WO2018004110A1 - Electrolyte solution for lithium-sulfur battery and lithium-sulfur battery comprising same - Google Patents
Electrolyte solution for lithium-sulfur battery and lithium-sulfur battery comprising same Download PDFInfo
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- WO2018004110A1 WO2018004110A1 PCT/KR2017/002607 KR2017002607W WO2018004110A1 WO 2018004110 A1 WO2018004110 A1 WO 2018004110A1 KR 2017002607 W KR2017002607 W KR 2017002607W WO 2018004110 A1 WO2018004110 A1 WO 2018004110A1
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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
- H01M10/056—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
- H01M10/056—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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a three-component lithium-sulfur battery electrolyte and a lithium-sulfur battery comprising the same.
- Lithium-sulfur battery is a secondary battery that uses a sulfur-based material having an SS bond (Sulfur-sulfur bond) as a positive electrode active material and a lithium metal as a negative electrode active material.
- Sulfur the main material of the positive electrode active material, is very rich in resources and toxic. This has the advantage of having a low weight per atom.
- the theoretical discharge capacity of the lithium-sulfur battery is 1672mAh / g-sulfur, and the theoretical energy density is 2,600 Wh / kg, and the theoretical energy density of other battery systems currently being studied (Ni-MH battery: 450 Wh / kg, Li- FeS cells: 480 Wh / kg, Li-MnO 2 batteries: 1,000 Wh / kg, Na-S cells: 800 Wh / kg) is very high compared to the attention has been attracting attention as a battery having a high energy density characteristics.
- the lithium-sulfur battery has not been commercialized yet. This is because, when sulfur is used as an active material, the ratio (sulfur utilization rate) used for the electrochemical reaction is low, so that a sufficient capacity as the theoretical capacity is not obtained. In order to overcome this problem, development of an anode material having an increased sulfur impregnation amount and an electrolyte solution capable of increasing sulfur utilization rate has been made.
- 1,3-dioxolane (DOL) and 1,2-dimethoxyethane (DME), which show excellent sulfur utilization, are used as electrolyte solvents of lithium-sulfur batteries. These are used alone or in combination, and Korean Patent Laid-Open Publication No. 10-2009-0086575 uses a polymer to separate 1,3-dioxolane in an anode and 1,2-dimethoxyethane in an unbalanced manner in a positive electrode. Lithium-sulfur batteries are disclosed.
- the solvent has a disadvantage in that it is easy to decompose during battery operation.
- gases such as hydrogen, methane, and ethene are generated, which causes swelling and eventually shortens the life of the battery.
- the present inventors studied the electrolyte solvent composition of the lithium-sulfur battery to solve the above problems, and as a result, the present invention was completed.
- an object of the present invention is to provide an electrolyte solution for lithium-sulfur batteries with excellent stability.
- Another object of the present invention to provide a lithium-sulfur battery comprising the electrolyte.
- the non-aqueous solvent is N-aqueous solvent
- the cyclic ether may be a 5 to 7 membered cyclic ether unsubstituted or substituted with a C1 to C4 alkyl or alkoxy group.
- the cyclic ether may be dioxolane or dioxane substituted or unsubstituted with an alkyl or alkoxy group of C1 to C4, and specifically, the cyclic ether may be 1,3-dioxolane, 4,5-diethyl -1,3-dioxolane, 4,5-dimethyl-1,3-dioxolane, 4-methyl-1,3-dioxolane, 4-ethyl-1,3-dioxolane, 1,3-dioxane, It may be one selected from the group consisting of 1,4-dioxane, 4-methyl-1,3-dioxane, and 2-methyl-1,3-dioxane.
- the glycol ether may be one selected from the group consisting of 1,2-dimethoxyethane, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.
- the linear ether may be one selected from the group consisting of ethylene glycol ethyl methyl ether, ethylene glycol diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, and diisobutyl ether.
- the cyclic ether may be included in 10 to 40% by volume of the total weight of the non-aqueous solvent.
- glycol ether and the linear ether may be included in a volume ratio of 1: 3 to 3: 1.
