CN111542963B - Electrolyte composition and secondary battery using same - Google Patents
Electrolyte composition and secondary battery using same Download PDFInfo
- Publication number
- CN111542963B CN111542963B CN201980007399.7A CN201980007399A CN111542963B CN 111542963 B CN111542963 B CN 111542963B CN 201980007399 A CN201980007399 A CN 201980007399A CN 111542963 B CN111542963 B CN 111542963B
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- CN
- China
- Prior art keywords
- electrolyte composition
- secondary battery
- chemical formula
- carbonate
- compound represented
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 72
- 239000003792 electrolyte Substances 0.000 title claims abstract description 68
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- 239000000126 substance Substances 0.000 claims description 53
- 150000001875 compounds Chemical class 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 21
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052799 carbon Inorganic materials 0.000 abstract description 14
- 230000000052 comparative effect Effects 0.000 description 15
- 239000007774 positive electrode material Substances 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 9
- 239000007773 negative electrode material Substances 0.000 description 9
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- 229910052782 aluminium Inorganic materials 0.000 description 7
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- 239000006183 anode active material Substances 0.000 description 6
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- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 5
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- 125000003545 alkoxy group Chemical group 0.000 description 4
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- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
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- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 2
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- 239000004743 Polypropylene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 229910052795 boron group element Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910052800 carbon group element Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
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- 150000005678 chain carbonates Chemical class 0.000 description 2
- 229910052798 chalcogen Inorganic materials 0.000 description 2
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- 125000004093 cyano group Chemical group *C#N 0.000 description 2
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- QKBJDEGZZJWPJA-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound [CH2]COC(=O)OCCC QKBJDEGZZJWPJA-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The present invention provides an electrolyte composition including a propane sultone compound in which carbon at a specific position is substituted with a specific substituent, and a secondary battery using the same. The electrolyte composition according to the present invention contains a propane sultone compound in which carbon at a specific position is substituted with a specific substituent to form a stable anode film, and thus can significantly improve the life characteristics of a secondary battery.
Description
Technical Field
The present invention relates to an electrolyte composition and a secondary battery using the same, and more particularly, to an electrolyte composition having excellent life characteristics by forming a stable negative electrode film, and a secondary battery using the same.
Background
At the initial charge of the lithium secondary battery, lithium ions from a positive electrode active material such as lithium metal oxide move to a negative electrode active material such as graphite and are intercalated between layers of the negative electrode active material. At this time, due toSince lithium ions have high reactivity, the electrolyte composition and carbon constituting the negative electrode active material react on the surface of the negative electrode active material such as graphite to form Li 2 CO 3 、Li 2 O、LiOH、Li 2 SO 4 And the like. These compounds form an SEI (solid electrolyte interface) film as a kind of protective film on the surface of a negative electrode active material such as graphite.
The SEI film serves as an ion tunnel, allowing only lithium ions to pass through. As an effect of such ion channels, the SEI film inserts lithium ions in the electrolyte composition together with high molecular weight organic solvent molecules moving together between layers of the anode active material to prevent damage to the anode structure. Therefore, by preventing contact of the electrolyte composition and the anode active material, decomposition of the electrolyte composition does not occur, and the amount of lithium ions in the electrolyte composition is reversibly maintained to maintain stable charge and discharge.
Accordingly, additives for improving life characteristics by forming a stable SEI film on the surface of a negative electrode are attracting more and more attention. For example, korean patent laid-open No. 10-1999-0088654 discloses an electrolyte composition using 1, 3-propane sultone as an electrolyte additive.
However, these electrolyte additives are harmful to the environment and limited in use, and since the flexibility of the formed film is small, cracks are generated due to repeated shrinkage and expansion of the anode when the long-term life is evaluated, so that it is difficult to suppress the decrease in battery capacity.
Disclosure of Invention
Technical problem
An object of the present invention is to provide an electrolyte composition having excellent life characteristics by forming a stable negative electrode film.
