WO2020091478A1 - Composite soufre-carbone, son procédé de préparation, et batterie secondaire au lithium le comprenant - Google Patents

Composite soufre-carbone, son procédé de préparation, et batterie secondaire au lithium le comprenant Download PDF

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WO2020091478A1
WO2020091478A1 PCT/KR2019/014640 KR2019014640W WO2020091478A1 WO 2020091478 A1 WO2020091478 A1 WO 2020091478A1 KR 2019014640 W KR2019014640 W KR 2019014640W WO 2020091478 A1 WO2020091478 A1 WO 2020091478A1
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sulfur
carbon
functional group
carbon composite
electron
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PCT/KR2019/014640
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English (en)
Korean (ko)
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김수현
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주식회사 엘지화학
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Priority to US17/257,679 priority Critical patent/US20210119216A1/en
Priority to CN201980049113.1A priority patent/CN112470309A/zh
Priority to JP2020572780A priority patent/JP7128303B2/ja
Priority to EP19880684.6A priority patent/EP3799162A4/fr
Priority claimed from KR1020190137949A external-priority patent/KR20200049685A/ko
Publication of WO2020091478A1 publication Critical patent/WO2020091478A1/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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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 sulfur-carbon composite and a lithium secondary battery comprising the same.
  • the electrochemical device is the area that is receiving the most attention in this aspect, and among them, the development of a rechargeable battery that can be charged and discharged has become a focus of interest, and recently, in order to improve capacity density and energy efficiency in developing such a battery. Research and development on new electrode and battery designs are in progress.
  • lithium secondary batteries developed in the early 1990s have the advantage of higher operating voltage and significantly higher energy density than conventional batteries such as Ni-MH, Ni-Cd, and sulfuric acid-lead batteries using aqueous electrolyte solutions. Is in the limelight.
  • a lithium-sulfur (Li-S) 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 uses lithium metal as a negative electrode active material.
  • Sulfur the main material of the positive electrode active material, is very rich in resources, non-toxic, and has the advantage of having a low weight per atom.
  • the theoretical discharge capacity of the lithium-sulfur battery is 1675mAh / g-sulfur, and the theoretical energy density is 2,600Wh / kg.
  • Ni-MH batteries 450Wh / kg
  • Li- FeS battery 480Wh / kg
  • Li-MnO 2 battery 1,000Wh / kg
  • Na-S battery 800Wh / kg
  • Patent Document 1 Korean Registered Patent No. 10-1592658 "Surface treated positive electrode active material and lithium secondary battery using the same"
  • the present inventors completed the present invention by confirming that the reactivity can be improved even when a high content of sulfur is loaded by coating a polymer having lithium ion conductivity and electron conductivity inside the porous carbon material. .
  • the present invention is to provide a sulfur-carbon composite and a method of manufacturing the sulfur-carrying material after drying by coating a polymer having lithium ion conductivity and electron conductivity inside the porous carbon material.
  • a sulfur-carbon composite comprising sulfur is provided on at least a portion of the interior and surface of the porous carbon material.
  • the present invention (a) a porous carbon material is mixed in a solution containing a polymer containing an ion-conducting functional group and an electron-conducting functional group, and then dried to form a porosity coated with a polymer containing an ion-conducting functional group and an electron-conducting functional group. Preparing a carbon material; And (b) mixing sulfur with a porous carbon material coated with a polymer containing the ion-conducting functional group and an electron-conducting functional group, followed by heat treatment to prepare a sulfur-carbon composite; a method for producing a sulfur-carbon composite comprising Gives
  • the present invention provides a positive electrode for a lithium secondary battery comprising the sulfur-carbon composite.
  • the present invention is the anode; cathode; And electrolyte; provides a lithium secondary battery comprising a.
  • the sulfur-carbon composite of the present invention in order to solve the problem of reduced reactivity when a high content of sulfur is loaded, and reduced reactivity during high rate charging / discharging, unlike general coating materials used in the prior art, lithium ions It has a feature of coating a polymer containing a functional group that increases mobility and a functional group that increases electron mobility on a porous carbon material.
