WO2017183810A1 - Électrolyte pour batterie lithium-soufre et batterie lithium-soufre le comprenant - Google Patents

Électrolyte pour batterie lithium-soufre et batterie lithium-soufre le comprenant Download PDF

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WO2017183810A1
WO2017183810A1 PCT/KR2017/002579 KR2017002579W WO2017183810A1 WO 2017183810 A1 WO2017183810 A1 WO 2017183810A1 KR 2017002579 W KR2017002579 W KR 2017002579W WO 2017183810 A1 WO2017183810 A1 WO 2017183810A1
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ether
lithium
group
electrolyte
sulfur battery
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PCT/KR2017/002579
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English (en)
Korean (ko)
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박인태
홍성원
송기석
옥유화
양두경
이창훈
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주식회사 엘지화학
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Priority claimed from KR1020170028619A external-priority patent/KR102050838B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201780004252.3A priority Critical patent/CN108292782B/zh
Priority to JP2018518616A priority patent/JP6595710B2/ja
Priority to EP17786079.8A priority patent/EP3355401B1/fr
Priority to US15/767,289 priority patent/US10629946B2/en
Publication of WO2017183810A1 publication Critical patent/WO2017183810A1/fr

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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
    • 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
    • H01M10/056—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
    • 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
    • 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 an electrolyte for a lithium-sulfur battery 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. There is no advantage, and it 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.
  • the theoretical energy density of other battery systems currently under investigation (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.
  • lithium-sulfur batteries have not been commercialized yet due to low sulfur utilization, insufficient capacity is secured as theoretical capacity, and a short circuit problem due to dendrite formation of lithium metal electrodes. Accordingly, in order to overcome the above problems, development of an anode material having an increased sulfur impregnation amount and an electrolyte solution capable of increasing sulfur utilization has been made.
  • a mixed solvent of 1,3-dioxolane (DOL) and 1,2-dimethoxyethane (DME) is most used as an electrolyte solvent of a lithium-sulfur battery.
  • the electrolyte solution using the solvent exhibits excellent properties in terms of sulfur utilization.
  • a swelling phenomenon in which gas was generated inside the battery during operation of the battery to which the electrolyte was applied was inflated was observed. Such swelling not only depletes the electrolyte solution and causes deformation of the battery, but also causes problems such as desorption of the active material from the electrode, thereby degrading battery performance.
  • 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 to provide an electrolyte for lithium-sulfur batteries that significantly reduces the amount of gas generated during battery operation.
  • Another object of the present invention to provide a lithium-sulfur battery comprising the electrolyte.
  • the non-aqueous solvent includes a cyclic ether and a linear ether containing one oxygen in the ring structure,
  • the bond dissociation energy of the C-O bond in the case of receiving one electron is greater than -19.9 kcal / mol to provide an electrolyte solution for a lithium-sulfur battery.
  • linear ether may be represented by the following formula (1).
  • R 1 and R 2 may be the same as or different from each other, and may each independently be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertbutyl group, a pentyl group, or a hexyl group.
  • the linear ether is 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.
  • the cyclic ether may be a 5- to 7-membered cyclic ether unsubstituted or substituted with a C1 to C4 alkyl group or an alkoxy group, and tetrahydrofuran or tetrahydropyranyl unsubstituted or substituted with a C1 to C4 alkyl group or alkoxy group Can be.
  • the cyclic ether is tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 2,3-dimethyltetrahydrofuran, 2,4-dimethyltetrahydrofuran, 2,5-dimethyltetra Hydrofuran, 2-methoxytetrahydrofuran, 3-methoxytetrahydrofuran, 2,5-dimethoxytetrahydrofuran, 2-ethoxytetrahydrofuran, 3-ethoxytetrahydrofuran, tetrahydropyran, 2 It may be one or more selected from the group consisting of -methyltetrahydropyran, 3-methyltetrahydropyran, and 4-methyltetrahydropyran.
  • the volume ratio of the cyclic ether and the linear ether may be 5:95 to 95: 5, preferably 30:70 to 70:30.
  • 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 , Lower aliphatic lithium carboxylate, 4-phenyl lithium borate, lithium imide, and a combination thereof may be selected from the group consisting of, the lithium salt may be included in a concentration of 0.1 to 4.0 M.
  • the electrolyte solution of the present invention 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, imidazolium nitrate Latex, pyridinium nitrate, ethyl nitrite, propyl nitrite, butyl nitrite, pentyl nitrite, octyl nitrite, nitromethane, nitropropane, nitrobutane, nitrobenzene, dinitrobenzene, nitro pyridine, dinitropyridine, It may be at least one selected from the group consisting of nitrotoluene, dinitrotoluene, pyridine N-oxide, alkylpyridine N-oxide, and tetra