Another object of the present invention is to provide a secondary battery using the electrolyte composition.
Technical proposal
In one aspect, the present invention provides an electrolyte composition including a compound represented by the following chemical formula 1 and a nonaqueous solvent.
[ chemical formula 1]
In the above-mentioned formula, the catalyst,
x is halogen, hydroxy, cyano, C 1 -C 4 Alkoxy, C 1 -C 4 Trialkylsiloxy or C 1 -C 4 Is a halogenated alkoxy group of (a).
In another aspect, the present invention provides a secondary battery using the electrolyte composition.
Advantageous effects
The electrolyte composition according to the present invention contains a propane sultone compound in which carbon at a specific position is substituted with a specific substituent, thereby forming a stable anode film, and thus can significantly improve the life characteristics of a secondary battery.
Drawings
Fig. 1 is a cycle-discharge capacity graph showing normal temperature life characteristics of a secondary battery using an electrolyte composition according to an embodiment of the present invention.
Fig. 2 is a cycle-discharge capacity graph showing high temperature life characteristics of a secondary battery using an electrolyte composition according to an embodiment of the present invention.
Detailed Description
The present invention will be described in more detail below.
An embodiment of the present invention relates to an electrolyte composition including a compound represented by the following chemical formula 1 and a nonaqueous solvent.
[ chemical formula 1]
In the above-mentioned formula, the catalyst,
x is halogen, hydroxy, cyano, C 1 -C 4 Alkoxy, C 1 -C 4 Trialkylsiloxy or C 1 -C 4 Is a halogenated alkoxy group of (a).
C as used in the present specification 1 -C 4 Alkoxy of (c) refers to straight or branched chain alkoxy groups having 1 to 4 carbon atoms and includes, but is not limited to methoxy, ethoxy, n-propoxy, and the like.
C as used in the present specification 1 -C 4 Is meant to be singly bound to a member which is substituted by three C' s 1 -C 4 And include, but are not limited to, trimethylsiloxy, triethylsiloxy, and the like.
C as used in the present specification 1 -C 4 The haloalkoxy group of (c) refers to a straight-chain or branched alkoxy group having 1 to 4 carbon atoms substituted with one or more halogens selected from the group consisting of fluorine, chlorine, bromine and iodine, and includes, but is not limited to, trichloromethoxy, trifluoroethoxy, and the like.
In one embodiment of the invention, X is C 1 -C 4 Trialkylsiloxy groups of (a).
In one embodiment of the invention, X is trimethylsilyloxy.
In one embodiment of the present invention, the compound represented by chemical formula 1 has a low LUMO (lowest unoccupied molecular orbital) and thus has a high tendency of reductive decomposition, and is reductively decomposed to form a stable film on the surface of the anode before a nonaqueous solvent in an electrolyte composition, so that life characteristics can be improved. In addition, a flexible film is formed by a propane sultone compound in which carbon at the 2 nd position is substituted with a specific substituent, and therefore generation of cracks is suppressed even during repeated charge and discharge, whereby long-term life characteristics can be ensured. In particular, from the viewpoint of long-term life characteristics, a propane sultone compound in which the carbon at the 2 nd position is substituted with trimethylsilyloxy group is preferable.
The compound represented by chemical formula 1 may be prepared and used using a commercially available product or by a method known in the art.
The compound represented by chemical formula 1 may be included in an amount of 0.05 to 15 wt% based on 100 wt% of the total electrolyte composition. When the compound represented by chemical formula 1 is contained in an amount of less than 0.05 wt%, the SEI film may be formed to be thin without affecting the life characteristics of the battery, and when the compound represented by chemical formula 1 is contained in an amount of more than 15 wt%, the SEI film is excessively formed, and thus the resistance of the battery increases due to the SEI film on the anode surface, which may deteriorate the life characteristics.
In one embodiment of the invention, the nonaqueous solvent serves as a medium through which ions associated with the electrochemical reaction of the cell can move.
