WO2016048106A1 - 비수성 전해액 및 이를 포함하는 리튬 이차 전지 - Google Patents
비수성 전해액 및 이를 포함하는 리튬 이차 전지 Download PDFInfo
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- WO2016048106A1 WO2016048106A1 PCT/KR2015/010243 KR2015010243W WO2016048106A1 WO 2016048106 A1 WO2016048106 A1 WO 2016048106A1 KR 2015010243 W KR2015010243 W KR 2015010243W WO 2016048106 A1 WO2016048106 A1 WO 2016048106A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—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
- H01M10/0568—Liquid materials characterised by the solutes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—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
- H01M10/0569—Liquid materials characterised by the solvents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention includes a non-aqueous electrolyte containing lithium bis (fluorosulfonyl) imide (LiFSI) and trimethylsilyl phosphate (TMSPa) additive, and lithium-nickel-manganese-cobalt oxide as a positive electrode active material. It relates to a lithium secondary battery comprising a positive electrode, a negative electrode, and a separator.
- LiFSI lithium bis (fluorosulfonyl) imide
- TMSPa trimethylsilyl phosphate
- TMSPa lithium-nickel-manganese-cobalt oxide
- lithium secondary batteries having high energy density and voltage among these secondary batteries are commercially used and widely used.
- Lithium metal oxide is used as a positive electrode active material of a lithium secondary battery, and lithium metal, a lithium alloy, crystalline or amorphous carbon or a carbon composite material is used as a negative electrode active material.
- the active material is applied to a current collector with a suitable thickness and length, or the active material itself is applied in a film shape to form an electrode group by winding or laminating together with a separator, which is an insulator, and then put it in a can or a similar container, and then injecting an electrolyte solution.
- a secondary battery is manufactured.
- lithium secondary battery In such a lithium secondary battery, charging and discharging progress while repeating a process of intercalating and deintercalating lithium ions from a lithium metal oxide of a positive electrode to a graphite electrode of a negative electrode.
- lithium is highly reactive and reacts with the carbon electrode to generate Li 2 CO 3 , LiO, LiOH and the like to form a film on the surface of the negative electrode.
- a film is called a solid electrolyte interface (SEI) film, and the SEI film formed at the beginning of charging prevents the reaction between lithium ions and a carbon anode or other material during charging and discharging. It also acts as an ion tunnel, allowing only lithium ions to pass through.
- the ion tunnel serves to prevent the organic solvents of a large molecular weight electrolyte which solvates lithium ions and move together and are co-intercalated with the carbon anode to decay the structure of the carbon anode.
- a solid SEI film must be formed on the negative electrode of the lithium secondary battery. Once formed, the SEI membrane prevents the reaction between lithium ions and the negative electrode or other materials during repeated charge / discharge cycles, and serves as an ion tunnel that passes only lithium ions between the electrolyte and the negative electrode. Will be performed.
- the problem to be solved by the present invention is to provide a non-aqueous electrolyte lithium secondary battery and a lithium secondary battery comprising the same, which can not only improve the output characteristics, but also improve the life characteristics.
- the present invention is a non-aqueous electrolyte containing lithium bis (fluorosulfonyl) imide (LiFSI) and trimethylsilyl phosphate (TMSPa) additive, lithium-nickel-manganese as a positive electrode active material It provides a lithium secondary battery comprising a positive electrode, a negative electrode, and a separator containing a cobalt-based oxide.
- LiFSI lithium bis (fluorosulfonyl) imide
- TMSPa trimethylsilyl phosphate
- the non-aqueous electrolyte solution may further include a lithium salt, the mixing ratio of the lithium salt and lithium bisfluoro sulfonyl imide is 1: 0.01 to 1: 1 in molar ratio, the lithium bisfluoro sulfonyl imide is
- the lithium secondary battery may have a concentration in the aqueous electrolyte of 0.01 mol / L to 2 mol / L.
- the lithium-nickel-manganese-cobalt-based oxide may include an oxide represented by Formula 1 below.
- a solid SEI film is formed at the negative electrode during initial charging of the lithium secondary battery including the same, and the output characteristics and capacity characteristics after high temperature storage are improved, as well as improving the output characteristics of the lithium secondary battery. Can improve.
- the non-aqueous electrolyte solution according to one embodiment of the present invention includes lithium bisfluorosulfonylimide (LiFSI).
