WO2018097695A1 - Matériau actif de cathode pour pile lithium-soufre, comportant des nanoparticules de sulfure métallique, et son procédé de fabrication - Google Patents

Matériau actif de cathode pour pile lithium-soufre, comportant des nanoparticules de sulfure métallique, et son procédé de fabrication Download PDF

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WO2018097695A1
WO2018097695A1 PCT/KR2017/013676 KR2017013676W WO2018097695A1 WO 2018097695 A1 WO2018097695 A1 WO 2018097695A1 KR 2017013676 W KR2017013676 W KR 2017013676W WO 2018097695 A1 WO2018097695 A1 WO 2018097695A1
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lithium
sulfur
active material
sulfur battery
positive electrode
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PCT/KR2017/013676
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English (en)
Korean (ko)
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이동욱
정종욱
손권남
양두경
황교현
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주식회사 엘지화학
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Priority to US16/308,316 priority Critical patent/US10770727B2/en
Priority to CN201780047753.XA priority patent/CN109565073A/zh
Priority to JP2018563903A priority patent/JP6872093B2/ja
Priority to EP17874276.3A priority patent/EP3457483B1/fr
Priority claimed from KR1020170159901A external-priority patent/KR102024900B1/ko
Publication of WO2018097695A1 publication Critical patent/WO2018097695A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/70—Compounds containing carbon and sulfur, e.g. thiophosgene
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • 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 positive electrode active material for a lithium-sulfur battery and a method for manufacturing the same, and more particularly, to a positive electrode active material for a lithium-sulfur battery including metal sulfide nanoparticles and a method for manufacturing the same.
  • a lithium-sulfur (Li-S) battery is a secondary battery using a sulfur-based material having an SS bond (Sulfur-sulfur bond) as a positive electrode active material and using lithium metal as a negative electrode active material.
  • Sulfur the main material of the positive electrode active material, is very rich in resources, has no toxicity, and has an advantage of having a low weight per atom.
  • the theoretical discharge capacity of the lithium-sulfur battery is 1675 mAh / 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 cells: 1,000 Wh / kg, Na-S cells: 800 Wh / kg) is very high compared to the most promising battery that has been developed to date.
  • a reduction reaction in a cyclic S 8 so that the lithium polysulfide is completely Reduction will eventually lead to the formation of lithium sulfide (Lithium sulfide, Li 2 S).
  • Discharge behavior of the lithium-sulfur battery by the process of reduction to each lithium polysulfide is characterized by showing the discharge voltage step by step unlike the lithium ion battery.
  • lithium polysulfides such as Li 2 S 8 , Li 2 S 6 , Li 2 S 4 , and Li 2 S 2
  • lithium polysulfides (Li 2 S x , usually x> 4) having high sulfur oxides are easily dissolved in the electrolyte.
  • the polysulfides (S 8 2- , S 6 2- ) dissolved in the electrolyte are diffused away from the anode where lithium polysulfide is formed due to the concentration difference.
  • the polysulfide eluted from the positive electrode is lost outside the positive electrode reaction region, so that stepwise reduction to lithium sulfide (Li 2 S) is impossible.
  • lithium polysulfide which is present in the dissolved state outside the positive electrode and the negative electrode, cannot participate in the charge / discharge reaction of the battery, the amount of sulfur material participating in the electrochemical reaction at the positive electrode decreases, and eventually lithium-sulfur It is a major factor causing a decrease in the charge capacity and energy of the battery.
  • the polysulfide diffused to the negative electrode in addition to being suspended or precipitated in the electrolyte, reacts directly with lithium and is fixed in the form of Li 2 S on the surface of the negative electrode, thereby causing a problem of corroding the lithium negative electrode.
  • Patent Document 1 Republic of Korea Patent Publication No. 10-0358809 "Lithium-sulfur battery showing a quick electrochemical reaction"
  • Non-Patent Document 1 Nano Lett., 2016, 16 (1), pp 519-527 "Powering Lithium-Sulfur Battery Performance by Propelling Polysulfide Redox at Sulfiphilic Hosts"
  • the lithium-sulfur battery has a problem in that the capacity and life characteristics of the battery decrease as the charge / discharge cycle progresses due to the polysulfide eluted from the positive electrode. Accordingly, the present inventors have attempted to develop a composite exhibiting performance in suppressing elution and adsorption of polysulfide as a cathode active material of a lithium-sulfur battery.