  • the present invention also provides a lithium-sulfur battery comprising the electrolyte solution.
  • the electrolyte solution for a lithium-sulfur battery according to the present invention is excellent in stability, so that the amount of gas generated during driving of the battery is remarkably small, thereby improving the swelling phenomenon of the battery.
  • FIG. 1 is a graph comparing gas generation in Experimental Example 1.
  • the bond dissociation energy of the CO bond in the case of receiving one electron is greater than -19.9 kcal / mol.
  • DOL 1,3-dioxolane
  • DME 1,2-dimethoxyethane
  • the electrolyte solution using the mixed solvent shows excellent performance in terms of suppression of battery capacity reduction, battery life and battery efficiency when applied to small batteries, but when applied to large batteries such as large area pouch cells, During operation, a significant amount of gas such as hydrogen, methane, and ethene was generated in the cell, thereby swelling the cell.
  • the mechanism of generation of gas generated in the battery is not clear, but it is confirmed that it is due to the decomposition of the electrolyte, and in particular, since it is characteristic of a lithium-sulfur battery, sulfur radicals, lithium sulfide, etc. generated during battery operation are electrolytic solutions. It is thought to affect decomposition. That is, the intramolecular bonds of the solvent molecules of the electrolyte solution are broken by sulfur radicals and the like, and it is believed that gases such as hydrogen, methane, and ethene are generated as the terminal hydrogen or alkyl group (eg, methyl or ethyl) of the solvent molecules dissociates.
  • the generated gas may expand in volume due to heat energy inside the battery, and as the battery is prolonged, the swelling may become serious, causing desorption of the active material from the electrode, and eventually causing problems such as an explosion. have.
  • the present inventors studied a stable solvent combination in order to suppress the gas generation phenomenon due to decomposition of the electrolyte, and variously examined the characteristics of the solvent that the gas generation is significantly lower during the operation of the battery, surprisingly, oxygen atoms of the linear ether
  • the bond dissociation energy of the terminal substituents attached to is closely related to electrolyte stability. That is, when the CO bond of DME, a linear ether used previously, is broken and the end group (methyl group) is dissociated, the stability of the electrolyte is greatly improved when the linear ether exhibiting a high bond dissociation energy is used.
  • the gas generation amount was markedly reduced. This effect was found to be particularly good when used with cyclic ethers containing one oxygen atom in the molecule.
  • the above-mentioned problems are selected by selecting an electrolyte solution having a minimum bond dissociation energy so that basic physical properties required as an electrolyte solution, that is, lithium ion transfer and the like can be smoothly prevented and decomposition of the electrolyte solution by electrons can be prevented. It suggests an electrolyte composition that can solve the problem.
  • the bond dissociation energy (BDE) of the CO bond when one electron is received is greater than -19.9 kcal / mol. It features.
  • the C-O bond means a bond between a terminal ether substituent of a linear ether (a substituent which does not include an oxygen atom such as an alkyl group, an aryl group, or an arylalkyl group) and an oxygen atom.
  • the terminal substituents of the linear ethers are different and there are non-equivalent C-O bonds in the molecule, they are based on the lowest BDE. That is, it is preferable that all of the C-O bonds in the linear ether molecule are more than -19.9 kcal / mol.
  • DFT Density Functional Theory
  • BDE of diisopropyl ether is the value which calculated the reaction energy of reaction shown by following Reaction Formula 1 by the said method.
  • the BDE of diisopropyl ether is -8.1 kcal / mol, which is one of the preferred linear ethers for use in the electrolyte of the present invention.
  • the linear ether of the present invention may be a linear ether represented by the following formula (1).
  • R 1 and R 2 are the same as or different from each other, and each independently a C 1 to C 6 alkyl group unsubstituted or substituted with one or more fluorine, a C 6 to C 12 aryl group unsubstituted or substituted with one or more fluorine, or one or more fluorine. Substituted or unsubstituted C7 to C13 arylalkyl group)
  • 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.
  • the linear ether may have the same symmetric structure with each other, or R 1 and R 2 may have different asymmetric structures.
  • the linear ether may be a compound having a symmetrical structure in which R 1 and R 2 are the same C1 to C6 alkyl group.
  • 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.
  • One or more hydrogen of the C1 to C6 alkyl group, C6 to C12 aryl group and C7 to C13 arylalkyl group may be substituted with fluorine.