- the lithium bisfluorosulfonylimide is added to the non-aqueous electrolyte as a lithium salt to form a solid, thin SEI film on the negative electrode to improve low temperature output characteristics, as well as to decompose positive electrode surfaces that may occur during high temperature cycle operation. It can suppress and prevent the oxidation reaction of electrolyte solution.
- the SEI film generated on the negative electrode has a small thickness so that the movement of lithium ions in the negative electrode can be more smoothly performed, thereby improving the output of the secondary battery.
- the lithium bisfluorosulfonylimide preferably has a concentration in the non-aqueous electrolyte of 0.01 mol / L to 2 mol / L, more preferably 0.01 mol / L to 1 mol / L. Do.
- the concentration of the lithium bisfluorosulfonylimide is less than 0.1 mol / L, the effect of improving the low temperature output and the high temperature cycle characteristics of the lithium secondary battery is insignificant, and the concentration of the lithium bisfluorosulfonylimide is When the amount exceeds 2 mol / l, side reactions in the electrolyte may be excessively generated during charging and discharging of the battery, and swelling may occur, and corrosion of the positive electrode or the negative electrode current collector made of metal in the electrolyte may occur.
- the non-aqueous electrolyte solution of the present invention may further include a lithium salt.
- the lithium salt may be used a lithium salt commonly used in the art, for example LiPF 6 , LiAsF 6 , LiCF 3 SO 3 , LiBF 6 , LiSbF 6 , LiN (C 2 F 5 SO 2 ) 2 , LiAlO 4 , LiAlCl 4 , LiSO 3 CF 3 and LiClO 4 may be any one selected from the group consisting of or a mixture of two or more thereof.
- the mixing ratio of the lithium salt and lithium bisfluoro sulfonyl imide is preferably 1: 0.01 to 1 as molar ratio.
- the mixing ratio of the lithium salt and lithium bisfluoro sulfonyl imide is greater than or equal to the molar ratio, side reactions in the electrolyte may occur excessively during charging and discharging of the battery, and a swelling phenomenon may occur. In this case, output improvement of the generated secondary battery may be reduced.
- the mixing ratio of the lithium salt and lithium bisfluoro sulfonyl imide is less than 1: 0.01
- a process of forming an SEI film in a lithium ion battery, and lithium ions solvated by a carbonate solvent In the process of being inserted between the negative electrode, a large number of irreversible reactions may occur, and by the peeling of the negative electrode surface layer (for example, the carbon surface layer) and the decomposition of the electrolyte, the low temperature output of the secondary battery may be improved, the high temperature storage may be performed, The effect of improving the dose characteristics may be insignificant.
- the mixing ratio of the lithium salt and the lithium bisfluoro sulfonyl imide is a molar ratio
- the ratio is greater than 1: 1
- lithium bisfluoro sulfonyl imide of excessive capacity is included in the electrolyte to prevent corrosion of the electrode current collector during charging and discharging. This may affect the stability of the secondary battery.
- the positive electrode active material which is the lithium-nickel-manganese-cobalt-based oxide may include an oxide represented by Formula 1 below.
- the positive electrode active material which is the lithium-nickel-manganese-cobalt-based oxide
- the positive electrode active material which is the lithium-nickel-manganese-cobalt-based oxide
- it may be combined with lithium bisfluoro sulfonyl imide to have a synergistic effect.
- Li + 1 ions and Ni + 2 ions in the layered structure of the cathode active material change as the amount of Ni in the transition metal increases. mixing) occurs and the structure thereof collapses, and the cathode active material causes side reactions with the electrolyte, or dissolution of transition metals. This occurs because Li +1 ions and Ni +2 ions have similar sizes.
- the performance of the battery is easily degraded due to electrolyte depletion and structural collapse of the positive electrode active material inside the secondary battery.
- LiFSI applied electrolyte to the positive electrode active material of Formula 1 to form a layer layer of the LiFSI-based components on the surface of the anode cation mixing of Li + 1 ions and Ni + 2 ions While suppressing the phenomenon, a range was found in which sufficient nickel transition metal amount for securing the capacity of the positive electrode active material could be secured.
- the positive electrode active material including the oxide according to Chemical Formula 1 of the present invention when using a LiFSI-applied electrolyte, it is possible to effectively suppress the electrolyte, side reactions, metal dissolution and the like.