  • the sulfur-carbon composite of the present invention provides an effect of reducing the overvoltage generated during driving of the battery and increasing the reactivity of the sulfur while containing a high content of sulfur.
  • FIG. 2 is a schematic diagram showing functions according to the structure of the polymer of the present invention.
  • Figure 3 is a graph showing the life characteristics of the lithium-sulfur battery made of the sulfur-carbon composite of Example 1 and Comparative Example 1 of the present invention.
  • Example 4 is a graph showing the overvoltage protection performance of the lithium-sulfur battery made of the sulfur-carbon composites of Example 1 and Comparative Example 1 of the present invention.
  • Example 5 is a graph showing the life characteristics of a lithium-sulfur battery made of the sulfur-carbon composites of Example 1 and Comparative Example 2 of the present invention.
  • Example 6 is a graph showing the life characteristics of a lithium-sulfur battery made of the sulfur-carbon composites of Example 1 and Comparative Example 3 of the present invention.
  • Example 7 is a graph showing the life characteristics of a lithium-sulfur battery made of the sulfur-carbon composites of Example 1 and Comparative Example 4 of the present invention.
  • composite used in the present specification means a substance that combines two or more materials to form physically and chemically different phases and expresses more effective functions.
  • a lithium-sulfur battery which is an embodiment of a lithium secondary battery, uses sulfur as a positive electrode active material and lithium metal as a negative electrode active material.
  • sulfur As a positive electrode active material and lithium metal as a negative electrode active material.
  • an oxidation reaction of lithium occurs at the negative electrode, and a reduction reaction of sulfur occurs at the positive electrode.
  • the reduced sulfur is combined with lithium ions that have been moved from the negative electrode and is converted into lithium polysulfide, and finally involves a reaction to form lithium sulfide.
  • Lithium-sulfur batteries have a much higher theoretical energy density than conventional lithium secondary batteries, and sulfur used as a positive electrode active material is abundant in resources and has low cost, so it is in the spotlight as a next-generation battery due to the advantage of lowering the manufacturing cost of the battery. have.
  • the porous carbon material provides a skeleton in which the positive electrode active material sulfur can be immobilized uniformly and stably, and complements the electrical conductivity of sulfur, so that the electrochemical reaction can proceed smoothly.
  • the porous carbon material can be generally produced by carbonizing precursors of various carbon materials.
  • the porous carbon material includes irregular pores therein, and the average diameter of the pores is in the range of 1 to 200 nm, and the porosity or porosity may range from 10 to 90% of the total volume of the porous. If the average diameter of the pores is less than the above range, impregnation of sulfur is impossible because the pore size is only at the molecular level. Conversely, when it exceeds the above range, the mechanical strength of the porous carbon is weakened, which is preferable for application in the electrode manufacturing process. Does not.
  • the shape of the porous carbon material may be spherical, rod-shaped, needle-shaped, plate-shaped, tubular, or bulk-type, and may be used without limitation as long as it is commonly used in lithium secondary batteries.
  • the porous carbon material may be either a porous structure or a high specific surface area as long as it is commonly used in the art.
  • the porous carbon material includes graphite; Graphene; Carbon blacks such as denka black, acetylene black, ketjen black, channel black, furnace black, lamp black, and summer black; Carbon nanotubes (CNT) such as single-walled carbon nanotubes (SWCNT) and multi-walled carbon nanotubes (MWCNT); Carbon fibers such as graphite nanofiber (GNF), carbon nanofiber (CNF), and activated carbon fiber (ACF); And it may be at least one selected from the group consisting of activated carbon, but is not limited thereto.
  • inorganic sulfur (S 8 ) can be used.
  • the weight ratio of the aforementioned sulfur and the porous carbon material may be 9: 1 to 7: 3. If the content of the sulfur is less than 70% by weight, the amount of binder added in the production of the positive electrode slurry increases as the content of the porous carbon material increases. The increase in the amount of the binder added eventually increases the sheet resistance of the electrode and acts as an insulator preventing electron pass, which can degrade cell performance. Conversely, when it exceeds 90% by weight, sulfur may be aggregated between them, and it may be difficult to directly participate in the electrode reaction due to difficulty receiving electrons.