As the nonaqueous solvent, nonaqueous solvents generally used in the art can be used without particular limitation. For example, a carbonate-based solvent, an ester-based solvent, an ether-based solvent, a ketone-based solvent, an alcohol-based solvent, or other aprotic solvents may be used as the nonaqueous solvent. These may be used singly or in combination of two or more.
As the carbonate solvent, a chain carbonate solvent, a cyclic carbonate solvent, a fluorinated carbonate solvent thereof, or a combination thereof may be used.
The chain carbonate solvent may be, for example, diethyl carbonate (diethyl carbonate, DEC), dimethyl carbonate (dimethyl carbonate, DMC), dipropyl carbonate (dipropyl carbonate, DPC), methylpropyl carbonate (methylpropyl carbonate, MPC), ethylpropyl carbonate (ethylpropyl carbonate, EPC), ethylmethyl carbonate (ethylmethyl carbonate, EMC) or combinations thereof, and the cyclic carbonate solvent may be, for example, ethylene carbonate (ethylene carbonate, EC), propylene carbonate (propylene carbonate, PC), butylene carbonate (butylene carbonate, BC), vinyl ethylene carbonate (vinylethylene carbonate, VEC) or combinations thereof.
The fluorocarbonate solvent may be, for example, fluoroethylene carbonate (FEC), 4, 5-difluoroethylene carbonate, 4, 5-trifluoroethylene carbonate, 4, 5-tetrafluoroethylene carbonate, 4-fluoro-5-methylethylene carbonate, 4-fluoro-4-methylethylene carbonate, 4, 5-difluoro-4-methylethylene carbonate, 4, 5-trifluoro-5-methylethylene carbonate, or a combination thereof.
As the ester solvent, methyl acetate, ethyl acetate, n-propyl acetate, methyl propionate, ethyl propionate, gamma-butyrolactone, decalactone, valerolactone, mevalonic acid lactone, caprolactone, methyl formate and the like can be used.
As the ether solvent, dibutyl ether, tetraethylene glycol dimethyl ether, diethylene glycol dimethyl ether, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, ethoxymethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, etc. can be used.
Cyclohexanone may be used as the ketone solvent.
As the alcohol solvent, ethanol, isopropanol and the like can be used.
As the other aprotic solvent, dimethyl sulfoxide, 1, 2-dioxolane, sulfolane, methyl sulfolane, 1, 3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, formamide, dimethylformamide, acetonitrile, nitromethane, trimethyl phosphate, triethyl phosphate, trioctyl phosphate, etc. can be used.
The electrolyte composition according to an embodiment of the present invention may further include a lithium salt.
The lithium salt serves as a supply source of lithium ions in the battery and to promote movement of lithium ions between the positive and negative electrodes.
Examples of the lithium salt may be LiPF 6 、LiBF 4 、LiSbF 6 、LiAsF 6 、LiN(SO 2 C 2 F 5 ) 2 、Li(CF 3 SO 2 ) 2 N、LiN(SO 3 C 2 F 5 ) 2 、LiC 4 F 9 SO 3 、LiClO 4 、LiAlO 2 、LiAlCl 4 、LiCl、LiI、LiB(C 2 O 4 ) 2 (lithium oxalato borate, liBOB) and the like. These may be used singly or in combination of two or more.
The concentration of the lithium salt may be 0.1 to 2.0M. If the concentration of the lithium salt is within the above range, the electrolyte composition may have appropriate conductivity and viscosity.
An embodiment of the present invention relates to a secondary battery comprising the above electrolyte composition.
The secondary battery according to the present invention includes the electrolyte composition of the present invention containing the compound represented by chemical formula 1 having a low LUMO, and thus can form a stable SEI film on the surface of a negative electrode at the time of first charge (chemical conversion step), thereby providing excellent life characteristics.
In an embodiment of the present invention, the secondary battery may be a lithium secondary battery, for example, a lithium ion secondary battery.
