing, the layers were separated. The aqueous layer was extracted with ethyl acetate (50 ml x 2). Anhydrous magnesium sulfate was added to the organic layer and stirred for 5 minutes, after which the solid was filtered. The filtrate was concentrated and purified by column chromatography. 6.2 g of compound 6 (yield: 70%) was obtained, and this 1 H-NMR and 13 Confirmed by 13C-NMR.

[0120] 1 H-NMR (400MHz, DMSO-d6) d7.93(s, 1H), 7.04-6.97(m, 1H), 6.37(dd, 2H, J=4Hz), 4.40-4.13(m, 1H), 4.13-4.04(m, 4H), 13 C-NMR (400MHz, DMSO-d6)d159.0, 132.6, 132.5, 71.5, 65.8, 50.8

[0121] <Manufacturing Example 7> Manufacturing of Compound 7 [ka] <Compound 7> In a 250 mL three-neck reactor, 4-hydroxymethyl-2-oxazolidinone (5 g, 0.04 mol) and triethylamine (6.5 g, 0.06 mol) were dissolved in dimethylformamide (20 ml), then ethyl acetate (80 ml) was added and the mixture was cooled to 0°C. Trifluoromethanesulfonyl chloride (8.6 g, 0.05 mol) was added dropwise, and the mixture was stirred for 1 hour.

[0122] 50 ml of ethyl acetate and 50 ml of water were added to a reactor and stirred vigorously. After standing, the layers were separated. The aqueous layer was extracted with ethyl acetate (50 ml x 2). Anhydrous magnesium sulfate was added to the organic layer and stirred for 5 minutes, after which the solid was filtered. The filtrate was concentrated and purified by column chromatography.

[0123] 7.9 g of compound 7 (yield: 73%) was obtained, and this 1 H-NMR, 13 C-NMR and 19 Confirmed by 1F-NMR.

[0124] 1 H-NMR (400MHz, DMSO-d6)d7.95(s, 1H), 4.43-4.37(m, 2H), 4.34-4.27(m, 1H), 4.13-4.07(m, 2H), 13 C-NMR (400MHz, DMSO-d6)d159.0, 128.2, 124.8, 121.5, 118.1, 70.7, 65.7, 51.5, 19 F-NMR (400MHz, DMSO-d6) d-78.8

[0125] <Manufacturing Example 8> Manufacturing of Compound 8 [ka] <Compound 8> 60% sodium hydride (1.65 g, 0.041 mol) was added to dimethylformamide (20 ml) in a 100 mL three-neck reactor and cooled to 0°C. In a separate flask, a solution of oxazolidinone (3 g, 0.034 mol) dissolved in dimethylformamide (40 ml) was prepared. Once the sodium hydride solution had cooled to 0°C, the oxazolidinone solution was added dropwise and stirred for 30 minutes. After cooling again to 0°C, allyl bromide (5.53 g, 0.052 mol) was added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 1 hour.

[0126] 40 mL of purified water was added to the reactor and stirred vigorously, then allowed to stand and separate the layers. The aqueous layer was extracted with ethyl acetate (50 mL x 2). Anhydrous magnesium sulfate was added to the organic layer and stirred for 5 minutes, after which the solid was filtered. The filtrate was then concentrated and purified by column chromatography.

[0127] 3.4 g of compound 8 (yield: 77.6%) was obtained, and this 1 H-NMR and 13 Confirmed by 13C-NMR.

[0128] 1H-NMR (400MHz, CDCl3-d)d5.81-5.71(m, 1H), 5.26-5.22(m, 2H), 4.34-4.30(m, 2H), 3.86-3.85(m, 2H), 3.53-3.49(m, 2H), 13 C-NMR (400MHz, CDCl3-d)d157.9, 131.8, 117.4, 63.3, 44.7, 51.8.

[0129] <Manufacturing Example 9> Manufacturing of Compound 9 [ka] <Compound 9> 60% sodium hydride (1.4g, 0.035mol) was placed in dimethylformamide (20ml) in a 100mL three-neck reactor and cooled to 0°C. In another flask, a solution of thiazolidinone (3g, 0.029mol) dissolved in dimethylformamide (40ml) was prepared. Once the sodium hydride solution had cooled to 0°C, the thiazolidinone solution was added dropwise and stirred for 30 minutes. After cooling again to 0°C, allyl bromide (4.67g, 0.044mol) was added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 1 hour.