- the lithium salt is LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiC 4 BO 8 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , CH 3 SO 3 Li, CF 3 SO 3 Li, (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 ) 2 NLi, (SO 2 F) 2 NLi, (CF 3 SO 2 ) 3 CLi, Chloro It may be one selected from the group consisting of lithium borane, lower aliphatic lithium carbonate, lithium 4-phenyl borate, lithium imide, and combinations thereof.
- the lithium salt may be included in a concentration of 0.1 to 4.0 M.
- the electrolyte may further include an additive having an intramolecular N-O bond.
- the additive is lithium nitrate, potassium nitrate, cesium nitrate, barium nitrate, ammonium nitrate, lithium nitrite, potassium nitrite, cesium nitrite, ammonium nitrite, methyl nitrate, dialkyl imidazolium nitrate, guanidine nitrate, imide Dazolium nitrate, pyridinium nitrate, ethyl nitrite, propyl nitrite, butyl nitrite, pentyl nitrite, octyl nitrite, nitromethane, nitropropane, nitrobutane, nitrobenzene, dinitrobenzene, nitro pyridine, di It may be one or more selected from the group consisting of nitropyridine, nitrotoluene, dinitrotolu
- the additive may be included in 0.01 to 10% by weight relative to 100% by weight of the electrolyte.
- the present invention also provides a lithium-sulfur battery comprising the electrolyte solution.
- the electrolyte solution for lithium-sulfur batteries according to the present invention shows excellent sulfur utilization when applied to lithium-sulfur batteries, and shows excellent stability. Therefore, the electrolyte solution for a lithium-sulfur battery according to the present invention can ensure the capacity characteristics of the lithium-sulfur battery and at the same time improve the life characteristics.
- FIG. 1 is a graph showing specific discharge capacities of batteries of Examples 1, 2 and Comparative Example 1.
- FIG. 2 is a graph showing specific discharge capacities of batteries of Examples 3 to 6 and Comparative Example 2.
- the most commonly used solvent for the electrolyte of lithium-sulfur batteries is a mixed solvent of 1,3-dioxolane (DOL) and 1,2-dimethoxyethane (DME).
- DOL 1,3-dioxolane
- DME 1,2-dimethoxyethane
- the electrolyte according to the present invention exhibits excellent solvent stability compared to conventional electrolytes, including cyclic ethers, glycol ethers, and linear ethers, and exhibits improved life characteristics.
- the present invention includes a lithium salt and a non-aqueous solvent in order to improve the battery life degradation due to decomposition of the electrolyte generated when driving the lithium-sulfur battery, the non-aqueous solvent is
- R 1 to R 4 are the same as or different from each other, and each independently an alkyl group of C1 to C6, an aryl group of C6 to C12, or an arylalkyl group of C7 to C13,
- x is an integer from 1 to 4,
- y is an integer from 0 to 4,
- the ether of Formula 1 is different from the ether of Formula 2)
- the alkyl group of C1 to C6 referred to herein is a linear or branched alkyl group, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, t-butyl group, pen Tyl group, hexyl group, etc. can be mentioned, It is not limited to these.
- C6 to C12 aryl group referred to herein may be, for example, a phenyl group unsubstituted or substituted with a C1 to C6 alkyl group, or a naphthyl group.
- the C7 to C13 arylalkyl group mentioned herein may be, for example, a benzyl group, a phenylethyl group, a phenylpropyl group, or a phenylbutyl group unsubstituted or substituted with a C1 to C6 alkyl group.
- R 1 and R 2 may be the same as or different from each other, and preferably may be a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, and more preferably, a methyl group, an ethyl group, or a propyl group.
- R 3 and R 4 are the same as or different from each other, preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, phenyl or benzyl.
- the electrolyte according to the present invention contains a cyclic ether containing two oxygens in the ring structure as the first solvent.
- the cyclic ether is a 5- or more-membered cyclic ether unsubstituted or substituted with an alkyl group, preferably a 5- to 7-membered cyclic ether unsubstituted or substituted with an alkyl group or an alkoxy group of C1 to C4, and more preferably C1.
- Dioxolane or dioxane unsubstituted or substituted with an alkyl group or an alkoxy group of C4.
