WO2019107752A1 - 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

Info

Publication number
WO2019107752A1
WO2019107752A1 PCT/KR2018/012795 KR2018012795W WO2019107752A1 WO 2019107752 A1 WO2019107752 A1 WO 2019107752A1 KR 2018012795 W KR2018012795 W KR 2018012795W WO 2019107752 A1 WO2019107752 A1 WO 2019107752A1
Authority
WO
WIPO (PCT)
Prior art keywords
sulfur
carbon composite
lithium
secondary battery
lithium secondary
Prior art date
Application number
PCT/KR2018/012795
Other languages
English (en)
Korean (ko)
Inventor
한승훈
손권남
김의태
양두경
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Publication of WO2019107752A1 publication Critical patent/WO2019107752A1/fr

Links

Images

Classifications

    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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, a process for producing the same, and a lithium secondary battery comprising the same.
  • a lithium-sulfur (Li-S) battery is a secondary battery in which a sulfur-based material having a sulfur-sulfur bond is used as a cathode active material and lithium metal is used as an anode active material.
  • Sulfur the main material of the cathode active material, is very rich in resources, has no toxicity, and has a low atomic weight.
  • the theoretical energy density of the lithium-sulfur battery is 1,675 mAh / g-sulfur and the theoretical energy density is 2,600 Wh / kg.
  • Ni-MH battery 450 Wh / kg, which is the most promising battery ever developed because it is much higher than that of Li-FeS battery: 480Wh / kg, Li-MnO 2 battery: 1,000Wh / kg, Na-S battery: 800Wh / kg.
  • Patent Document 1 Korean Patent Publication No. 10-2015-0135961 (2015.12.04), "a method for producing a sulfur-carbon composite through dual dry complexation"
  • Sulfur-carbon nanotube composite a method for producing the same, a cathode active material for a lithium-sulfur battery including the same, and a lithium sulfur battery including the sulfur active material for the lithium-sulfur battery are disclosed in Korean Patent Publication No. 10-2016-0037084 (2016.04.05)
  • an object of the present invention is to provide a cathode active material for a lithium secondary battery which can solve the problem caused by lithium polysulfide.
  • a coating layer positioned on the surface of the sulfur-carbon composite and containing iron hydroxide (FeOOH);
  • the content of the coating layer is 5 to 20 parts by weight based on 100 parts by weight of the sulfur-carbon composite.
  • the content of the coating layer is 10 to 15 parts by weight based on 100 parts by weight of the sulfur-carbon composite.
  • the thickness of the coating layer is 500 nm to 2 ⁇ ⁇ .
  • the sulfur-carbon composite contains 60 to 80 parts by weight of sulfur relative to 100 parts by weight of the sulfur-carbon composite.
  • the sulfur-carbon composite comprises a carbonaceous material having a diameter of 5 to 50 nm and a length of 500 nm to 10 ⁇ .
  • the particle size of the sulfur-carbon composite is 10 to 50 mu m.
  • the mean diameter of the particles of the iron hydroxide is 50 to 500 nm.
  • the iron hydroxide is lepidocrocite (? -FeOOH).
  • the lepidocrocite is a plate-shaped.
  • the present invention also provides a positive electrode for a lithium secondary battery comprising the above-described positive electrode active material for a lithium secondary battery, a binder and a conductive material.
  • dry mixing is a ball mill mixing or a blade mixing.
  • the dry mixing is performed at a weight ratio of sulfur-carbon composite to iron hydroxide in a weight ratio of 5: 1 to 20: 1.
  • the coating layer is formed to a thickness of 500 nm to 2 ⁇ ⁇ .
  • the ball mill mixing is performed at a speed of 100 to 300 rpm.
  • the ball mill mixing is performed for 1 to 3 hours.
  • One embodiment of the present invention is that the blade blending is performed at a speed of 1000 to 3000 rpm.
  • One embodiment of the present invention is that the blade mixing is performed for 30 minutes to 1 hour.
  • the lithium secondary battery includes sulfur in the anode.
  • the cathode active material for a lithium secondary battery according to the present invention includes a coating layer containing iron hydroxide on the surface of a cathode active material, thereby solving the problem caused by lithium polysulfide generated in the anode of the lithium secondary battery and suppressing side reactions with the electrolyte.
  • the lithium secondary battery provided with the anode including the cathode active material can be realized in a high capacity battery because the capacity of sulfur is not lowered and the sulfur can be stably applied by high loading and there is no problem such as short or heat of the battery, .
  • such a lithium secondary battery has an advantage that the charging and discharging efficiency of the battery is high and the life characteristic is improved.
  • FIG. 1 is a schematic view of a method of coating a sulfur-carbon composite according to the present invention with iron hydroxide.
  • FIG. 2 is a schematic view of an anode structure according to an embodiment of the present invention.
  • FIG 3 is a schematic view of an anode structure according to a comparative example of the present invention.
  • FIG. 4 is a SEM photograph of a cathode active material coated with iron hydroxide according to the present invention.
  • FIG. 5 is a SEM photograph of a cathode active material coated with iron hydroxide according to the present invention.