[0130] 40 mL of purified water was added to the reactor and stirred vigorously, then allowed to stand and separate the layers. The aqueous layer was extracted with ethyl acetate (50 mL x 2). Anhydrous magnesium sulfate was added to the organic layer and stirred for 5 minutes, after which the solid was filtered. The filtrate was then concentrated and purified by column chromatography.

[0131] 3.1 g of compound 9 (yield: 74.4%) was obtained, and this 1 H-NMR and 13 Confirmed by 13C-NMR.

[0132] 1 H-NMR (400MHz, CDCl3-d)d5.79-5.70(m, 1H), 5.24-5.19(m, 2H), 3.92-3.90(m, 2H), 3.60-3.57(m, 2H), 3.28-3.24(m, 2H), 13C-NMR (400MHz, CDCl3-d)d171.4, 117.4, 131.8, 53.0, 43.5, 29.0

[0133] <Manufacturing Example 10> Manufacturing of Compound 10 [ka] <Compound 10> 4-hydroxymethyl-2-oxazolidinone (3.5 g, 0.03 mol) and triethylamine (6.7 g, 0.066 mol) were dissolved in dimethylformamide (30 ml) in a 100 mL three-neck reactor and stirred.

[0134] Perfluorobutanoic acid (6.42 g, 0.03 mol) was dissolved in dimethylformamide (2.63 g, 0.036 mol) in a 50 mL three-neck reactor, and then thionyl chloride (3.75 g, 0.032 mol) was added dropwise for 30 minutes. This solution was added dropwise to a 100 mL three-neck reactor for 10 minutes and stirred for 2 hours.

[0135] The reaction mixture was filtered and washed with dichloromethane, and the filtrate was concentrated. Dichloromethane was added to the concentrate and dissolved, then anhydrous magnesium sulfate was added and the mixture was stirred for 5 minutes. The solid was filtered and the filtrate was concentrated and purified by column.

[0136] 6.5 g of compound 10 (yield: 69%) was obtained, and this 1 Confirmed by 1H-NMR.

[0137] 1 H-NMR (400MHz, CDCl3)d6.55(s, 1H), 4.59-4.54(m, 1H), 4.52-4.48(m, 1H), 4.39-4.35(m, 1H), 4.27-4.21(m, 2H)

[0138] <Manufacturing Example 11> Manufacturing of Compound 11 [ka] <Compound 11> Thiazolidinone (5g, 0.049mol) and triethylamine (9.82g, 0.097mol) were added to dichloromethane (50ml) in a 100mL three-neck reactor. The mixture was stirred at room temperature for 30 minutes, then cooled to -10°C. After cooling was complete, methanesulfonyl chloride (7.0g, 0.058mol) was added dropwise, and the mixture was stirred for 1 hour.

[0139] Water (50 mL) was added to the reactor and stirred vigorously, then allowed to stand and separate the layers. The aqueous layer was extracted with dichloromethane (50 mL x 2). Anhydrous magnesium sulfate was added to the organic layer and stirred for 5 minutes, after which the solid was filtered. The filtrate was concentrated and purified by column chromatography.

[0140] 6.8 g of compound 11 was obtained (yield: 77.3%), and this 1 H-NMR and 13 Confirmed by 13C-NMR.

[0141] 1 H-NMR (400MHz, CDCl3-d)d4.18-4.14(m, 2H), 3.42-3.40(m, 2H), 3.31(s, 3H), 13 C-NMR (400MHz, CDCl3-d)d173.2, 45.6, 36.8, 27.5

[0142] <Manufacturing Example 12> Manufacturing of Compound 12 [ka] <Compound 12> In a 250 mL three-neck reactor, 4-hydroxymethyl-2-oxazolidinone (5 g, 0.04 mol) and triethylamine (6.5 g, 0.06 mol) were dissolved in dimethylformamide (20 ml), then ethyl acetate (80 ml) was added and the mixture was cooled to 0°C. Propargyl chloroformate (6 g, 0.05 mol) was added dropwise, and the mixture was stirred for 1 hour.