- Non-limiting examples of the cyclic ethers include 1,3-dioxolane, 1,3-dioxolane, 4,5-diethyl-dioxolane, 4,5-dimethyl-dioxolane, 4-methyl-1, 3-dioxolane, 4-ethyl-1,3-dioxolane, 1,3-dioxane, 1,4-dioxane, 4-methyl-1,3-dioxane, 2-methyl-1,3-di Oxane etc. can be mentioned, Preferably 1, 3- dioxolane can be used.
- the cyclic ether has a low viscosity, good ion mobility, and high reduction stability, thus showing high stability even for long-term operation of the battery.
- the first solvent is preferably included in 10 to 40% by volume, more preferably in 10 to 30% by volume relative to the total volume of the non-aqueous solvent. If the above range is exceeded, there may be a problem in that electrolyte stability is lowered, thereby making it difficult to secure an effect of improving battery life characteristics.
- the electrolyte according to the present invention includes a glycol ether represented by Chemical Formula 1 as the second solvent.
- the glycol ether is, for example, 1,2-dimethoxyethane, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl Ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, and the like, and preferably, 1,2-dimethoxyethane, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, Triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.
- Such glycol ethers may have high solubility of sulfur-based materials to increase sulfur utilization.
- the third solvent of the electrolyte according to the present invention may be a linear ether represented by Formula 2, a glycol ether as described above, or an ether including one oxygen in a molecule.
- the third solvent is a glycol ether, this is a different compound from the second solvent.
- Non-limiting examples of ethers containing one oxygen in the molecular structure include dimethyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, dihexyl ether, ethyl methyl ether, methyl Propyl ether, butyl methyl ether, ethyl propyl ether, butyl propyl ether, phenyl methyl ether, diphenyl ether, dibenzyl ether and the like.
- the third solvent is preferably ethylene glycol ethyl methyl ether, ethylene glycol diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether or diisobutyl ether.
- Such linear ethers exhibit dissolution and solvent degradation inhibitory effects of polysulfides, contributing to electrolyte stability.
- the 1,2-dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and the like are excellent in solubility of sulfur-based materials and contribute to improving capacity characteristics of the battery by increasing sulfur utilization.
- ethylene glycol ethyl methyl ether, ethylene glycol diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether and the like are excellent in stability and do not easily decompose during battery operation. Therefore, when the solvent is used in a suitable mixture, there is an advantage in that the sulfur utilization and the stability of the electrolyte can be secured at the same time.
- the second solvent and the third solvent is preferably included at least 60% by volume relative to the total volume of the non-aqueous solvent.
- the relative ratio of the second solvent and the third solvent may be appropriately adjusted according to the type of the electrode used, the battery capacity, etc., each of which is at least 10% by volume based on the total weight of the non-aqueous solvent, It is preferable in terms of stability.
- the second solvent and the third solvent are preferably mixed in a volume ratio of 1: 3 to 3: 1, and more preferably in a volume ratio of 1: 2 to 2: 1.
- the non-aqueous solvent of the electrolyte solution is 1,3-dioxolane as the first solvent, 1,2-dimethoxyethane as the second solvent, and as the third solvent.
- Ethylene glycol ethylmethyl ether or dipropyl ether, and the volume ratio thereof may be 1: 1: 1 to 1: 2: 2.
- the sulfur utilization rate of the lithium-sulfur battery can be increased, thereby ensuring the capacity characteristics of the battery and improving the battery life. Therefore, it is advantageous for a battery including a high capacity, high loading electrode.
- 1,3-dioxolane as the first solvent ethylene glycol ethyl methyl ether as the second solvent, ethylene glycol diethyl ether, dipropyl ether, or diisobutyl ether as the third solvent is 1 It may be included in a volume ratio of 1: 1 to 1: 2: 2.
- electrolyte stability is greatly improved, and the life characteristics of the battery can be significantly improved.
- the electrolyte may be suitably used in high temperature operating batteries requiring high electrolyte stability.
- the electrolyte solution of the present invention may be prepared to meet various characteristics required in a battery by appropriately selecting a solvent combination.
- the electrolyte solution for lithium-sulfur batteries of the present invention includes a lithium salt added to the electrolyte to increase the ionic conductivity.
- the lithium salt is not particularly limited in the present invention, and may be used without limitation as long as it is commonly used in a lithium secondary battery.