  • an object of the present invention is to provide a lithium-sulfur battery in which elution and diffusion of lithium polysulfide are suppressed.
  • the present invention is a sulfur / carbon composite; And it provides a cathode active material for a lithium-sulfur battery comprising a metal sulfide nanoparticles.
  • the present invention is prepared by mixing the metal sulfide nanoparticles in the sulfur / carbon composite
  • the method for producing the metal sulfide nanoparticles is i) preparing a sulfur precursor solution and a metal precursor solution; ii) mixing the sulfur precursor solution and the metal precursor solution; iii) reacting the mixed solution at 50 to 100 ° C. for 5 to 24 hours; iv) washing and purifying the solution; And v) drying.
  • the method provides a method of manufacturing a cathode active material for a lithium-sulfur battery, including the step of drying.
  • the present invention provides a positive electrode and a lithium-sulfur battery including the positive electrode active material.
  • Metal sulfide nanoparticles having a large specific surface area applied to the cathode active material for a lithium-sulfur battery according to the present invention act as a redox mediator during charging and discharging of a lithium-sulfur battery, thereby suppressing elution of polysulfide itself.
  • the shuttle reaction is reduced by adsorbing it and preventing it from being diffused into the electrolyte solution, thus improving the capacity and life characteristics of the lithium-sulfur battery.
  • the metal sulfide nanoparticles used in the present invention can be dispersed in water, since the particles are small in water, it is possible to disperse when the pre-dispersed aqueous dispersion is added during slurry production.
  • the metal used is economical because it is relatively inexpensive compared to expensive precious metals applied as a conventional catalyst, and the manufacturing process is simple.
  • FIG. 1 is a schematic cross-sectional view of a lithium-sulfur battery of the present invention.
  • Example 6 is a charge and discharge curve of Example 2 and Comparative Examples 1 and 2 of the present invention.
  • Example 7 is data showing the life retention rates of Example 2 and Comparative Examples 1 and 2 of the present invention.
  • the present invention is a sulfur / carbon composite; And a cathode active material for a lithium-sulfur battery including metal sulfide nanoparticles.
  • the metal sulfide nanoparticles may be sporadically distributed on at least part of the surface of the sulfur / carbon composite, or may be located at an interface between carbon and sulfur supported on porous carbon.
  • the metal sulfide nanoparticles according to the present invention act as a catalyst as a redox mediator.
  • the metal sulfide nanoparticles according to the present invention can be dispersed due to their particle size.
  • metal sulfide nanoparticles are applied as a redox mediator, polysulfides are adsorbed without diffusion from the carbon surface toward the electrolyte or the cathode. At this time, electron transfer is facilitated by catalysis, and the reaction of reducing to Li 2 S 2 or Li 2 S which is not eluted in the solid phase is promoted, and thus the reaction rate (Kinetics) of the overall sulfur discharge reaction (reduction reaction) is accelerated and eluted. The amount of polysulfide is reduced.
  • the metal sulfide nanoparticles are represented by M x S y (an integer of 0 ⁇ x ⁇ 5 and 0 ⁇ y ⁇ 5), and M is cobalt (Co), molybdenum (Mo), titanium (Ti), nickel (Ni), copper (Cu), iron (Fe), cadmium (Cd), lead (Pb), manganese (Mn), antimony (Sb), arsenic (As), silver (Ag) and mercury (Hg) It may be at least one selected from the group.
  • the metal sulfide is CoS 2 , MoS 2 , TiS 2 , Ag 2 S, As 2 S 3 , CdS, CuS, Cu 2 S, FeS, FeS 2 , HgS, MoS 2 , Ni 3 S 2 , NiS, NiS 2 , PbS, TiS 2 , MnS and Sb 2 S 3 .
  • the metal sulfide nanoparticles are preferably used as redox mediators because the amount of adsorption of polysulfide ions per unit area and the adsorption energy are larger than those of the carbon material used for the composite and serve as a catalyst as well as adsorption. Applicable
  • the average particle diameter of the metal sulfide nanoparticles is used 0.1 to 200 nm, preferably 10 to 100 nm, more preferably 20 to 50 nm.
  • the smaller the average particle diameter of the nanoparticles the larger the specific surface area, and thus the better the adsorption capacity of the eluted polysulfide.