[0143] 50 ml of ethyl acetate and 50 ml of water were added to a reactor and stirred vigorously. After standing, the layers were separated. The aqueous layer was extracted with ethyl acetate (50 ml x 2). Anhydrous magnesium sulfate was added to the organic layer and stirred for 5 minutes, after which the solid was filtered. The filtrate was concentrated and purified by column chromatography.

[0144] 4.3 g of compound 12 (yield: 75%) was obtained, and this 1 H-NMR and 13 Confirmed by 13C-NMR.

[0145] 1 H-NMR (400MHz, DMSO-d6)d7.89(s, 1H), 4.79(S, 2H), 4.40-4.31(m, 1H), 4.16-4.04(m, 4H), 3.67(S, 1H), 13 C-NMR (400MHz, DMSO-d6)d159.1, 154.3, 78.7, 69.8, 66.14, 55.9, 50.7

[0146] <Manufacturing Example 13> Manufacturing of Compound 13 [ka] <Compound 13> In a 250 mL three-neck reactor, 1,3-oxazolidine-2-thion (5 g, 0.05 mol) and triethylamine (9.8 g, 0.1 mol) were dissolved in methylene chloride (50 ml), and then cooled to 0°C. Propargyl chloroformate (6.9 g, 0.06 mol) was added dropwise, and the mixture was stirred for 2 hours.

[0147] Water (80 mL) was added to the reactor and stirred vigorously, then allowed to stand and separate the layers. The aqueous layer was extracted with methylene chloride (100 mL x 2). Anhydrous magnesium sulfate was added to the organic layer and stirred for 5 minutes, after which the solid was filtered. The filtrate was concentrated and purified by column chromatography.

[0148] Compound 13 was obtained in a yield of 7.2 g (80.2%) and confirmed by ESI-MS. ESI-MS m / z 185.01 [M+H] +

[0149] <Manufacturing Example 14> Manufacturing of Compound 14 [ka] <Compound 14> In a 250 mL three-neck reactor, dissolve 1-amino-2-propanol (6.4 g, 0.09 mol) in methylene chloride (70 ml), then add triethylamine (25.9 g, 0.26 mol), stir under nitrogen, then add triphosgene (12.6 g, 0.04 mol), and stir at room temperature for 20 hours. Terminate the reaction with aqueous ammonium chloride (10 ml).

[0150] Water (80 mL) was added to the reactor and stirred vigorously, then allowed to stand and separate the layers. The aqueous layer was extracted with methylene chloride (100 mL x 2). Anhydrous magnesium sulfate was added to the organic layer and stirred for 5 minutes, after which the solid was filtered. The filtrate was concentrated and purified by column chromatography.

[0151] 4 g of compound 14 (yield: 46.4%) was obtained and confirmed by ESI-MS. ESI-MS m / z 102 [M+H] +

[0152] <Example 1> Production of electrolyte for secondary batteries 1.0 M LiPF6 was dissolved in a solvent prepared by mixing ethylene carbonate (EC), ethyl methyl carbonate (EMC), and dimethyl carbonate (DMC) in a volume ratio of 20:40:40.

[0153] Based on the total weight (100 wt%) of the aforementioned electrolyte, the electrolytes of the examples and comparative examples were prepared by adding additives according to Table 1 below.

[0154] [Table 1-1] [Table 1-2] [Table 1-3]

[0155] <Example 2> Manufacturing of button-type batteries A slurry of 96% by weight of artificial graphite (S360-L2-H Tiangin BTR New energy technology Co.,Ltd.), 1% by weight of SuperP (TIMCAL), 1.5% by weight of styrene-butadiene rubber (SBR) binder (ZEON), and 1.5% by weight of carboxymethylcellulose (CMC, Sigma-Aldrich) was mixed, then added to distilled water and stirred for 60 minutes using a mechanical stirrer to produce a negative electrode active material slurry. The slurry was coated onto a 30 μm thick copper current collector to a thickness of approximately 60 μm using a doctor blade, dried in a hot air dryer at 100°C for 1 hour, dried again under vacuum conditions for 8 hours, and then rolled (roll pressed) to produce a negative electrode plate. LiRing 0.6 Mn 0.2 Co 0.2 A cathode active material slurry was prepared by mixing 2% by weight of superP(TIMCAL) and 2% by weight of polyvinylidene fluoride (PVDF, Sigma-Aldrich) as O296 wt% conductive material, adding the mixture to N-methyl-2-pyrrolidone solvent, and stirring for 30 minutes using a mechanical stirrer. The slurry was then coated to a thickness of 60 μm onto a 20 μm thick aluminum current collector using a doctor blade, dried in a 100°C hot air dryer for 1 hour, dried again under vacuum conditions for 8 hours, and then rolled (roll pressed) to produce a cathode plate. A lithium battery was manufactured using 14 μm thick polypropylene as the separator and the organic electrolytes prepared in Examples 1 to 19 as the electrolyte.