  • the weight ratio of sulfur to the porous carbon material in the sulfur-carbon composite of the present invention may be 9: 1 to 7.5: 2.5.
  • the sulfur is located on the surface as well as inside the pores of the porous carbon material, wherein less than 100%, preferably 1 to 95%, more preferably 60 to 90% of the entire outer surface of the porous carbon material is present Can be.
  • the sulfur is within the above range on the surface of the porous carbon material, it can exhibit the maximum effect in terms of electron transfer area and wettability of the electrolyte.
  • the sulfur is thinly and evenly impregnated on the surface of the porous carbon material in the above-described range region, it is possible to increase the area of the electron transfer contact during charging and discharging.
  • the porous carbon material is completely covered with sulfur, so that the wettability of the electrolyte decreases and the contact property with the conductive material contained in the electrode does not receive electron transfer and participate in the reaction. It becomes impossible.
  • the sulfur-carbon composite is capable of supporting a high content of sulfur due to pores of various sizes and three-dimensional interconnection in the structure and regularly aligned pores. Due to this, even if soluble polysulfide is generated by the electrochemical reaction, if it can be located inside the sulfur-carbon composite, the three-dimensional entangled structure is maintained even when the polysulfide is eluted to suppress the collapse of the anode structure. have. As a result, the lithium secondary battery including the sulfur-carbon composite has an advantage that a high capacity can be realized even at high loading.
  • the sulfur-loading amount of the sulfur-carbon composite according to the present invention may be 5 to 20 mg / cm 2 .
  • the inner and outer surfaces of the porous carbon material are coated with a polymer containing an ion-conducting functional group and an electron-conducting functional group, as shown in FIG.
  • the coated CNT despite the high sulfur loading, lithium ions can be input and output (the role of a block part that functions as an ion conductivity in FIG. 1 (a)), and the overvoltage is improved (in FIG. 1 (a). It acts as a block part that functions as an electron-conducting function, thereby improving the overall reactivity.
  • the sulfur-carbon composite of the present invention is coated with a polymer comprising an ion-conducting functional group and an electron-conducting functional group on the inner and outer surfaces of the porous carbon material.
  • the polymer containing the ion-conducting functional group and the electron-conducting functional group may include any one or more compounds selected from the group consisting of PEG and Poly Ethylene oxide; And PEDOT, Thiophene and any one or more compounds selected from the group consisting of Pyrrole; may include.
  • the polymer containing an ion-conducting functional group and an electron-conducting functional group used in the present invention contains a compound such as PEG and Poly Ethylene oxide, which can serve as an ion-conducting functional group, and also includes compounds such as PEDOT, Thiophene, and Pyrrole. It can serve as an electron-conducting functional group.
  • the polymer comprising the ion-conducting functional group and the electron-conducting functional group may be a compound of Formula 1 below.
  • the weight average molecular weight of Formula 1 is 1,000 to 1,000,000.
  • R and R ' are each independently a C 5 to C 15 hydrocarbon group, and specific examples of R and R' are C 12 H 25 may be used.
  • the content of the polymer containing the ion-conducting functional group and the electron-conducting functional group used in the present invention may be 0.5 to 5.0% by weight based on the total weight of the sulfur-carbon composite, and preferably 1.0 to 3.0% by weight. If the content of the polymer containing the lithium ion is less than 0.5% by weight, the effect is negligible, and if it exceeds 5% by weight, there is a problem that overvoltage occurs.
  • a porous carbon material is mixed in a solution containing a polymer containing an ion-conducting functional group and an electron-conducting functional group, and then dried to obtain a polymer containing an ion-conducting functional group and an electron-conducting functional group. Preparing a coated porous carbon material;
  • the method of manufacturing the sulfur-carbon composite of the present invention includes a porous carbon material in a solution containing a polymer containing an ion-conducting functional group and an electron-conducting functional group, and then dried to include an ion-conducting functional group and an electron-conducting functional group. It includes the step (a) of preparing a porous carbon material coated with a polymer.