- the lithium salt is LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiC 4 BO 8 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , CH 3 SO 3 Li, CF 3 SO 3 Li, (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 ) 2 NLi, (SO 2 F) 2 NLi, (CF 3 SO 2 ) 3 CLi,
- lower aliphatic lithium carbonate lower aliphatic may mean, for example, aliphatic having 1 to 5 carbon atoms
- 4-phenyl lithium borate lithium imide and combinations thereof
- One selected may be possible, and preferably (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 ) 2 NLi, (SO 2 F) 2 NLi, or the like may be possible, and preferably (CF 3 SO 2 )
- the concentration of the lithium salt may be determined in consideration of ionic conductivity and the like, and preferably, 0.1 to 4.0 M, or 0.5 to 2.0 M. If the concentration of the lithium salt is less than the above range it is difficult to secure the ionic conductivity suitable for driving the battery, if it exceeds the above range, the viscosity of the electrolyte may be increased to reduce the mobility of lithium ions and the decomposition reaction of the lithium salt itself increases to increase the battery Since the performance of may be degraded, it is appropriately adjusted within the above range.
- the electrolyte solution for a lithium-sulfur battery of the present invention may further include an additive having an intramolecular NO bond.
- the additive has an effect of forming a stable film on the lithium electrode and greatly improves the charge and discharge efficiency.
- Such additives may be nitric acid or nitrous acid compounds, nitro compounds and the like.
- Examples include lithium nitrate, potassium nitrate, cesium nitrate, barium nitrate, ammonium nitrate, lithium nitrite, potassium nitrite, cesium nitrite, ammonium nitrite, methyl nitrate, dialkyl imidazolium nitrate, guanidine nitrate, imidazolium nitrate , Pyridinium nitrate, ethyl nitrite, propyl nitrite, butyl nitrite, pentyl nitrite, octyl nitrite, nitromethane, nitropropane, nitrobutane, nitrobenzene, dinitrobenzene, nitropyridine, dinitropyridine, nitro One or more selected from the group consisting of toluene, dinitrotoluene, pyridine N-oxide, alkylpyridine N-oxide, and tetramethyl piperidinyloxy
- the additive is used in the range of 0.01 to 10% by weight, preferably 0.1 to 5% by weight based on 100% by weight of the total electrolyte composition. If the content is less than the above range, the above-described effects cannot be secured. On the contrary, if the content exceeds the above range, the resistance may be increased by the film, so that the above-mentioned range is appropriately adjusted.
- the lithium-sulfur battery electrolyte according to the present invention uses a mixed solvent of a cyclic ether and a linear ether as a solvent in order to secure electrolyte stability, thereby suppressing gas generation in the battery during charging and discharging of the battery.
- the swelling phenomenon can be improved.
- the preparation method of the electrolyte according to the present invention is not particularly limited in the present invention, and may be prepared by conventional methods known in the art.
- the lithium-sulfur battery according to the present invention includes a positive electrode and a negative electrode and a separator and an electrolyte interposed therebetween, and use the electrolyte solution for a lithium-sulfur battery according to the present invention as an electrolyte.
- the lithium-sulfur battery according to the present invention has improved electrolyte stability and shows excellent life characteristics.
- the structure of the positive electrode, the negative electrode, and the separator of the lithium-sulfur battery is not particularly limited in the present invention, and is known in the art.
- the positive electrode according to the present invention includes a positive electrode active material formed on a positive electrode current collector.
- any one that can be used as a current collector in the technical field is possible, and specifically, it may be preferable to use foamed aluminum, foamed nickel, and the like having excellent conductivity.
- the cathode active material may include elemental sulfur (S8), a sulfur-based compound, or a mixture thereof.
- the conductive material may be porous. Therefore, the conductive material may be used without limitation as long as it has porosity and conductivity, and for example, a carbon-based material having porosity may be used. As such a carbon-based material, carbon black, graphite, graphene, activated carbon, carbon fiber, or the like can be used. Moreover, metallic fibers, such as a metal mesh; Metallic powders such as copper, silver, nickel and aluminum; Or organic conductive materials, such as a polyphenylene derivative, can also be used. The conductive materials may be used alone or in combination.
- the positive electrode may further include a binder for coupling the positive electrode active material and the conductive material and the current collector.
- the binder may include a thermoplastic resin or a thermosetting resin.