The lithium secondary battery comprises a positive electrode, a negative electrode and the electrolyte composition.
The positive electrode includes a positive electrode collector and a positive electrode active material layer formed on the positive electrode collector.
The positive electrode collector may be used without particular limitation as long as the positive electrode collector has conductivity while not causing chemical changes in the battery. Specifically, the positive electrode current collector includes aluminum, copper, stainless steel, nickel, titanium, calcined carbon, a substance formed by surface treatment of copper or stainless steel with carbon, nickel, titanium, silver, or the like, an aluminum-cadmium alloy, or the like, and in particular, aluminum may be used. The positive electrode current collector may have various shapes such as a foil, a mesh, and a porous body, and fine irregularities may be formed on the surface to enhance the binding force of the positive electrode active material.
The thickness of the positive electrode collector may be 3 to 500 μm.
The positive electrode active material layer includes a positive electrode active material, a binder, and optionally a conductive material.
As the positive electrode active material, a compound capable of reversibly intercalating and deintercalating lithium can be used. Specifically, as the positive electrode active material, one or more of a composite oxide of a metal of cobalt, manganese, nickel, aluminum, iron, or a combination thereof and lithium or a composite phosphorus oxide may be used. More specifically, lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt aluminum oxide, lithium iron phosphate, and the like can be used as the positive electrode active material.
The binder is used to attach the positive electrode active material particles to each other and to attach the positive electrode active material to the positive electrode current collector. Specifically, the binder includes polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, an ethylene oxide-containing polymer, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylic styrene-butadiene rubber, epoxy resin, nylon, and the like.
The conductive material is used to impart conductivity to the electrode, and may be used without limitation as long as it has electron conductivity without causing chemical change. Specifically, the conductive material includes carbon-based substances such as natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, and carbon fiber; metal species such as copper, nickel, aluminum, and silver; conductive polymers such as polyphenylene derivatives; etc.
The negative electrode includes a negative electrode collector and a negative electrode active material layer formed on the negative electrode collector.
The negative electrode collector may be used without particular limitation as long as the negative electrode collector has conductivity while not causing chemical changes in the battery. Specifically, the negative electrode current collector includes copper, aluminum, stainless steel, nickel, titanium, calcined carbon, a substance formed by surface treatment with carbon, nickel, titanium, silver, or the like on the surface of copper or stainless steel, an aluminum-cadmium alloy, or the like, and in particular, copper may be used. The negative electrode current collector may have various shapes such as a foil, a mesh, and a porous body, and fine irregularities may be formed on the surface to enhance the binding force of the negative electrode active material.
The thickness of the negative electrode current collector may be 3 to 500 μm.
The anode active material layer includes an anode active material, a binder, and optionally a conductive material.
As the negative electrode active material, a material capable of reversibly intercalating and deintercalating lithium ions, lithium metal, an alloy of lithium metal, a material capable of doping and dedoping lithium, a transition metal oxide, and the like can be used.
The substance capable of reversibly intercalating and deintercalating lithium ions may use crystalline carbon, amorphous carbon, or a combination thereof as a carbon-based substance. Examples of the crystalline carbon include amorphous, plate-like, flake-like, spherical or fibrous graphite, and may be natural graphite or artificial graphite. Examples of the amorphous carbon may be soft or hard carbon, mesophase pitch carbide, calcined coke, and the like.
As the alloy of lithium metal, an alloy of lithium and a metal selected from the group consisting of Na, K, rb, cs, fr, be, mg, ca, sr, si, sb, pb, in, zn, ba, ra, ge, al and Sn can be used.
The substances capable of doping and dedoping lithium can be Si, si-C complex, siO x (0 < x < 2), si-Q alloy (wherein Q is an element selected from the group consisting of alkali metals, alkaline earth metals, group 13 elements, group 14 elements, group 15 elements, group 16 elements, transition metals, rare earth elements, and combinations thereof, si is not Si), sn, snO 2 An Sn-R alloy (wherein R is an element selected from the group consisting of alkali metals, alkaline earth metals, group 13 elements, group 14 elements, group 15 elements, group 16 elements, transition metals, rare earth elements, and combinations thereof, and Sn is not n), or at least one of them and SiO may be mixed 2 And used. The elements Q and R may be selected from the group consisting of 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 and combinations thereof.