  • a volatile solvent such as volatile ethanol or THF is a polymer containing an ion-conducting functional group and an electron-conducting functional group.
  • a coating composition mixed with.
  • the porous carbon material is mixed with the composition, and then dried. Upon drying, the prepared porous carbon material may be dried at 70 to 150 ° C. for 15 minutes to 1 hour.
  • the characteristics of the polymer and the porous carbon material including the ion-conducting functional group and the electron-conducting functional group used in step (a) are the same as those described above.
  • sulfur is mixed with a porous carbon material coated with a polymer containing the ion-conducting functional group and an electron-conducting functional group, and then heat-treated to prepare a sulfur-carbon composite ( b) step.
  • the weight ratio of the sulfur and the porous carbon material may be 9: 1 to 7: 3. If the content of sulfur is less than the above weight ratio range, as the content of the porous carbon material increases, the amount of binder addition required in preparing the positive electrode slurry increases. The increase in the amount of the binder added eventually increases the sheet resistance of the electrode and acts as an insulator preventing electron pass, which can degrade cell performance. Conversely, when the content of sulfur exceeds the above weight ratio range, sulfur may be aggregated among them, and it may be difficult to directly participate in the electrode reaction due to difficulty receiving electrons.
  • the weight ratio of sulfur to the porous carbon material in the sulfur-carbon composite of the present invention may be 9: 1 to 7.5: 2.5.
  • step (b) When the sulfur and the porous carbon material mixed in step (b) are heat-treated to support sulfur on the porous carbon material to prepare a sulfur-carbon composite, a general heat treatment method used in the art may be used, and preferably melted. Heat treatment may be performed through melt diffusion.
  • the sulfur-carbon composite presented in the present invention can be preferably used as a positive electrode active material of a lithium secondary battery.
  • the positive electrode is produced by applying and drying a composition for forming a positive electrode active material layer on a positive electrode current collector.
  • the composition for forming the positive electrode active material layer is prepared by mixing the above-described sulfur-carbon composite with a conductive material and a binder, and then drying at 40 to 70 ° C. for 4 to 12 hours.
  • a conductive material may be added to the positive electrode composition.
  • the conductive material plays a role for the electrons to move smoothly within the anode, and is not particularly limited as long as it is capable of providing excellent conductivity and a large surface area without causing chemical changes to the battery, but is preferably carbon-based. Use materials.
  • the carbon-based materials include natural graphite, artificial graphite, expanded graphite, graphite-based graphite, active carbon-based, channel black, furnace black, and thermal.
  • Carbon black such as Thermal black, Contact black, Lamp black, Acetylene black;
  • Carbon fiber, carbon nanotubes (CNT), carbon nanostructures such as fullerene (Fullerene), and a combination thereof may be used.
  • metallic fibers such as a metal mesh depending on the purpose;
  • Metallic powders such as copper (Cu), silver (Ag), nickel (Ni), and aluminum (Al);
  • organic conductive materials such as polyphenylene derivatives can also be used. The conductive materials may be used alone or in combination.
  • a binder may be additionally included in the positive electrode composition.
  • the binder should be well soluble in a solvent, not only should a well-constructed conductive network between the positive electrode active material and the conductive material, but also should have adequate impregnation properties of the electrolyte.
  • the binder applicable to the present invention may be all binders known in the art, and specifically, a fluorine resin-based binder including polyvinylidene fluoride (PVdF) or polytetrafluoroethylene (PTFE) ; Rubber-based binders including styrene-butadiene rubber, acrylonitrile-butadiene rubber, and styrene-isoprene rubber; Cellulose-based binders including carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, and regenerated cellulose; Poly alcohol-based binders; Polyolefin-based binders including polyethylene and polypropylene; Polyimide-based binder, polyester-based binder, silane-based binder; may be a mixture or copolymer of one or more selected from the group consisting of, but is not limited to, of course.