- Li + 1 is also ionized by the layer layer formed of LiFSI on the electrode surface described above. And Ni +2 may not suppress cation mixing of ions.
- the nickel transition metal having a d-orbit should have an octahedral structure in coordination bond under high temperature or the like due to the variation in the oxidation number of Ni, but in order of energy level by external energy supply. Is reversed, or the oxidation number is varied (disproportionation reaction) to form a distorted octahedron. As a result, the crystal structure of the positive electrode active material including the nickel transition metal is deformed to increase the probability of eluting nickel metal in the positive electrode active material.
- the present inventors have confirmed that while producing a high output when the positive electrode active material including the oxide according to the formula (1) range and the LiFSI salt combination, it shows excellent efficiency in high temperature stability and capacity characteristics.
- LiPF 6 Lithium Salt In the case of, the electrolyte lacking thermal safety easily decomposes in the cell to form LiF and PF 5 . At this time, the LiF salt reduces the conductivity and the number of free Li + ions, thereby increasing the resistance of the cell and consequently reducing the capacity of the cell. That is, phosphate functional groups of trimethylsilyl phosphate (TMSPa) act as anion receptors to stably form PF 6 - by the above decomposition of PF 6 - ions at the anode surface which may occur during high temperature cycle operation.
- TMSPa trimethylsilyl phosphate
- LiPF 6 which is a lithium salt
- lithium bisfluorosulfonylimide by lowering the interfacial resistance at high temperature, a large amount of lithium bisfluorosulfonylimide is generated. It has the effect of preventing possible side reactions.
- the trimethylsilyl phosphate (TMSPa) compound may be added to the electrolyte to serve to form a solid SEI film on the surface of the negative electrode together with lithium bisfluorosulfonylimide.
- the negative electrode surface and the electrolyte may react within the battery to suppress the gas generated due to decomposition of the electrolyte, thereby improving life characteristics of the lithium secondary battery. Therefore, the lithium secondary battery to which trimethylsilyl phosphate (TMSPa) is added according to an embodiment of the present invention can increase the output characteristics more effectively, and the lifespan characteristics can be improved.
- the content of the trimethylsilyl phosphate (TMSPa) compound may be, for example, 0.01 to 5% by weight based on the total amount of the electrolyte.
- the amount of the trimethylsilyl phosphate (TMSPa) compound is less than 0.01% by weight, it is difficult to sufficiently exhibit the effect of forming a solid SEI film and an anion receptor upon addition, and the amount of the trimethylsilyl phosphate (TMSPa) compound is 5 If the weight% is exceeded, the degree of effect increase is limited, but the problem of increasing the irreversible capacity or forming the thickness of the SEI film too thick may increase the resistance of the negative electrode.
- the trimethylsilyl phosphate (TMSPa) compound can be adjusted according to the amount of lithium bis fluoro sulfonyl imide added. This is to more effectively prevent side reactions that may occur with the addition of a large amount of lithium bis fluorosulfonyl imide.
- non-aqueous organic solvent that can be included in the non-aqueous electrolyte, decomposition by the oxidation reaction or the like during the charging and discharging process of the battery can be minimized
- Nitrile solvents cyclic carbonates, linear carbonates, esters, ethers or ketones. These may be used alone, or two or more thereof may be used in combination.
- Carbonate-based organic solvents of the organic solvents can be easily used, the cyclic carbonate is any one selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC) and butylene carbonate (BC) or two of them A mixture of two or more species, the linear carbonate consists of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), ethylmethyl carbonate (EMC), methylpropyl carbonate (MPC) and ethylpropyl carbonate (EPC) It may be any one selected from the group or a mixture of two or more thereof.
- DMC dimethyl carbonate
- DEC diethyl carbonate
- DPC dipropyl carbonate
- EMC ethylmethyl carbonate
- MPC methylpropyl carbonate
- EPC ethylpropyl carbonate
- the nitrile solvents include acetonitrile, propionitrile, butyronitrile, valeronitrile, caprylonitrile, heptanenitrile, cyclopentane carbonitrile, cyclohexane carbonitrile, 2-fluorobenzonitrile and 4-fluorobenzonitrile , Difluorobenzonitrile, trifluorobenzonitrile, phenylacetonitrile, 2-fluorophenylacetonitrile, 4-fluorophenylacetonitrile may be one or more selected from the group consisting of, one embodiment of the present invention Acetonitrile may be used as the non-aqueous solvent according to the example.