The transition metal oxide may be vanadium oxide, lithium titanium oxide, or the like.
The binder is used to attach the anode active material particles to each other and to attach the anode active material to the anode current collector. Specifically, the binder may be the same as the binder used for the positive electrode active material layer.
The conductive material is used to impart conductivity to the electrode, and may be used without limitation as long as it has electron conductivity without causing chemical change. Specifically, the conductive material may be the same as that used for the positive electrode active material layer.
The positive electrode and the negative electrode may be manufactured by manufacturing methods known in the art.
Specifically, the positive electrode and the negative electrode are prepared by mixing the corresponding active material, binder, and optional conductive material in a solvent to prepare an active material composition, and coating the active material composition onto a current collector.
As the solvent, N-methylpyrrolidone (NMP), acetone, water, or the like can be used.
The positive electrode and the negative electrode may be separated by a separator. The separator may be used without particular limitation as long as it is generally used in the art. In particular, it is suitable to have low ion migration resistance in the electrolyte composition and to have excellent moisture absorption ability of the electrolyte composition. The separator may be a material selected from the group consisting of glass fiber, polyester, teflon, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), and combinations thereof, and may be in the form of a non-woven fabric or a woven fabric. The membrane may have a pore size of 0.01 to 10 μm and a thickness of 3 to 100 μm. The separator may be a single film or a multilayer film.
The lithium secondary battery may be manufactured by a manufacturing method well known in the art.
Specifically, the lithium secondary battery is manufactured by: a separator is interposed between the positive electrode and the negative electrode to obtain a laminate, and then the laminate is wound or folded to be contained in a battery container, into which an electrolyte composition is injected, and sealed with a sealing member.
The battery container may be cylindrical, angular, film-shaped, etc.
The secondary battery may be used in a mobile phone, a portable computer, an electric vehicle, and the like. In addition, the secondary battery may be used in combination with an internal combustion engine, a fuel cell, a super capacitor, etc. in a hybrid vehicle, etc., and may also be used in an electric bicycle, an electric tool, etc. that require high power, high voltage, and high temperature driving.
Hereinafter, the present invention will be described in more detail with reference to examples, comparative examples and experimental examples. It is obvious to those skilled in the art that these examples, comparative examples and experimental examples are only for describing the present invention, and the scope of the present invention is not limited thereto.
Example 1: preparation of electrolyte composition
In a mixed solvent in which Ethylene Carbonate (EC) and dimethyl carbonate (DMC) are mixed in a volume ratio of 3:7, liPF is added 6 The compound represented by the following chemical formula 2 was added in an amount of 1 wt% based on 100 wt% of the total electrolyte composition to make it 1.0M, thereby preparing an electrolyte composition.
[ chemical formula 2]
Example 2: preparation of electrolyte composition
An electrolyte composition was prepared in the same manner as in example 1, except that the compound represented by the following chemical formula 3 was used instead of the compound represented by chemical formula 2.
[ chemical formula 3]
Example 3: preparation of electrolyte composition
An electrolyte composition was prepared in the same manner as in example 1, except that the compound represented by the following chemical formula 4 was used instead of the compound represented by chemical formula 2.
[ chemical formula 4]
Example 4: preparation of electrolyte composition
An electrolyte composition was prepared in the same manner as in example 1, except that the compound represented by the following chemical formula 5 was used instead of the compound represented by chemical formula 2.
[ chemical formula 5]
Example 5: preparation of electrolyte composition
An electrolyte composition was prepared in the same manner as in example 1, except that the compound represented by the following chemical formula 6 was used instead of the compound represented by chemical formula 2.