- polyethylene polyethylene oxide, polypropylene, polytetrafluoro ethylene (PTFE), polyvinylidene fluoride (PVDF), styrene-butadiene rubber, tetrafluoroethylene-perfluoro alkylvinyl ether copolymer, vinyl fluoride Liden-hexafluoropropylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene, vinylidene fluoride-pentafluoro propylene copolymer, propylene Tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, vinylidene fluoride-he
- the positive electrode as described above may be manufactured according to a conventional method. Specifically, a positive electrode active material layer-forming composition prepared by mixing a positive electrode active material, a conductive material, and a binder on an organic solvent is applied and dried on a current collector, and optionally In order to improve the electrode density, the current collector may be manufactured by compression molding.
- the organic solvent may uniformly disperse the positive electrode active material, the binder, and the conductive material, and preferably evaporates easily. Specifically, acetonitrile, methanol, ethanol, tetrahydrofuran, water, isopropyl alcohol, etc. are mentioned.
- the negative electrode according to the present invention includes a negative electrode active material formed on the negative electrode current collector.
- the negative electrode current collector may be specifically selected from the group consisting of copper, stainless steel, titanium, silver, palladium, nickel, alloys thereof, and combinations thereof.
- the stainless steel may be surface treated with carbon, nickel, titanium, or silver, and an aluminum-cadmium alloy may be used as the alloy.
- calcined carbon, a nonconductive polymer surface-treated with a conductive material, or a conductive polymer may be used.
- a material capable of reversibly intercalating or deintercalating lithium ions (Li + ), a material capable of reacting with lithium ions to form a reversibly lithium-containing compound, a lithium metal or a lithium alloy can be used.
- the material capable of reversibly occluding or releasing the lithium ions (Li + ) may be, for example, crystalline carbon, amorphous carbon or a mixture thereof.
- the material capable of reacting with the lithium ions (Li + ) to form a lithium-containing compound reversibly may be, for example, tin oxide, titanium nitrate or silicon.
- the lithium alloy is, for example, lithium (Li) and sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), francium (Fr), beryllium (Be), magnesium (Mg), calcium ( It may be an alloy of a metal selected from the group consisting of Ca), strontium (Sr), barium (Ba), radium (Ra), aluminum (Al) and tin (Sn).
- the negative electrode may further include a binder for coupling the negative electrode active material and the conductive material and the current collector.
- the binder is the same as described above for the binder of the positive electrode.
- a conventional separator may be interposed between the positive electrode and the negative electrode.
- the separator is a physical separator having a function of physically separating the electrode, and can be used without particular limitation as long as it is used as a conventional separator, and in particular, it is preferable that the separator has a low resistance to electrolyte migration and excellent electrolyte-moisture capability.
- the separator enables the transport of lithium ions between the positive electrode and the negative electrode while separating or insulating the positive electrode and the negative electrode from each other.
- a separator may be made of a porous and nonconductive or insulating material.
- the separator may be an independent member such as a film or a coating layer added to the anode and / or the cathode.
- 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 may be used alone. It may be used as a lamination or or a conventional porous non-woven fabric, for example, a non-woven fabric made of glass fibers, polyethylene terephthalate fibers of high melting point, etc. may be used, but is not limited thereto.
- the positive electrode, the negative electrode, and the separator included in the lithium-sulfur battery may be prepared according to conventional components and manufacturing methods, respectively, and the appearance of the lithium-sulfur battery is not particularly limited, but may be cylindrical, rectangular, or pouch using a can. It may be a pouch type or a coin type.
- LiTFSI (CF 3 SO 2 ) 2 NLi) was added to the mixed solvent having the composition shown in Table 1 at a concentration of 1.0 M, and 1% by weight of LiNO 3 was added based on 100% by weight of the electrolyte.
- a non-aqueous electrolyte solution of Example 1 was prepared. The solvent used at this time is as follows.
- EGEME Ethyleneglycol ethylmethyl ether
- a positive electrode active material slurry was prepared by mixing 65 wt% sulfur, 25 wt% carbon black, and 10 wt% polyethylene oxide with acetonitrile.
- the positive electrode active material slurry was coated on an aluminum current collector and dried to prepare a positive electrode having a loading amount of 5 mAh / cm 2 having a size of 30 ⁇ 50 mm 2 .