  • the average particle diameter extends to the micro range, the reactivity of the electrode is rather reduced because of the decrease in water dispersibility.
  • the metal sulfide nanoparticles having a particle diameter of 200 nm or less described above can be achieved by using a surfactant.
  • the nanoparticles When the surfactant is used in the preparation of the slurry, the nanoparticles may be mixed well with a solvent, an active material, and a conductive material to prepare a stable slurry without precipitation and phase separation.
  • the functional group is attached to the surface of the nanoparticles to reduce the aggregation phenomenon of the particles in the solvent, and the dispersion is facilitated by the interaction between hydrophilic functional groups, resulting in water dispersibility. This is improved.
  • the metal sulfide nanoparticles are preferably contained in 1 to 20% by weight, preferably 5 to 10% by weight based on the total weight of the positive electrode active material. If the content is less than 1% by weight, the effect of inhibiting the formation and dissolution of polysulfide is insignificant, whereas if it exceeds 20% by weight, the content of the sulfur / carbon composite is relatively reduced, rather the battery performance is reduced.
  • the metal sulfide nanoparticles of the present invention may be prepared by a solution synthesis method by performing the following steps.
  • thiacetamide (TAA) and thiourea ( Thiourea) and sodium sulfide (Na 2 S) may be a solution in which at least one selected from the group is dissolved in water or ethanol.
  • the sulfur precursor solution may include a predetermined surfactant, and may include about 1 to 5 mol% based on the sulfur precursor.
  • the surfactant that can be used in the present invention is not particularly limited, but in particular, when using a surfactant containing an electron-rich functional group, the functional group is attached to the surface of the particles to reduce the aggregation phenomenon of the particles in the solvent, etc.
  • the dispersion between the hydrophilic functional groups facilitates the dispersion and improves the water dispersibility.
  • SDS Sodium Dodecyl Sulfate
  • the metal precursor solution is cobalt (Co), molybdenum (Mo), titanium (Ti), nickel (Ni), copper (Cu), iron (Fe), cadmium (Cd), lead (Pb), manganese (Mn), Acetates, hydroxides, nitrates, nitrides, sulfates, sulfides, alkoxides and the like containing at least one metal selected from the group consisting of antimony (Sb), arsenic (As), silver (Ag) and mercury (Hg); It is a solution containing at least one compound selected from the group consisting of halides.
  • the solvent for dissolving such a metal precursor is not particularly limited, but according to one embodiment of the present invention, a solution dissolved in water or ethanol using Co (NO 3 ) 2 .6H 2 O as a cobalt precursor is possible. Do.
  • the mixed solution is heated to a temperature of 50 to 100 °C, and reacted for 5 to 24 hours.
  • This process is a method of thermally decomposing the sulfur precursor and the metal precursor and synthesizing it on a high temperature solution. This method is to uniformly control the size and shape of the nanoparticles and to synthesize a large amount of nanocrystals having excellent crystallinity. Is preferred.
  • to remove impurities of the synthesized metal sulfide nanoparticles are washed two or more times alternately with water and ethanol, and then centrifuged to separate the precipitated metal sulfide nanoparticles.
  • the metal sulfide nanoparticles are obtained by drying.
  • the drying temperature may vary depending on the type of the solvent used, it may be 50 to 100 °C according to an embodiment of the present invention.
  • the carbon-sulfur composite of the present invention is intended to impart conductivity to a nonconductive sulfur material, and is a combination of a carbon (C) -based material and sulfur (S) particles, and has a shape in which sulfur particles are supported on a porous carbon-based material. It is preferable.
  • the carbon-based material constituting the sulfur / carbon composite according to the present invention is not limited as long as it is conductive carbon, and may be crystalline or amorphous carbon.
  • a porous carbon powder or carbon structure having a large specific surface area and high electrical conductivity is used as a particle or structure having a size of nano units.
  • natural graphite, artificial graphite, expanded graphite, graphite such as graphene, active carbon, channel black, furnace black, thermal black Carbon blacks such as contact black, lamp black, acetylene black It may be at least one selected from the group consisting of carbon nanostructures such as carbon fiber-based, carbon nanotubes (CNTs), and fullerenes.
  • the sulfur particles supported on the carbonaceous material may include elemental sulfur (S 8 ), a sulfur-based compound, or a mixture thereof.