- the lithium secondary battery according to an embodiment of the present invention may include a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode and the non-aqueous electrolyte.
- the positive electrode and the negative electrode may each include the positive electrode active material and the negative electrode active material according to an embodiment of the present invention.
- the negative electrode active material includes amorphous carbon or crystalline carbon, specifically, carbon such as non-graphitized carbon, graphite-based carbon; LixFe 2 O 3 (0 ⁇ x ⁇ 1), LixWO 2 (0 ⁇ x ⁇ 1 ), SnxMe 1 - x Me ' y O z (Me: Mn, Fe, Pb, Ge; Me': Al, B, P , Metal complex oxides such as Si, Group 1, 2, 3 Group elements of the periodic table, halogen, 0 ⁇ x ⁇ 1, 1 ⁇ y ⁇ 3, 1 ⁇ z ⁇ 8); Lithium metal; Lithium alloys; Silicon-based alloys; Tin-based alloys; SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , GeO, GeO 2 , Bi 2 O 3 , Bi 2 O
- the separator is a porous polymer film, for example, a porous polymer film made of a polyolefin-based polymer such as ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymer and ethylene / methacrylate copolymer This may be a single or two or more laminated.
- a porous nonwoven fabrics such as high-melting glass fibers, polyethylene terephthalate fibers, and the like may be used, but are not limited thereto.
- the secondary battery is various according to the purpose of performing the cylindrical, square, pouch type and the like, and is not limited to the configuration known in the art.
- Lithium secondary battery according to an embodiment of the present invention may be a pouch type secondary battery.
- EMC ethyl methyl carbonate
- a non-aqueous electrolyte was prepared by mixing lithium bisfluorosulfonylimide and 0.5 wt% trimethylsilyl phosphate (TMSPa) compound based on the total weight of the non-aqueous electrolyte as an additive.
- TMSPa trimethylsilyl phosphate
- Li (Ni 0.6 Co 0.2 Mn 0.2 ) O 2 as a positive electrode active material
- carbon black as a conductive agent
- PVdF polyvinylidene fluoride
- NMP 2-pyrrolidone
- the positive electrode mixture slurry was applied to a thin film of aluminum (Al), which is a positive electrode current collector having a thickness of about 20 ⁇ m, dried to prepare a positive electrode, and then subjected to roll press to prepare a positive electrode.
- a negative electrode mixture slurry was prepared by adding carbon powder as a negative electrode active material, PVdF as a binder, and carbon black as a conductive agent at 96 wt%, 3 wt%, and 1 wt%, respectively, to NMP as a solvent.
- the negative electrode mixture slurry was applied to a thin film of copper (Cu), which is a negative electrode current collector having a thickness of 10 ⁇ m, and dried to prepare a negative electrode, followed by a roll press to prepare a negative electrode.
- Cu copper
- the positive electrode and the negative electrode prepared as described above were manufactured with a polymer battery by a conventional method with a separator composed of three layers of polypropylene / polyethylene / polypropylene (PP / PE / PP), followed by pouring the prepared non-aqueous electrolyte solution into a lithium secondary battery. The manufacture of the battery was completed.
- LiPF 6 based on the total amount of the non-aqueous electrolyte A non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1 except that 0.7 mol / l and 0.3 mol / l of lithium bisfluorosulfonylimide were used.
- LiPF 6 based on the total amount of the non-aqueous electrolyte A non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1 except that 0.6 mol / l and 0.4 mol / l of lithium bisfluorosulfonylimide were used.
- LiPF 6 based on the total amount of the non-aqueous electrolyte A non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1 except that 0.5 mol / l and 0.5 mol / l of lithium bisfluorosulfonylimide were used.
- LiPF 6 based on the total amount of the non-aqueous electrolyte A non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1 except that 0.4 mol / l and 0.6 mol / l of lithium bisfluorosulfonylimide were used.
- a non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 2 except that the additive was not used.
- a non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 2 except that Li (Ni 0.5 Co 0.3 Mn 0.2 ) O 2 was used as the cathode active material.
- the output was calculated using the voltage difference generated when the secondary batteries prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were charged and discharged at ⁇ 30 ° C. at 0.5C for 10 seconds. At this time, the output of Comparative Example 1 was 4.2W. Based on Comparative Example 1, the outputs of Examples 1 to 4 and Comparative Examples 2 to 3 were calculated as percentages. The results are shown in Table 1 below. The test was performed at 50% SOC (state of charge).