- a lithium metal having a thickness of 150 ⁇ m was used as the negative electrode.
- the positive electrode and the negative electrode prepared above were disposed to face each other, and a polyethylene separator having a thickness of 20 ⁇ m was interposed therebetween, followed by filling with the electrolyte solutions of Examples and Comparative Examples.
- the battery of Comparative Example 1 can be seen that the discharge capacity drops sharply after 10 cycles. However, it can be seen that the batteries of Examples 1 and 2 are stably maintained in the discharge capacity even up to 20 cycles. In addition, in the battery of Comparative Example 1, a swelling phenomenon was observed due to gas generation as the battery was driven, but the swelling phenomenon was not observed in the batteries of Examples 1 and 2.
- EGEME Ethyleneglycol ethylmethyl ether
- EGDEE Ethyleneglycol diethyl ether
- a positive electrode active material slurry was prepared by mixing 60 wt% sulfur, 30 wt% carbon black, and 10 wt% polyethylene oxide with acetonitrile.
- the positive electrode active material slurry was coated on an aluminum current collector and dried to prepare a positive electrode having a loading amount of 5 mAh / cm 2 having a size of 30 ⁇ 50 mm 2 .
- a lithium metal having a thickness of 150 ⁇ m was used as the negative electrode.
- the positive electrode and the negative electrode prepared above were disposed to face each other, and a polyethylene separator having a thickness of 20 ⁇ m was interposed therebetween, followed by filling with the electrolyte solutions of Examples and Comparative Examples.
- the battery of Comparative Example 2 showed a tendency that the initial capacity greatly decreased after about 15 charge / discharge cycles. This result is considered to be due to the decomposition of the electrolyte during battery operation due to the low stability of the solvent itself.
- the electrolyte composition of the three-component combination of the present invention increases the retention rate of the initial charge and discharge capacity of the battery, and also improves the life characteristics of the battery compared to the electrolyte of the existing combination.
- the electrolyte of the present invention exhibits better battery life improvement when the content of the cyclic ether is 40% or less of the total weight of the solvent.
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Description
Claims (14)
- 리튬염 및 비수계 용매를 포함하고,Including lithium salts and non-aqueous solvents,상기 비수계 용매는 The non-aqueous solvent isi) 고리구조 내 두 개의 산소를 포함하는 고리형 에테르;i) a cyclic ether comprising two oxygens in the ring structure;ii) 하기 화학식 1로 표시되는 글리콜 에테르; 및ii) glycol ethers represented by the following formula (1); Andiii) 하기 화학식 2로 표시되는 선형 에테르; 를 포함하는 것을 특징으로 하는 리튬-설퍼 전지용 전해액.iii) a linear ether represented by the following formula (2); Lithium-sulfur battery electrolyte, characterized in that it comprises a.[화학식 1][Formula 1]R1-O-(CH2CH2O)x-R2 R 1 -O- (CH 2 CH 2 O) x -R 2[화학식 2][Formula 2]R3-O-(CH2CH2O)y-R4 R 3 -O- (CH 2 CH 2 O) y -R 4(상기 화학식 1 및 2에서,(In Chemical Formulas 1 and 2,R1 내지 R4는 서로 같거나 다르며, 각각 독립적으로 C1 내지 C6의 알킬기, 또는 C6 내지 C12의 아릴기이고, 또는 C7 내지 C13의 아릴알킬기이고,R 1 to R 4 are the same as or different from each other, and each independently an alkyl group of C1 to C6, an aryl group of C6 to C12, or an arylalkyl group of C7 to C13,x는 1 내지 4의 정수이고,x is an integer from 1 to 4,y는 0 내지 4의 정수이며,y is an integer from 0 to 4,상기 화학식 1의 에테르는 상기 화학식 2의 에테르와 상이하다)The ether of Formula 1 is different from the ether of Formula 2)
- 제1항에 있어서,The method of claim 1,상기 고리형 에테르는 C1 내지 C4의 알킬기 또는 알콕시기로 치환 또는 비치환된 5 내지 7원 고리형 에테르인 것을 특징으로 하는 리튬-설퍼 전지용 전해액.The cyclic ether is a 5-7 membered cyclic ether unsubstituted or substituted with an alkyl or alkoxy group of C1 to C4.