  • PVdF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • the content of the binder resin may be 0.5 to 30% by weight based on the total weight of the positive electrode, 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 deteriorate and the positive electrode active material and the conductive material may drop off, and when it exceeds 30% by weight, the ratio of the active material and the conductive material in the positive electrode is relatively reduced. Battery capacity can be reduced.
  • the solvent for preparing the positive electrode composition in a slurry state should be easy to dry, and can dissolve the binder well, but it is most preferable that 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 includes an organic solvent including one or more selected from the group consisting of dimethylformamide, isopropyl alcohol, acetonitrile, methanol, ethanol, and tetrahydrofuran. It is possible.
  • the positive electrode composition may be mixed by a conventional method using a conventional mixer, such as a rate mixer, a high-speed shear mixer, or a homo mixer.
  • a conventional mixer such as a rate mixer, a high-speed shear mixer, or a homo mixer.
  • the positive electrode composition may be applied to a current collector and dried in vacuum to form an positive electrode.
  • the slurry may be coated on the current collector to an appropriate thickness depending on the viscosity of the slurry and the thickness of the anode to be formed, and may be appropriately selected within a range of 10 to 300 ⁇ m.
  • the method of coating the slurry is not limited, for example, doctor blade coating, dip coating, gravure coating, slit die coating, and spin coating ( Spin coating, comma coating, bar coating, reverse roll coating, screen coating, and cap coating may be performed.
  • the positive electrode current collector may be generally 3 to 500 ⁇ m thick, and is not particularly limited as long as it has high conductivity without causing chemical changes in the battery.
  • a conductive metal such as stainless steel, aluminum, copper, or titanium can be used, and preferably, an aluminum current collector can be used.
  • the positive electrode current collector may be in various forms such as a film, sheet, foil, net, porous body, foam, or nonwoven fabric.
  • the lithium secondary battery includes the positive electrode described above; A negative electrode comprising a 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 containing a lithium salt and an organic solvent, preferably the lithium secondary battery may be a lithium-sulfur battery containing a sulfur compound in a positive electrode active material in the positive electrode. have.
  • the negative electrode is a negative electrode active material capable of reversibly intercalating or deintercalating lithium ions (Li + ), a material capable of reversibly forming a lithium-containing compound by reacting with lithium ions , Lithium metal or lithium alloy can be used.
  • the material capable of reversibly intercalating or deintercalating the lithium ions may be, for example, crystalline carbon, amorphous carbon, or a mixture thereof.
  • a material capable of reversibly forming a lithium-containing compound by reacting with the lithium ion 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.
  • the sulfur used as the positive electrode active material is changed to an inactive material, and may be attached to the surface of the lithium negative electrode.
  • inactive sulfur refers to sulfur in a state in which sulfur can no longer participate in the electrochemical reaction of the positive electrode through various electrochemical or chemical reactions, and inactive sulfur formed on the surface of the lithium negative electrode protects the protective film of the lithium negative electrode. layer). Therefore, a lithium metal and an inert sulfur formed on the lithium metal, for example lithium sulfide, can also be used as the negative electrode.
  • the negative electrode of the present invention may further include a pre-treatment layer made of a lithium ion conductive material and a lithium metal protection layer formed on the pre-treatment layer in addition to the negative electrode active material.
  • 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.
  • the separator is an insulator having high ion permeability and mechanical strength, and may be an independent member such as a thin film or a film, or 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 to 10 ⁇ m, and the thickness is generally 5 to 300 ⁇ m, and as the separator, a glass electrolyte, a polymer electrolyte, or a ceramic electrolyte may be used.
  • a glass electrolyte such as chemically and hydrophobic polypropylene, sheets or non-woven fabrics made of glass fiber or polyethylene, or the like are used.
  • Typical examples currently on the market include the Celgard series (Celgard R 2400, 2300 Hoechest Celanese Corp.), polypropylene separator (manufactured by Ube Industries Ltd. or Pall RAI), and polyethylene series (Tonen or Entek).
  • the solid electrolyte separator may contain less than about 20% by weight of a non-aqueous organic solvent, and in this case, may further include an appropriate gel-forming compound to reduce the fluidity of the organic solvent.