[ chemical formula 6]
Example 6: preparation of electrolyte composition
An electrolyte composition was prepared in the same manner as in example 1, except that the compound represented by the following chemical formula 7 was used instead of the compound represented by chemical formula 2.
[ chemical formula 7]
Example 7: preparation of electrolyte composition
An electrolyte composition was prepared in the same manner as in example 3, except that the compound represented by chemical formula 4 was added in an amount of 5 wt% based on 100 wt% of the total electrolyte composition.
Comparative example 1: preparation of electrolyte composition
An electrolyte composition was prepared in the same manner as in example 1, except that the compound represented by chemical formula 2 was not added.
Comparative example 2: preparation of electrolyte composition
An electrolyte composition was prepared in the same manner as in example 1, except that the compound represented by the following chemical formula a was used instead of the compound represented by chemical formula 2.
[ chemical formula a ]
Comparative example 3: preparation of electrolyte composition
An electrolyte composition was prepared in the same manner as in example 1, except that the compound represented by the following chemical formula b was used instead of the compound represented by chemical formula 2.
[ chemical formula b ]
Comparative example 4: preparation of electrolyte composition
An electrolyte composition was prepared in the same manner as in example 1, except that the compound represented by the following chemical formula c was used instead of the compound represented by chemical formula 4.
[ chemical formula c ]
Comparative example 5: preparation of electrolyte composition
An electrolyte composition was prepared in the same manner as in example 3, except that the compound represented by chemical formula 4 was added in an amount of 20 wt% based on 100 wt% of the total electrolyte composition.
Experimental example 1
Secondary batteries were prepared as follows using the electrolyte compositions prepared in the examples and comparative examples, and normal-temperature and high-temperature life characteristics at this time were measured in the following manner.
< preparation of Secondary Battery >
LiNi as a positive electrode active material was mixed at a weight ratio of 90:5:5 1/3 Co 1/3 Mn 1/3 O 2 N-methylpyrrolidone was added as a solvent to a mixture of the powder, a carbon conductive material (Super-P; timcal ltd.) and PVDF (polyvinylidene fluoride) binder so that the solid content was 60 wt%, thereby preparing a positive electrode slurry. The positive electrode slurry was coated to a thickness of about 40 μm on a 15 μm thick aluminum foil. It was dried at room temperature, dried again at 120 ℃, and rolled to prepare a positive electrode.
N-methylpyrrolidone was added to a mixture of artificial graphite, styrene-butadiene rubber and carboxymethyl cellulose as negative electrode active materials mixed in a weight ratio of 90:5:5 so that the solid content was 60% by weight, thereby preparing a negative electrode slurry. The negative electrode slurry was coated to a thickness of about 40 μm on a 10 μm thick aluminum foil. It was dried at room temperature, dried again at 120 ℃, and rolled to prepare a negative electrode.
The positive electrode, the negative electrode and the electrolyte composition are used to manufacture a secondary battery using a separator made of polyethylene.
The prepared secondary battery was charged at 25 deg.c with a constant current of 0.2C until the voltage reached 4.2V, and then discharged at a constant current of 0.2C until the voltage reached 2.5V. Subsequently, charging was performed at a constant current of 0.5C until the voltage reached 4.2V, and charging was performed at a constant voltage while maintaining 4.2V until the current became 0.05C. Subsequently, discharge was performed at a constant current of 0.5C until the voltage reached 2.5V (chemical conversion step).
(1) Life characteristics at ordinary temperature
The secondary battery subjected to the chemical conversion step was charged at 25 ℃ with a constant current of 1.0C until the voltage reached 4.2V, and charged at a constant voltage while maintaining 4.2V until the current reached 0.05C. Subsequently, at the time of discharge, discharge was performed at a constant current of 1.0C until the voltage reached 2.5V, and the above cycle was repeated 100 times.
The capacity retention (%) of each secondary battery at the 100 th cycle was calculated by the following equation 1, and the results thereof are shown in table 1 and fig. 1 below.