- the outputs were calculated using the voltage difference generated when the secondary batteries prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were charged and discharged at 23 ° C. for 0.5 seconds at 0.5 ° C. At this time, the output of Comparative Example 1 was 43.4W. Based on Comparative Example 1, the outputs of Examples 1 to 4 and Comparative Examples 2 to 3 were calculated as percentages. The results are shown in Table 1 below. The test was performed at 50% SOC (state of charge).
- the secondary batteries prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were stored for 24 weeks at 60 ° C., and then the output was calculated using the voltage difference generated when charging and discharging for 10 seconds at 23 ° C. for 5 seconds. At this time, the output of Comparative Example 1 was 37.3W. Based on Comparative Example 1, the outputs of Examples 1 to 4 and Comparative Examples 2 to 3 were calculated as percentages. The results are shown in Table 1 below. The test was performed at 50% SOC (state of charge).
- the secondary batteries of Examples 1 to 4 exhibited excellent output at values of about 3 to 12% than the secondary batteries of Comparative Examples 1 to 3 at low temperature and room temperature output.
- the secondary batteries of Examples 1 to 4 have increased stability at high temperature by using a trimethylsilyl phosphate-based (TMSPa) compound as an additive, so that the output characteristics after high temperature storage are 28% higher than those of the secondary batteries of Comparative Examples 1 to 3. It was found that the abnormal output characteristics were excellent.
- TMSPa trimethylsilyl phosphate-based
- the lithium secondary batteries of Examples 1 to 4 and Comparative Examples 1 to 3 were charged at 1 C to 4.2 V / 38 mA in constant current / constant voltage (CC / CV) conditions at 23 ° C., and then to 2.5 V in constant current (CC) conditions. It discharged at 3C and the discharge capacity was measured. This was repeated 1 to 800 cycles, and the discharge capacity measured by calculating the percentage of the 800th cycle as a percentage (800th capacity / 1st capacity * 100 (%)) based on the first cycle is shown in Table 2.
- the lithium secondary batteries of Examples 1 to 4 and Comparative Examples 1 to 3 were charged at 1 C to 4.2 V / 38 mA at constant current / constant voltage (CC / CV) conditions at 45 ° C., and then to 2.5 V at constant current (CC) conditions. It discharged at 3C and the discharge capacity was measured. This was repeated 1 to 800 cycles, and the discharge capacity measured by calculating the percentage of the 800th cycle as a percentage (800th capacity / 1st capacity * 100 (%)) based on the first cycle is shown in Table 2.
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Abstract
Description
출력 특성(%)- 비교예 1 대비 | |||
저온 출력 | 상온 출력 | 고온저장 후 출력 | |
실시예 1 | 3.25 | 1.89 | 7.21 |
실시예 2 | 8.87 | 4.27 | 18.36 |
실시예 3 | 5.32 | 3.39 | 12.87 |
실시예 4 | 2.91 | 2.11 | 7.5 |
비교예 1 | - | - | - |
비교예 2 | -0.95 | -1.63 | -6.32 |
비교예 3 | -4.12 | -2.31 | -9.89 |
수명 특성(%) | ||
상온 수명 특성 | 고온 수명 특성 | |
실시예 1 | 81.3 | 77.1 |
실시예 2 | 86.6 | 81.9 |
실시예 3 | 83.1 | 78.7 |
실시예 4 | 81.2 | 76.5 |
비교예 1 | 78.4 | 73.2 |
비교예 2 | 76.6 | 72.6 |
비교예 3 | 68.9 | 63.9 |
Claims (11)
- 리튬 비스플루오로 설포닐 이미드(Lithium bis(fluorosulfonyl)imide; LiFSI) 및 트리메틸실릴 포스페이트(TMSPa) 첨가제를 포함하는 비수성 전해액; 양극 활물질로서 리튬-니켈-망간-코발트계 산화물을 포함하는 양극; 음극; 및 분리막을 포함하는 리튬 이차전지.
- 제 1 항에 있어서,상기 비수성 전해액은 리튬염을 더 포함하는 리튬 이차전지.
- 제 2 항에 있어서,상기 리튬염과 리튬 비스플루오로 설포닐 이미드의 혼합비는 몰비로서 1:0.01 내지 1:1인 리튬 이차전지.