  • gel-forming compounds include polyethylene oxide, polyvinylidene fluoride, and polyacrylonitrile.
  • the negative electrode, the positive electrode and the electrolyte impregnated in the separator are lithium salts and non-aqueous electrolytes containing lithium salts.
  • the electrolytes include non-aqueous organic solvents, organic solid electrolytes, and inorganic solid electrolytes.
  • Lithium salt of the present invention is a material that is soluble in a 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 , lithium chloroborane, lower aliphatic lithium carboxylate, lithium 4-phenyl borate, lithium imide, and combinations thereof One or more may be included.
  • the concentration of the lithium salt is 0.2 to 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 conditions for charging and discharging the cell, the working temperature and other factors known in the lithium battery field. Specifically, it may be 0.6 to 2 M, more specifically 0.7 to 1.7 M. When used below 0.2 M, the conductivity of the electrolyte may be lowered, resulting in deterioration of electrolyte performance, and when used above 2 M, the viscosity of the electrolyte may increase and mobility of lithium ions (Li + ) may decrease.
  • the non-aqueous organic solvent should dissolve a lithium salt well, and as the non-aqueous organic solvent of the present invention, for example, N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, di Ethyl carbonate, ethylmethyl carbonate, gamma-butyrolactone, 1,2-dimethoxy ethane, 1,2-diethoxy ethane, tetrahydroxy franc, 2-methyl tetrahydrofuran, dimethyl sulfoxide, 1, 3-dioxolane, 4-methyl-1,3-dioxene, diethyl ether, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphoric acid triester, trime Non-proton such as methoxymethane, dioxolane derivatives, sulfolane, methyl s
  • organic solid electrolyte examples include, for example, polyethylene derivatives, polyethylene oxide derivatives, polypropylene oxide derivatives, phosphoric acid ester polymers, poly agitation lysine, polyester sulfide, polyvinyl alcohol, polyvinylidene fluoride, and ionic dissociation. Polymers containing groups and the like can be used.
  • the inorganic solid electrolyte for example, Li 3 N, LiI, Li 5 NI 2 , Li 3 N-LiI-LiOH, LiSiO 4 , LiSiO 4 -LiI-LiOH, Li 2 SiS 3 , Li 4 SiO 4 , Li 4 Li nitrides such as SiO 4 -LiI-LiOH, Li 3 PO4-Li 2 S-SiS 2 , halides, sulfates, and the like can be used.
  • pyridine triethylphosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme (glyme), hexaphosphate triamide, nitro Benzene derivatives, sulfur, quinone imine dyes, N-substituted oxazolidinones, N, N-substituted imidazolidines, ethylene glycol dialkyl ethers, ammonium salts, pyrrole, 2-methoxy ethanol, aluminum trichloride, etc.
  • pyridine triethylphosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme (glyme), hexaphosphate triamide, nitro Benzene derivatives, sulfur, quinone imine dyes, N-substituted oxazolidinones, N, N-substituted imidazolidines, ethylene glycol dialkyl ethers, ammonium
  • a halogen-containing solvent such as carbon tetrachloride or ethylene trifluoride may be further included, or carbon dioxide gas may be further included to improve high temperature storage characteristics, and FEC (Fluoro-ethylene) carbonate), PRS (Propene sultone), FPC (Fluoro-propylene carbonate), and the like.
  • 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 electrodes further includes a separator made of porous glass, plastic, ceramic, or polymer.
  • a coating solution was prepared by dissolving 0.2 g of PEG-block-PEDOT (Sigma-aldrich) in THF.
  • a sulfur-carbon composite was prepared in the same manner as in Example 1 except that 0.4 g of PEG-block-PEDOT (product name, sigma-aldrich) was dissolved in THF to prepare 5 g of a coating solution.
  • PEG-block-PEDOT product name, sigma-aldrich
  • a sulfur-carbon composite was prepared in the same manner as in Example 1, except that a carbon nanotube without PEG-block-PEDOT coating was used.