  • the sulfur / carbon composite according to the present invention is not limited thereto, but may be a composite of sulfur and carbon nanotubes (S / CNT) according to one embodiment of the present invention.
  • the sulfur particles and the carbon-based material may be mixed in a weight ratio of 5: 5 to 8: 2: 2 to prepare a sulfur / carbon composite, and the method of supporting the sulfur particles on the carbon-based material may apply various known methods.
  • the present invention does not limit this.
  • the sulfur / carbon composite and the metal sulfide nanoparticles may be mixed to produce a cathode active material.
  • Lithium-sulfur battery positive electrode after mixing the sulfur / carbon composites and the metal sulfide nanoparticles by a ball milling method to prepare a positive electrode active material, a positive electrode composition slurry containing the positive electrode active material It is applied to a predetermined positive electrode current collector and dried to prepare a positive electrode for a lithium-sulfur battery.
  • the positive electrode composition of the lithium-sulfur battery of the present invention may further include a conductive material, a binder, a solvent, and other materials described later in addition to the positive electrode active material.
  • a conductive material may be added to the cathode composition.
  • the conductive material serves to smoothly move electrons in the positive electrode, and the conductive material is not particularly limited as long as it has excellent conductivity and can provide a large surface area without causing chemical changes to the battery. Use substance.
  • the carbonaceous material may be natural graphite, artificial graphite, expanded graphite, graphite-based graphite such as graphene, active carbon-based, channel black, furnace black, thermal Carbon blacks such as thermal black, contact black, lamp black, acetylene black; Carbon fiber-based, carbon nanotubes (CNT), carbon nanostructures such as fullerene (Fullerene) and one selected from the group consisting of a combination thereof may be used.
  • metallic fibers such as metal meshes according to the purpose;
  • Metallic powders such as copper (Cu), silver (Ag), nickel (Ni) and aluminum (Al);
  • organic conductive materials such as a polyphenylene derivative, can also be used.
  • the conductive materials may be used alone or in combination.
  • a binder may be additionally included in the cathode composition in order to provide adhesion to a current collector in the cathode active material.
  • the binder must be well dissolved in a solvent, must not only form a conductive network of the positive electrode active material and the conductive material, but also must have an impregnation property of the electrolyte.
  • the binder applicable to the present invention may be all binders known in the art, and specifically, a fluororesin binder including polyvinylidene fluoride (PVdF) or polytetrafluoroethylene (PTFE) ; Rubber-based binders including styrene-butadiene rubber, acrylonitrile-butadiene rubber and styrene-isoprene rubber; Cellulose binders including carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose; Poly alcohol-based binders; Polyolefin-based binders including polyethylene and polypropylene; Polyimide-based binders, polyester-based binders, silane-based binders; may be one or a mixture of two or more selected from the group consisting of, but is not limited thereto.
  • PVdF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • Rubber-based binders including
  • the content of the binder resin may be 0.5 to 30% by weight based on the total weight of the positive electrode for a lithium-sulfur battery, but is not limited thereto.
  • the content of the binder resin is less than 0.5% by weight, the physical properties of the positive electrode may be lowered and the positive electrode active material and the conductive material may be dropped, and when the content of the binder resin exceeds 30% by weight, the ratio of the active material and the conductive material in the positive electrode may be relatively reduced. Battery capacity can be reduced.
  • the solvent for preparing the lithium-sulfur battery positive electrode composition in a slurry state should be easy to dry and can dissolve the binder well, but most preferably, the positive electrode active material and the conductive material can be maintained in a dispersed state without dissolving.
  • the solvent according to the present invention may be water or an organic solvent, and the organic solvent may be organic containing at least one selected from the group consisting of dimethylformamide, isopropyl alcohol, acetonitrile, methanol, ethanol, and tetrahydrofuran. Solvents are applicable.
  • Mixing of the positive electrode composition may be stirred in a conventional manner using a conventional mixer such as a latex mixer, a high speed shear mixer, a homo mixer, and the like.
  • a conventional mixer such as a latex mixer, a high speed shear mixer, a homo mixer, and the like.
  • the positive electrode composition may be applied to a current collector and vacuum dried to form a positive electrode for a lithium-sulfur battery.
  • the slurry may be coated on the current collector in an appropriate thickness according to the viscosity of the slurry and the thickness of the positive electrode to be formed, preferably, may be appropriately selected within the range of 10 to 300 ⁇ m.