[ equation 1]
Capacity retention [% ] = [ discharge capacity of 100 th cycle/discharge capacity of 1 st cycle ] ×100
(2) High temperature life characteristics
The measurement was performed in the same manner as the normal temperature lifetime property measurement method except that the measurement conditions were set to 45 ℃ instead of 25 ℃ and performed 300 times, the results of which are shown in table 1 and fig. 2 below.
TABLE 1
| Life characteristics at ordinary temperature | High temperature life characteristics | |
| Example 1 | 95％ | 84％ |
| Example 2 | 91％ | 80％ |
| Example 3 | 96％ | 83％ |
| Example 4 | 93％ | 81％ |
| Example 5 | 94％ | 84％ |
| Example 6 | 95％ | 84％ |
| Example 7 | 90％ | 79％ |
| Comparative example 1 | 35％ | 22％ |
| Comparative example 2 | 81％ | 74％ |
| Comparative example 3 | 82％ | 72％ |
| Comparative example 4 | 89％ | 76％ |
| Comparative example 5 | 85％ | 58％ |
As shown in table 2 above, it was confirmed that the secondary batteries prepared using the electrolyte composition comprising the propane sultone compound in which carbon at a specific position was substituted with a specific substituent according to the present invention had more excellent life characteristics not only at normal temperature but also at high temperature as compared with the secondary batteries prepared using the electrolyte compositions of comparative examples 1 to 5.
In addition, when example 3 and comparative example 5 were compared, it was confirmed that when more than 15% by weight of the propane sultone compound in which carbon at a specific position according to the present invention was substituted with a specific substituent was added based on 100% by weight of the total electrolyte composition, life characteristics were deteriorated.
While specific portions of the present invention have been described in detail above, it will be apparent to those skilled in the art that the specific techniques are merely preferred embodiments, and the scope of the present invention is not limited thereto. Based on the foregoing, one of ordinary skill in the art to which this invention pertains will be able to make various applications and modifications within the scope of the invention.
Accordingly, the substantial scope of the present invention will be defined by the appended claims and equivalents thereof.
Claims (6)
1. An electrolyte composition comprising a compound represented by the following chemical formula 1 and a nonaqueous solvent, and comprising the compound represented by the following chemical formula 1 in an amount of 0.05 to 5% by weight based on 100% by weight of the total electrolyte composition:
[ chemical formula 1]
In the above-mentioned formula, the catalyst,
x is C 1 -C 4 Alkoxy or C of (2) 1 -C 4 Trialkylsiloxy groups of (a).
2. The electrolyte composition of claim 1, wherein X is C 1 -C 4 Trialkylsiloxy groups of (a).
3. The electrolyte composition of claim 1, wherein X is trimethylsiloxy.
4. The electrolyte composition of claim 1, further comprising a lithium salt.
5. A secondary battery comprising the electrolyte composition according to any one of claims 1 to 4.
6. The secondary battery according to claim 5, wherein the secondary battery is a lithium secondary battery.
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| WO2020111633A1 (en) * | 2018-11-26 | 2020-06-04 | 동우 화인켐 주식회사 | Electrolyte solution composition and secondary battery using same |
| KR102138128B1 (en) | 2018-11-26 | 2020-07-27 | 동우 화인켐 주식회사 | Electrolyte Composition and Secondary Battery Using the Same |
| KR102463257B1 (en) * | 2020-07-06 | 2022-11-04 | 주식회사 테크늄 | Electrolyte for lithium secondary battery and lithium secondary battery comprising the same |
| KR102467447B1 (en) * | 2020-09-03 | 2022-11-15 | 주식회사 테크늄 | Electrolyte for lithium secondary battery and lithium secondary battery comprising the same |
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| KR101941401B1 (en) | 2019-01-22 |
| CN111542963A (en) | 2020-08-14 |
| WO2019156434A1 (en) | 2019-08-15 |
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