  • a sulfur-carbon composite was prepared in the same manner as in Example 1, except that 2 g of sulfur / carbon composite (sulfur 1.5 g) was evenly mixed and polyethyleneimide was coated on the sulfur-carbon composite instead of PEG-block-PEDOT.
  • a sulfur-carbon composite was prepared by uniformly mixing 2 g of sulfur / carbon composite (sulfur 1.5 g) and melt diffusion at 155 ° C. for 30 minutes. Then, after dissolving 0.2 g of PEG-block-PEDOT (igma-aldrich) in THF to prepare 5 g of a coating solution, 2 g of sulfur / carbon complex was stirred in the solution for 15 minutes, and then in an oven at 80 ° C. for 30 minutes. By drying, a PEG-block-PEDOT-coated sulfur / carbon composite was prepared.
  • a sulfur-carbon composite was prepared in the same manner as in Example 1, except that 2 g of the sulfur / carbon composite was evenly mixed and a polyimide was coated instead of PEG-block-PEDOT.
  • a sulfur-carbon composite was prepared in the same manner as in Example 1, except that polyethylene oxide was used instead of PEG-block-PEDOT (product name, sigma-aldrich).
  • the produced coin cells were measured with a capacity from 1.8 to 2.6 V using a charge / discharge measuring device. Specifically, 0.1 / 0.1, 0.3 / 0.3, and 0.5 / 0.5 charging / discharging cycles were repeated until the degeneration time of the cells to perform cell testing. The results obtained at this time are shown in FIGS. 3 and 4.
  • the lithium secondary battery made of the sulfur-carbon composite of Example 1 has improved life characteristics compared to the lithium secondary battery made of the sulfur-carbon composite of Comparative Example 1 and Comparative Example 5. .
  • the lithium-sulfur battery made of the sulfur-carbon composite of Example 1 is coated with a cationic conductive polymer on the carbon material compared to the lithium secondary battery made of the sulfur-carbon composite of Comparative Example 1 and Comparative Example 5 When it was done, it was found that the overvoltage was reduced compared to the reference electrode.

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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Abstract

La présente invention concerne un composite soufre-carbone et son procédé de préparation, le composite comprenant : un matériau carboné poreux dont la surface interne et la surface externe sont revêtues d'un polymère comprenant un groupe fonctionnel conducteur d'ions et un groupe fonctionnel conducteur d'électrons; et du soufre sur au moins une partie des surfaces et de l'intérieur du matériau carboné poreux.
PCT/KR2019/014640 2018-10-31 2019-10-31 Composite soufre-carbone, son procédé de préparation, et batterie secondaire au lithium le comprenant WO2020091478A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US17/257,679 US20210119216A1 (en) 2018-10-31 2019-10-31 Sulfur-carbon composite, method for preparing same, and lithium secondary battery comprising same
CN201980049113.1A CN112470309A (zh) 2018-10-31 2019-10-31 硫碳复合物、其制备方法和包含其的锂二次电池
JP2020572780A JP7128303B2 (ja) 2018-10-31 2019-10-31 硫黄－炭素複合体、この製造方法及びこれを含むリチウム二次電池
EP19880684.6A EP3799162A4 (fr) 2018-10-31 2019-10-31 Composite soufre-carbone, son procédé de préparation, et batterie secondaire au lithium le comprenant

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KR20180132423 2018-10-31
KR10-2018-0132423 2018-10-31
KR1020190137949A KR20200049685A (ko) 2018-10-31 2019-10-31 황-탄소 복합체, 이의 제조방법 및 이를 포함하는 리튬 이차전지
KR10-2019-0137949 2019-10-31

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KR20180132423A (ko) 2017-06-03 2018-12-12 백종원 분리가능한 신발 먼지함으로 구성된 신발장
KR20190137949A (ko) 2017-06-29 2019-12-11 주식회사 씨젠 검출용 조성물 준비 장치의 제어 방법 및 기기

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KR20180132423A (ko) 2017-06-03 2018-12-12 백종원 분리가능한 신발 먼지함으로 구성된 신발장
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