  • the cyclic ether including one oxygen in the cyclic structure is a 5 or more membered cyclic ether unsubstituted or substituted with an alkyl group, and preferably a 5 to 7 membered ring unsubstituted or substituted with a C1 to C4 alkyl group or an alkoxy group. It is a type ether, More preferably, they are tetrahydrofuran or tetrahydropyran unsubstituted or substituted by the C1-C4 alkyl group or the alkoxy group.
  • tetrahydrofuran 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 2,3-dimethyltetrahydrofuran, 2,4-dimethyltetrahydrofuran, 2,5-dimethyltetrahydrofuran , 2-methoxytetrahydrofuran, 3-methoxytetrahydrofuran, 2,5-dimethoxytetrahydrofuran, 2-ethoxytetrahydrofuran, 3-ethoxytetrahydrofuran, tetrahydropyran, 2-methyl Tetrahydropyran, 3-methyltetrahydropyran, 4-methyltetrahydropyran and the like.
  • the cyclic ether has a low viscosity, good ion mobility, and high redox stability, thus showing high stability even for long-term operation of the battery.
  • the linear ether is a linear ether containing one oxygen in the molecular structure and one or more hydrogen in the molecule is substituted or unsubstituted with fluorine
  • non-limiting examples include dimethyl ether, diethyl ether, dipropyl ether, diiso Propyl ether, dibutyl ether, diisobutyl ether, dipentyl ether, dihexyl ether, ethyl methyl ether, methyl propyl ether, butyl methyl ether, ethyl propyl ether, butyl propyl ether, phenylmethyl ether, diphenyl ether, dibenzyl Ether, bis (fluoromethyl) ether, 2-fluoromethylether, 1,1,2,2-tetrafluoroethyl2,2,3,3-tetrafluoropropylether, bis (2,2,2 -Trifluoroethyl) ether, propyl 1,1,2,2-tetra
  • the cyclic ether may be tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, tetrahydropyran, or 2-methyltetrahydropyran, wherein the linear ether is dipropyl Ether, diisopropyl ether, dibutyl ether, diisobutyl ether, or bis (fluoromethyl) ether.
  • the volume ratio of the cyclic ether and the linear ether is 5:95 to 95: 5, preferably 30:70 to 70:30. If it is out of the above range, the gas generation suppression effect during driving of the battery is insignificant, so that the desired effect cannot be obtained.
  • the electrolyte 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
  • 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 non-aqueous electrolyte solution for lithium-sulfur batteries of the present invention may further include an additive having an intramolecular N-O bond.
  • the additive has an effect of forming a stable film on the lithium electrode and greatly improves the charge and discharge efficiency.
  • the additive has the effect of increasing the sulfur utilization of the positive electrode, stabilizing the electrolyte solution to improve battery characteristics.
  • 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
  • the additive is used within the range of 0.01 to 10% by weight, preferably 0.1 to 5% by weight within 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 occurrence of the swelling may be described in various ways, but in the present invention, whether or not swelling has been quantitatively confirmed by measuring a gas generation amount.
  • the gas generation amount inside the battery measured after driving the battery has a value of 300 ⁇ L or less, preferably 100 ⁇ L or less.
  • the smaller the value means that the gas generation amount is less, the reduction of the gas generation amount is a value that does not significantly affect the battery stability even if the swelling phenomenon that the battery is hardly generated or occurs. That is, compared with the gas generation amount at the level of about 500 ⁇ L in the case of using another electrolyte solution (see Comparative Example 1), the gas generation amount is significantly lower when using the electrolyte solution provided in the present invention.
  • the electrolyte solution of the present invention overcomes the problems of deterioration of battery performance and quality deterioration due to battery deformation due to the swelling phenomenon, and significantly reduces the amount of gas generation without deteriorating battery characteristics such as battery life and efficiency when driving a lithium-sulfur battery. Is reduced.
  • the preparation method of the electrolyte according to the present invention is not particularly limited in the present invention, it may be prepared by conventional methods known in the art.
  • the lithium-sulfur battery according to the present invention uses the non-aqueous electrolyte solution for the lithium-sulfur battery according to the present invention as the electrolyte.
  • the amount of gas generated such as hydrogen gas during driving is significantly reduced, thereby improving the battery performance caused by detachment of the active material from the electrode and the quality deterioration caused by the deformation of the battery.
  • 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 of Table 1 at a concentration of 1.0 M, and NO additives were added to prepare the non-aqueous electrolyte solutions of Examples 1 to 6 and Comparative Example 1. At this time, LiTFSI ((CF 3 SO 2 ) 2 NLi) was used as the lithium salt, and the solvent used was as follows.
  • 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 cathode.
  • 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 cells of Examples 1 to 6 have a gas generation amount of 8.8 to 27.3 ⁇ L, which is remarkably effective in inhibiting gas generation compared to 473 ⁇ L of Comparative Example 1.