  • the method of coating the slurry is not limited, and for example, doctor blade coating, dip coating, gravure coating, slit die coating, spin coating ( It may be manufactured by performing spin coating, comma coating, bar coating, reverse roll coating, screen coating, cap coating, or the like.
  • the positive electrode current collector may be generally made of a thickness of 3 ⁇ 500 ⁇ m, and is not particularly limited as long as it has a high conductivity without causing chemical changes in the battery.
  • a conductive metal such as stainless steel, aluminum, copper, titanium, or the like can be used, and preferably an aluminum current collector can be used.
  • the positive electrode current collector may be in various forms such as film, sheet, foil, net, porous body, foam, or nonwoven fabric.
  • a lithium-sulfur battery includes a positive electrode for a lithium-sulfur battery comprising the positive electrode composition described above; A negative electrode containing lithium metal or a lithium alloy as a negative electrode active material; A separator interposed between the anode and the cathode; And an electrolyte impregnated in the negative electrode, the positive electrode, and the separator and including a lithium salt and an organic solvent.
  • the negative electrode is a negative electrode active material, a material capable of reversibly intercalating or deintercalating lithium ions (Li + ), and a material capable of reacting with lithium ions to reversibly form a lithium-containing compound.
  • Lithium metal or lithium alloy can be used.
  • the material capable of reversibly intercalating or deintercalating the lithium ions (Li + ) may be, for example, crystalline carbon, amorphous carbon or mixtures 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 may be, for example, an alloy of lithium and a metal selected from the group consisting of Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Al, and Sn.
  • sulfur used as a cathode active material may be changed into an inert material and adhered to the surface of the lithium anode.
  • inactive sulfur refers to sulfur in which sulfur is no longer able to participate in the electrochemical reaction of the anode through various electrochemical or chemical reactions
  • inactive sulfur formed on the surface of the lithium anode is a protective film of the lithium cathode. It also has the advantage of acting as a layer. Therefore, lithium metal and inert sulfur formed on the lithium metal, for example lithium sulfide, may be used as the negative electrode.
  • the negative electrode of the present invention may further include a pretreatment layer made of a lithium ion conductive material and a lithium metal protective layer formed on the pretreatment layer.
  • the separator interposed between the positive electrode and the negative electrode separates or insulates the positive electrode and the negative electrode from each other, and enables transport of lithium ions between the positive electrode and the negative electrode and may be made of a porous non-conductive or insulating material.
  • a separator may be an independent member such as a thin film or a film as an insulator having high ion permeability and mechanical strength, or may be a coating layer added to the anode and / or the cathode.
  • a solid electrolyte such as a polymer
  • the solid electrolyte may also serve as a separator.
  • the pore diameter of the separator is generally 0.01 ⁇ 10 ⁇ m, the thickness is generally 5 ⁇ 300 ⁇ m is preferred, such a separator, a glass electrolyte (Glass electrolyte), a polymer electrolyte or a ceramic electrolyte may be used.
  • Glass electrolyte Glass electrolyte
  • a polymer electrolyte or a ceramic electrolyte may be used.
  • sheets, nonwoven fabrics, kraft papers, etc. made of olefinic polymers such as polypropylene, chemical resistance and hydrophobicity, glass fibers or polyethylene, and the like are used.
  • Typical examples currently on the market include Celgard series (Celgard R 2400, 2300 Hoechest Celanese Corp.), polypropylene separator (Ube Industries Ltd. or Pall RAI), and polyethylene series (Tonen or Entek).
  • the electrolyte separator in the solid state may include less than about 20% by weight of a non-aqueous organic solvent, and in this case, may further include an appropriate gelling agent to reduce the fluidity of the organic solvent.
  • gel-forming compounds include polyethylene oxide, polyvinylidene fluoride, polyacrylonitrile and the like.
  • the electrolyte impregnated in the negative electrode, the positive electrode, and the separator is a non-aqueous electrolyte containing lithium salt, and is composed of a lithium salt and an electrolyte, and a non-aqueous organic solvent, an organic solid electrolyte, an inorganic solid electrolyte, and the like are used as the electrolyte.