- 제1항에 있어서,The method of claim 1,상기 고리형 에테르는 C1 내지 C4의 알킬기 또는 알콕시기로 치환 또는 비치환된 디옥솔란, 또는 디옥산인 것을 특징으로 하는 리튬-설퍼 전지용 전해액.The cyclic ether is a dioxolane or dioxane substituted or unsubstituted with an alkyl or alkoxy group of C1 to C4, an electrolyte for a lithium-sulfur battery.
- 제1항에 있어서,The method of claim 1,상기 고리형 에테르는 1,3-디옥솔란, 4,5-디에틸-1,3-디옥솔란, 4,5-디메틸-1,3-디옥솔란, 4-메틸-1,3-디옥솔란, 4-에틸-1,3-디옥솔란, 1,3-디옥산, 1,4-디옥산, 4-메틸-1,3-디옥산, 및 2-메틸-1,3-디옥산으로 이루어진 군에서 선택되는 1종인 것을 특징으로 하는 리튬-설퍼 전지용 전해액.The cyclic ethers include 1,3-dioxolane, 4,5-diethyl-1,3-dioxolane, 4,5-dimethyl-1,3-dioxolane, 4-methyl-1,3-dioxolane, Group consisting of 4-ethyl-1,3-dioxolane, 1,3-dioxane, 1,4-dioxane, 4-methyl-1,3-dioxane, and 2-methyl-1,3-dioxane The electrolyte solution for lithium-sulfur battery, characterized in that one kind selected from.
- 제1항에 있어서, The method of claim 1,상기 글리콜 에테르는 1,2-디메톡시에탄, 에틸렌글리콜 에틸메틸에테르, 디에틸렌글리콜 디메틸에테르, 트리에틸렌글리콜 디메틸에테르, 및 테트라에틸렌글리콜 디메틸에테르로 이루어지는 군에서 선택되는 1종인 것을 특징으로 하는 리튬-설퍼 전지용 전해액.The glycol ether is lithium-, characterized in that one selected from the group consisting of 1,2-dimethoxyethane, ethylene glycol ethylmethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether. Electrolyte for Sulfur Battery.
- 제1항에 있어서,The method of claim 1,상기 선형 에테르는 에틸렌글리콜 에틸메틸에테르, 에틸렌글리콜 디에틸에테르, 디프로필에테르, 디이소프로필에테르, 디부틸에테르, 및 디이소부틸에테르 에테르로 이루어지는 군에서 선택되는 1종인 것을 특징으로 하는 리튬-설퍼 전지용 전해액.The linear ether is lithium-sulfur, which is selected from the group consisting of ethylene glycol ethyl methyl ether, ethylene glycol diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, and diisobutyl ether ether. Battery electrolyte.
- 제1항에 있어서,The method of claim 1,상기 고리형 에테르는 비수계 용매 총 중량의 10 내지 40 부피%로 포함되는 것을 특징으로 하는 리튬-설퍼 전지용 전해액.The cyclic ether is a lithium-sulfur battery electrolyte, characterized in that it comprises 10 to 40% by volume of the total weight of the non-aqueous solvent.
- 제1항에 있어서,The method of claim 1,상기 글리콜 에테르 및 선형 에테르는 1:3 내지 3:1 의 부피비로 포함되는 것을 특징으로 하는 리튬-설퍼 전지용 전해액.The glycol ether and linear ether is an electrolyte solution for a lithium-sulfur battery, characterized in that it is included in a volume ratio of 1: 3 to 3: 1.
- 제1항에 있어서,The method of claim 1,상기 리튬염은 LiCl, LiBr, LiI, LiClO4, LiBF4, LiB10Cl10, LiPF6, LiCF3SO3, LiCF3CO2, LiC4BO8, LiAsF6, LiSbF6, LiAlCl4, CH3SO3Li, CF3SO3Li, (CF3SO2)2NLi, (C2F5SO2)2NLi, (SO2F)2NLi, (CF3SO2)3CLi, 클로로 보란 리튬, 저급지방족 카르본산 리튬, 4-페닐 붕산 리튬, 리튬 이미드 및 이들의 조합으로 이루어진 군에서 선택된 1종을 포함하는 것을 특징으로 하는 리튬-설퍼 전지용 전해액.The lithium salt is LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiC 4 BO 8 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , CH 3 SO 3 Li, CF 3 SO 3 Li, (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 ) 2 NLi, (SO 2 F) 2 NLi, (CF 3 SO 2 ) 3 CLi, chloroborane lithium The lower aliphatic lithium carboxylate, 4-phenyl lithium borate, lithium imide, and a combination of one selected from the group consisting of a lithium-sulfur battery electrolyte.