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Abstract

La présente invention concerne un électrolyte pour batterie lithium-soufre et une batterie lithium-soufre comprenant celui-ci. L'électrolyte pour batterie lithium-soufre selon la présente invention présente une excellente stabilité et permet d'inhiber la génération de gaz pendant le fonctionnement de la batterie lithium-soufre, ce qui permet de diminuer le phénomène de gonflement.
PCT/KR2017/002579 2016-04-22 2017-03-10 Électrolyte pour batterie lithium-soufre et batterie lithium-soufre le comprenant WO2017183810A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201780004252.3A CN108292782B (zh) 2016-04-22 2017-03-10 锂-硫电池用电解质和包含其的锂-硫电池
JP2018518616A JP6595710B2 (ja) 2016-04-22 2017-03-10 リチウム−硫黄電池用電解液及びこれを含むリチウム−硫黄電池
EP17786079.8A EP3355401B1 (fr) 2016-04-22 2017-03-10 Électrolyte pour batterie lithium-soufre et batterie lithium-soufre le comprenant
US15/767,289 US10629946B2 (en) 2016-04-22 2017-03-10 Electrolyte for lithium-sulfur battery, and lithium-sulfur battery comprising same

Applications Claiming Priority (4)

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KR10-2016-0049531 2016-04-22
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CN110416597A (zh) * 2018-04-27 2019-11-05 宁德时代新能源科技股份有限公司 一种醚类电解液以及锂硫二次电池
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CN114512722A (zh) * 2022-03-09 2022-05-17 东莞理工学院 一种金属锂基二次电池电解液及其应用
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JP2021508148A (ja) * 2018-04-30 2021-02-25 エルジー・ケム・リミテッド リチウム−硫黄電池用電解質溶液及びこれを含むリチウム−硫黄電池
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US11961970B2 (en) 2019-01-17 2024-04-16 Sceye Sa LiS battery with low solvating electrolyte
CN114512722A (zh) * 2022-03-09 2022-05-17 东莞理工学院 一种金属锂基二次电池电解液及其应用

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