  • Lithium salt of the present invention is a good material to dissolve in the non-aqueous organic solvent, for example, LiSCN, LiCl, LiBr, LiI, LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiB 10 Cl 10 , LiCH 3 SO 3 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiClO 4 , LiAlCl 4 , Li (Ph) 4 , LiC (CF 3 SO 2 ) 3 , LiN (FSO 2 ) 2 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (SFO 2 ) 2 , LiN (CF 3 CF 2 SO 2 ) 2 , group consisting of lithium chloroborane, lower aliphatic lithium carbonate, lithium 4-phenylborate, lithium imide and combinations thereof One or more from may be included.
  • LiSCN LiCl, LiBr, LiI, LiPF 6
  • the concentration of the lithium salt is 0.2-2 M, depending on several factors, such as the exact composition of the electrolyte mixture, the solubility of the salt, the conductivity of the dissolved salt, the charging and discharging conditions of the cell, the operating temperature and other factors known in the lithium battery art. 0.6 to 2M, and more specifically 0.7 to 1.7M. If the amount is less than 0.2M, the conductivity of the electrolyte may be lowered, and thus the performance of the electrolyte may be lowered. If the concentration is more than 2M, the viscosity of the electrolyte may be increased, thereby reducing the mobility of lithium ions (Li + ).
  • the non-aqueous organic solvent should dissolve the lithium salt well, and the non-aqueous organic solvent of the present invention, for example, N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate , Dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, gamma-butylo lactone, 1,2-dimethoxy ethane, 1,2-diethoxy ethane, tetrahydroxy franc, 2-methyl Tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolon, 4-methyl-1,3-dioxene, diethyl ether, formamide, dimethylformamide, dioxorone, acetonitrile, nitromethane, methyl formate Methyl acetate, phosphate triester, trimethoxy methane, dioxorone derivative, sulfolane, methyl sulfolane, 1,3-di
  • organic solid electrolyte examples include polyethylene derivatives, polyethylene oxide derivatives, polypropylene oxide derivatives, phosphate ester polymers, poly etchation lysine, polyester sulfides, polyvinyl alcohol, polyvinylidene fluoride, and ionic dissociation. Polymers containing groups and the like can be used.
  • the electrolyte of the present invention includes, for example, pyridine, triethylphosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphate triamide, nitro, for the purpose of improving charge and discharge characteristics, flame retardancy, and the like.
  • Benzene derivatives, sulfur, quinone imine dyes, N-substituted oxazolidinones, N, N-substituted imidazolidines, ethylene glycol dialkyl ethers, ammonium salts, pyrroles, 2-methoxy ethanol, aluminum trichloride and the like may be added. .
  • a halogen-containing solvent such as carbon tetrachloride and ethylene trifluoride may be further included, and carbon dioxide gas may be further included to improve high temperature storage characteristics, and FEC (Fluoro-ethylene) may be further included.
  • the electrolyte may be used as a liquid electrolyte, or may be used in the form of a solid electrolyte separator.
  • a physical separator having a function of physically separating an electrode further includes a separator made of porous glass, plastic, ceramic, or polymer.
  • the SEM image of the CoS 2 nanoparticles obtained is shown in FIG. 2, and the EDS composition analysis results are shown in Table 1 below.
  • the overall composition of the nanoparticles was uniform, and it was confirmed that the S / Co value, which is the ratio of sulfur and cobalt, was 1.67 to 1.78, indicating that CoS 2 - x was slightly deficient in sulfur.
  • the SEM image of the CoS 2 nanoparticles obtained is shown in FIG. 3, and the EDS composition analysis results are shown in Table 2 below.
  • the composition analysis of the CoS 2 nanoparticles showed that the composition of the nanoparticles was uniform throughout, and the S / Co value, which is the component ratio of sulfur and cobalt, was 1.94 to 2.09, which was almost close to CoS 2 .
  • the modified carbon powder (CNT) and sulfur powder were ball-milled and pulverized, and then placed in a 155 ° C. oven for 30 minutes to prepare a sulfur / carbon composite.
  • 0.2 g of Denka black and 5 g of carboxymethyl cellulose (CMC) dispersion were added, and 10 wt% of CoS 2 nanoparticles prepared in Preparation Example 1 was added and mixed with the zirconia ball. Thereafter, 3.6 g of the sulfur / carbon composite prepared above and a predetermined amount of water are mixed and mixed again. Finally, 0.35 g of SBR was added and mixed again to prepare a slurry.
  • a slurry was prepared in the same manner as in Example 1, except that the CoS 2 nanoparticles were not added.