- 제1항에 있어서,The method of claim 1,상기 리튬염은 0.1 내지 4.0 M 농도로 포함되는 것을 특징으로 하는 리튬-설퍼 전지용 전해액.The lithium salt is a lithium-sulfur battery electrolyte, characterized in that it is included in a concentration of 0.1 to 4.0 M.
- 제1항에 있어서,The method of claim 1,상기 전해액은 분자 내 N-O 결합을 갖는 첨가물을 더 포함하는 것을 특징으로 하는 리튬-설퍼 전지용 전해액.The electrolyte solution further comprises an additive having an intramolecular N-O bond.
- 제11항에 있어서,The method of claim 11,상기 첨가물은 질산리튬, 질산칼륨, 질산세슘, 질산바륨, 질산암모늄, 아질산리튬, 아질산칼륨, 아질산세슘, 아질산암모늄, 메틸 니트레이트, 디알킬 이미다졸륨 니트레이트, 구아니딘 니트레이트, 이미다졸륨 니트레이트, 피리디늄 니트레이트, 에틸 니트라이트, 프로필 니트라이트, 부틸 니트라이트, 펜틸 니트라이트, 옥틸 니트라이트, 니트로메탄, 니트로프로판, 니트로부탄, 니트로벤젠, 디니트로벤젠, 니트로 피리딘, 디니트로피리딘, 니트로톨루엔, 디니트로톨루엔, 피리딘 N-옥사이드, 알킬피리딘 N-옥사이드, 및 테트라메틸 피페리디닐옥실로 이루어지는 군에서 선택되는 1종 이상인 것을 특징으로 하는 리튬-설퍼 전지용 전해액.The additives include lithium nitrate, potassium nitrate, cesium nitrate, barium nitrate, ammonium nitrate, lithium nitrite, potassium nitrite, cesium nitrite, ammonium nitrite, methyl nitrate, dialkyl imidazolium nitrate, guanidine nitrate, imidazolium nitrate Latex, pyridinium nitrate, ethyl nitrite, propyl nitrite, butyl nitrite, pentyl nitrite, octyl nitrite, nitromethane, nitropropane, nitrobutane, nitrobenzene, dinitrobenzene, nitro pyridine, dinitropyridine, An electrolyte solution for lithium-sulfur batteries, which is at least one member selected from the group consisting of nitrotoluene, dinitrotoluene, pyridine N-oxide, alkylpyridine N-oxide, and tetramethyl piperidinyloxyl.
- 제11항에 있어서,The method of claim 11,상기 첨가물은 전해액 100 중량% 에 대하여 0.01 내지 10 중량% 로 포함되는 것을 특징으로 하는 리튬-설퍼 전지용 전해액.The additive is an electrolyte solution for a lithium-sulfur battery, characterized in that contained in 0.01 to 10% by weight relative to 100% by weight of the electrolyte.
- 제1항 내지 제13항 중 어느 한 항의 전해액을 포함하는 리튬-설퍼 전지.A lithium-sulfur battery comprising the electrolyte solution of any one of claims 1 to 13.
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US16/082,400 US10923759B2 (en) | 2016-06-28 | 2017-03-10 | Electrolyte solution for lithium-sulfur battery and lithium-sulfur battery comprising same |
CN201780026038.8A CN109075393B (en) | 2016-06-28 | 2017-03-10 | Electrolyte for lithium-sulfur battery and lithium-sulfur battery comprising same |
EP17820387.3A EP3422460B1 (en) | 2016-06-28 | 2017-03-10 | Electrolyte solution for lithium-sulfur battery and lithium-sulfur battery comprising same |
JP2018545612A JP6699877B2 (en) | 2016-06-28 | 2017-03-10 | Lithium-sulfur battery electrolyte and lithium-sulfur battery containing the same |
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