[0156] <Experimental Example 1> Evaluation of lifespan performance at room temperature A lithium secondary battery was charged at 25°C under constant current / constant voltage (CC / CV) conditions to 4.2V at a rate of 1.0C. Then, while maintaining 4.2V in constant voltage mode, it was cut off at a rate of 0.05C, and finally discharged to 2.7V at a rate of 1.0C. The charge and discharge conditions were repeated for one cycle. The analysis results are shown in Table 2 and Figures 2 to 5.

[0157]

Table 2

[0158] From Table 2, Figure 2 and Figure 5, it was confirmed that as a result of repeating cycle charge and discharge at 25°C, the examples using the compound of the present invention as an additive had better normal temperature life than the comparative examples.

[0159] Also, from Table 2, Figure 3 and Figure 4, it was confirmed that when vinylene carbonate (VC) and lithium salt (LiPO2F2) additives were combined, the life was extended compared to when used alone.

[0160] <Experimental Example 2> Resistance Improvement Performance Evaluation After charging the battery manufactured according to the example to 4.2V at 1C and then discharging it to SOC5%0, it was discharged for 10 seconds at each of 4 C-rates (0.5, 1, 2, 3C) to measure the initial DC resistance (DC-IR). After charging to 4.2V at 1C and then performing 200 charge and discharge cycles at normal temperature, the DC resistance (DC-IR) was measured in the same manner as the initial DC resistance measurement method, and the ratio to the initial DC-IR was expressed as a percentage and shown in Table 3.

[0161]

Table 3

[0162] As can be confirmed from Table 3, in the examples using the compound manufactured according to the present invention, although the initial discharge resistance value was higher than that of the comparative examples, the discharge resistance after 200 charges showed a tendency to be lower than that of the comparative examples. That is, it was confirmed that the DC-IR increase rate was lower than that of the comparative examples. As a result, when using the compound produced by the present invention, it shows a low resistance increase rate, confirming that a film facilitating the movement of lithium has been formed. In particular, it was confirmed that when the additives vinylene carbonate (VC) and lithium salt (LiPO2F2) are combined, the DC-IR increase rate becomes remarkably low.

[0163] The above description of the present invention is for illustrative purposes. Those with ordinary knowledge in the technical field to which the present invention pertains will be able to understand that it can be easily transformed into other specific forms without changing the technical idea and essential features of the present invention. Therefore, it should be understood that the embodiments described above are exemplary in all aspects and not restrictive. For example, each component described in a single form can be implemented dispersedly, and similarly, the components described as being dispersed can also be implemented in a combined form. The scope of the present invention is indicated by the claims described below, and all changes or modified forms derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included within the scope of the present invention.

Explanation of Reference Numerals

[0164] 1: Secondary battery 10: Top case 20: Spring 30: Spacer 40: Positive electrode 50: Separator 60: Negative electrode

Claims

1. Electrolytes for secondary batteries containing the compound represented by the following chemical formula 1, or its isomers: [Chemical Formula 1] 【Chemistry 1】 In the above chemical formula 1, the carbon atoms in the ring are linked by single or double bonds, X is oxygen or sulfur, Y is oxygen or sulfur, Z １ 、Z ２ 、and Z ３ are each independently hydrogen, substituted or unsubstituted Ｃ１－１０ alkyl, substituted or unsubstituted C １－１０ alkenyl, substituted or unsubstituted C １－１０ amine, substituted or unsubstituted C １－１０ acyl, substituted or unsubstituted C １－１０ alkynyl, substituted or unsubstituted C ３－１０ cycloalkyl, substituted or unsubstituted silyl, substituted or unsubstituted C １－１０ alkoxy, substituted or unsubstituted C １－１２ heteroalkyl, substituted or unsubstituted C １－６ heterocycloalkyl, -SO ２ R １ 、-P(=G)(OR １ ) ２ and -P(=G)(R １ ) ２ selected from the group consisting of Said Z １ and Z ２ They may or may not be bonded to each other to form a ring. The aforementioned G is oxygen or sulfur, The aforementioned R １ C is either substituted or non-substituted. １－６ Alkyl, C ２－６ Alkenil, C ２－６ Alkinyl or C ６－２０ It is Ariel.