  • the slurry was prepared in the same manner as in Example 1, using the CoS 2 microparticles prepared in Comparative Preparation Example 1.
  • the slurry prepared in Examples 1 to 3, Comparative Examples 1 and 2 was poured onto aluminum foil, coated with a blade coater to a predetermined thickness, and dried in an oven at 50 ° C. to prepare a cathode for a lithium-sulfur battery.
  • the anode is punched to fit the coin cell size, and assembled in an argon glove box.
  • the coin cell was assembled by placing a positive electrode, a separator (Polyethylene), a lithium negative electrode, a gasket, a stainless steel coin, a spring, and a stainless steel upper plate in the stainless steel lower plate.
  • Electrolyte solution was injected with a mixed solution of 1,3-dioxolane (DOL) and diethylene glycol dimethyl ether (DEGDME) in which 1M LiFSI and 1wt% LiNO 3 were dissolved on the anode. Used.
  • DOL 1,3-dioxolane
  • DEGDME diethylene glycol dimethyl ether
  • Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Initial discharge capacity (mAh / g) 1213 1237 1133 1073 605 Discharge Capacity (@ 30 th cycle, mAh / g) 538 576 518 404 414
  • FIG. 6 is a charge and discharge curve of the produced lithium-sulfur battery
  • Figure 7 is a data showing the life retention rate.
  • the first stabilization period (1st plateu: S8 ⁇ S4, eluted with soluble polysulfide)
  • the second stabilization period (2nd plateu: S4 ⁇ ) S2, S1
  • the discharge capacity is higher than that of the comparative example after the long-term cycle evaluation with high life retention.

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  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne un matériau actif de cathode pour une pile lithium-soufre et son procédé de fabrication et, plus précisément, un matériau actif de cathode pour une pile lithium-soufre, comportant des nanoparticules de sulfure métallique, et un procédé de fabrication du matériau actif de cathode. Selon la présente invention, les nanoparticules de sulfure métallique qui sont appliquées à un matériau actif de cathode pour une pile lithium-soufre et qui ont une grande surface spécifique, servent de médiateur redox lors de la charge et de la décharge de la pile lithium-soufre, ce qui permet d'inhiber la génération d'un polysulfure qui peut être élué, et, même si le polysulfure est élué, d'absorber le polysulfure et de l'empêcher de se diffuser dans un électrolyte, ce qui permet de réduire une " réaction navette ", améliorant ainsi les propriétés de capacité et de durée de vie de la pile lithium-soufre.
PCT/KR2017/013676 2016-11-28 2017-11-28 Matériau actif de cathode pour pile lithium-soufre, comportant des nanoparticules de sulfure métallique, et son procédé de fabrication WO2018097695A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US16/308,316 US10770727B2 (en) 2016-11-28 2017-11-28 Cathode active material for lithium-sulfur battery, comprising metal sulfide nanoparticles, and method for producing same
CN201780047753.XA CN109565073A (zh) 2016-11-28 2017-11-28 包含金属硫化物纳米粒子的锂硫电池用正极活性材料及其制造方法
JP2018563903A JP6872093B2 (ja) 2016-11-28 2017-11-28 金属硫化物ナノ粒子を含むリチウム−硫黄電池用正極活物質及びこの製造方法
EP17874276.3A EP3457483B1 (fr) 2016-11-28 2017-11-28 Matériau actif de cathode pour pile lithium-soufre, comportant des nanoparticules de sulfure métallique, et son procédé de fabrication

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KR10-2016-0159418 2016-11-28
KR20160159418 2016-11-28
KR10-2017-0159901 2017-11-28
KR1020170159901A KR102024900B1 (ko) 2016-11-28 2017-11-28 금속 황화물 나노입자를 포함하는 리튬-황 전지용 양극 활물질 및 이의 제조방법

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CN109742359A (zh) * 2019-01-07 2019-05-10 清华大学深圳研究生院 锂硫电池正极材料、其制备方法、正极片及锂硫电池
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CN109742359A (zh) * 2019-01-07 2019-05-10 清华大学深圳研究生院 锂硫电池正极材料、其制备方法、正极片及锂硫电池
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CN111517360A (zh) * 2020-02-21 2020-08-11 郑州轻工业大学 一种基于含磷钼多金属氧酸盐的纳米复合材料及其制备方法、适体传感器及其电极

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