- 제 1 항에 있어서,상기 리튬 비스플루오로 설포닐 이미드는 비수성 전해액 중의 농도가 0.01 mol/ℓ 내지 2 mol/ℓ인 리튬 이차전지.
- 제 2 항에 있어서,상기 리튬염은 LiPF6, LiAsF6, LiCF3SO3, LiN(CF3SO2)2, LiBF6, LiSbF6, LiN(C2F5SO2)2, LiAlO4, LiAlCl4, LiSO3CF3 및 LiClO4로 이루어진 군에서 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물을 포함하는 리튬 이차전지.
- 제 1 항에 있어서,상기 리튬-니켈-망간-코발트계 산화물은 하기 화학식 1로 표시되는 산화물을 포함하는 리튬 이차전지:[화학식 1]Li1+x(NiaCobMnc)O2상기 화학식 1에서, 0.55≤a≤0.65, 0.18≤b≤0.22, 0.18≤c≤0.22, -0.2≤x≤0.2, 및 x+a+b+c+=1이다.
- 제 1 항에 있어서,상기 비수성 유기 용매는 니트릴계 용매, 선형 카보네이트, 환형 카보네이트, 에스테르, 에테르, 케톤 또는 이들의 조합을 포함하는 리튬 이차전지.
- 제 7 항에 있어서,상기 환형 카보네이트는 에틸렌 카보네이트(EC), 프로필렌카보네이트(PC) 및 부틸렌 카보네이트(BC)로 이루어진 군에서 선택된 어느 하나 또는 이들 중 2종 이상의 혼합물이고, 선형 카보네이트는 디메틸카보네이트(DMC), 디에틸 카보네이트(DEC), 디프로필 카보네이트(DPC), 에틸메틸카보네이트(EMC), 메틸프로필카보네이트(MPC) 및 에틸프로필 카보네이트(EPC)로 이루어진 군에서 선택된 어느 하나 또는 이들 중 2종 이상의 혼합물인 리튬 이차전지.
- 제 7 항에 있어서,상기 니트릴계 용매는 아세토니트릴, 프로피오니트릴, 부티로니트릴, 발레로니트릴, 카프릴로니트릴, 헵탄니트릴, 싸이클로펜탄 카보니트릴, 싸이클로헥산 카보니트릴, 2-플루오로벤조니트릴, 4-플루오로벤조니트릴, 다이플루오로벤조니트릴, 트리플루오로벤조니트릴, 페닐아세토니트릴, 2-플루오로페닐아세토니트릴, 4-플루오로페닐아세토니트릴로 이루어진 군에서 선택되는 1종 이상인 리튬 이차전지.
- 제 1 항에 있어서,상기 트리메틸실릴 포스페이트(TMSPa) 첨가제는 상기 비수 전해액 총 중량을 기준으로 0.01~5 중량%인 리튬 이차전지.
- 제 1 항 내지 제 10 항 중 어느 한 항의 이차전지는 파우치형 리튬 이차전지인 리튬 이차전지.
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EP3528332B1 (en) | 2017-03-17 | 2021-06-02 | LG Chem, Ltd. | Electrolyte for lithium secondary battery and lithium secondary battery comprising same |
KR101950088B1 (ko) * | 2017-04-13 | 2019-02-19 | 인천대학교 산학협력단 | 실릴포스페이트계 전해액 첨가제, 및 이를 포함하는 리튬이차전지 |
PL3648233T3 (pl) * | 2018-02-12 | 2024-06-10 | Lg Energy Solution, Ltd. | Niewodny roztwór elektrolitu dla litowej baterii akumulatorowej i zawierająca go litowa bateria akumulatorowa |
JP7206556B2 (ja) * | 2018-03-30 | 2023-01-18 | 三井化学株式会社 | 電池用非水電解液及びリチウム二次電池 |
JP7169763B2 (ja) * | 2018-04-09 | 2022-11-11 | 日産自動車株式会社 | 非水電解質二次電池 |
CN111512480A (zh) * | 2018-05-11 | 2020-08-07 | 株式会社Lg化学 | 锂二次电池 |
KR102594515B1 (ko) * | 2018-10-26 | 2023-10-27 | 주식회사 엘지에너지솔루션 | 리튬 이차 전지용 전극의 제조방법 및 이를 이용하여 제조한 리튬 이차 전지용 전극 |
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