2. Said Z １ Each of these is independently hydrogen, substituted, or unsubstituted C. １－１０ Alkyl, substituted, or unsubstituted C １－１０ Alkenyl, substituted, or unsubstituted C １－１０ Amine, substituted or unsubstituted C １－１０ Acyl, substituted, or unsubstituted C １－１０ Alkynyl, substituted, or unsubstituted C ３－１０ Cycloalkyl, substituted or unsubstituted silyl, -SO ２ R １ and -P(=G)(OR １ ) ２ Selected from the group consisting of, The aforementioned R １ And G is as defined in claim 1, Said Z ２ and Z ３ These are, 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 C １－１２ An electrolyte for a secondary battery according to claim 1, selected from the group consisting of heteroalkyls.

3. Said Z １ These are, independently, hydrogen, substituted or unsubstituted C. １－１０ Alkenyl, substituted, or unsubstituted C １－１０ Acyl, substituted, or unsubstituted C １－１０ Alkinyl, -SO ２ R １ Selected from the group consisting of, The aforementioned R １ This is as defined in claim 1, Said Z ２ and Z ３ These are, independently, hydrogen, substituted or unsubstituted C １－１０ An electrolyte for a secondary battery according to claim 1, selected from the group consisting of alkyl groups.

4. The electrolyte for a secondary battery according to claim 1, wherein the substituted alkyl, alkenyl, amine, acyl, alkynyl, cycloalkyl, silyl, alkoxy, heteroalkyl, and heterocycloalkyl groups are each independently substituted with one or more substituents selected from the group consisting of alkoxy groups, alkynyloxy groups, heteroaryl groups, alkenyl groups, heterocycloalkyl groups, carbonyl groups, halogen groups, hydroxyl groups, alkenyloxy groups, carboxyl groups, carbonate groups, alkyl groups, alkynyl groups, amine groups, cycloalkyl groups, silyl groups, sulfonate groups, phosphate groups, thiophosphate groups, nitro groups, cyano groups, heteroalkyl groups, cycloalkyl groups, aryl groups, and ether groups.

5. The electrolyte for the secondary battery is LiPO ２ F ２ The electrolyte for a secondary battery according to claim 1, which may further comprise one or more additives selected from the group consisting of unsaturated cyclic carbonates, cyclic sultones, cyclic sulfetralactones, and nitrile compounds.

6. The electrolyte for a secondary battery according to claim 5, wherein the unsaturated cyclic carbonate is selected from the group consisting of vinylene carbonate, phenyl carbonate, vinyl carbonate, and allyl carbonate.

7. The electrolyte for a secondary battery according to claim 1, comprising at least one compound selected from the group represented by the following chemical formula, or an isomer thereof: 【Chemistry 2-1】 【Chemistry 2-2】 [Chemistry 2-3] [Chemistry 2-4] 【Chemistry 2-5】 【Chemistry 2-6】 【Chemistry 2-7】 【Chemistry 2-8】 【Chemistry 2-9】 【Chemistry 2-10】 【Chemistry 2-11】 【Chemistry 2-12】

8. The electrolyte for a secondary battery according to claim 1, further comprising an organic solvent.

9. The electrolyte for a secondary battery according to claim 1, wherein the compound represented by the chemical formula 1 is provided as an electrolyte additive.

10. The electrolyte for a secondary battery according to claim 1, wherein the secondary battery is a lithium-ion battery.

11. An electrode assembly including a positive electrode, a negative electrode, and a separator for separating the positive electrode and the negative electrode. A case for housing the electrode assembly, and A secondary battery comprising an electrolyte for a secondary battery according to claim 1, which is housed in the case and immersed in the electrode assembly.

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