  • FIG. 6 is a graph showing the discharge capacity of a lithium-sulfur battery made of a sulfur-carbon composite material according to Examples and Comparative Examples of the present invention.
  • &quot refers to a material that combines two or more materials to form a physically and chemically distinct phase while exhibiting a more effective function.
  • Lithium-sulfur battery has much higher discharging capacity and theoretical energy density than existing lithium secondary batteries, and sulfur, which is used as a cathode active material, is attracting attention as a next-generation battery because of its abundant reserves, low cost, and environment friendliness.
  • the theoretical capacity and the energy density are not realized in actual operation. This is because the low lithium ion conductivity of sulfur, the cathode active material, is very low in the proportion of sulfur participating in the actual electrochemical redox reaction.
  • the capacity and efficiency of the lithium-sulfur battery may vary depending on the amount of lithium ions delivered to the anode. Therefore, it is important to increase the lithium ion conductivity of the positive electrode to increase the capacity and high efficiency of the lithium-sulfur battery.
  • the lithium polysulfide formed in the anode during the charge and discharge reactions is lost outside the anode reaction region, and a shuttle phenomenon occurs in which it moves between the anode and the cathode.
  • lithium sulfide is fixed on the surface of the lithium metal due to the side reaction between the lithium polysulfide eluted from the anode and the lithium metal as the negative electrode, so that the reaction activity is lowered and the lithium ion is unnecessarily consumed, A problem arises.
  • the present invention provides a positive electrode for a lithium secondary battery improved by solving the disadvantages of a positive electrode for a lithium secondary battery and a problem of lowering of the continuous reactivity of the electrode due to polysulfide dissolution and shuttle phenomenon, and a problem of reduction in discharge capacity.
  • the cathode active material provided in the present invention solves the above problems by forming a coating layer containing iron hydroxide having a function of adsorbing lithium polysulfide on the sulfur-carbon composite.
  • the positive electrode active material according to an embodiment of the present invention forms a coating layer containing iron hydroxide on the surface of the sulfur-carbon composite, thereby adsorbing lithium polysulfide generated in the lithium secondary battery by iron hydroxide in the coating layer, Can be greatly improved.
  • the content of the coating layer may be 5 to 20 parts by weight based on 100 parts by weight of the sulfur-carbon composite, and preferably 10 to 15 parts by weight with respect to 100 parts by weight of the sulfur-carbon composite. If the content of the coating layer is less than 5 parts by weight based on 100 parts by weight of the sulfur-carbon composite, the effect of adsorbing lithium polysulfide may be insignificant. When the amount exceeds 20 parts by weight, the coating layer may act as a resistor, , And is appropriately adjusted in the above range.
  • inorganic sulfur (S 8 ) can be used.
  • the carbon of the sulfur-carbon composite according to the present invention may have a porous structure or a high specific surface area, as long as it is commonly used in the art.
  • the porous carbon material may include graphite; Graphene; Carbon black such as denka black, acetylene black, ketjen black, channel black, furnace black, lamp black, and summer black; Carbon nanotubes (CNTs) such as single wall carbon nanotubes (SWCNTs) and multiwall carbon nanotubes (MWCNTs); Carbon fibers such as graphite nanofibers (GNF), carbon nanofibers (CNF), and activated carbon fibers (ACF); And activated carbon, but the present invention is not limited thereto, and its form can be used without limitation as long as it is generally used in a lithium secondary battery in a spherical shape, rod shape, needle shape, plate shape, tubular shape or bulk shape.
  • the thickness of the coating layer may be 500 nm to 2 ⁇ ⁇ .
  • the thickness of the coating layer is less than 500 nm, the effect of improving the charging / discharging efficiency and lifetime characteristics of the battery may be small and the resistance of the lithium polysulfide may be decreased. The efficiency of the battery may deteriorate. Therefore, it is suitably adjusted in the above range.
  • the sulfur-carbon composite may contain 60 to 80 parts by weight of sulfur relative to 100 parts by weight of the sulfur-carbon composite, and preferably 70 parts by weight of sulfur. If the content of sulfur is less than the above-mentioned weight ratio, the amount of the binder added during the preparation of the positive electrode slurry is increased as the content of the porous carbonaceous material is increased. Such an increase in the amount of the binder increases the sheet resistance of the electrode, and acts as an insulator to prevent electron transfer, which may degrade the cell performance. On the contrary, when the content of sulfur exceeds the above-mentioned weight ratio range, the sulfur becomes aggregated with each other, and it is difficult to participate in the electrode reaction because it is difficult to receive electrons.
  • the sulfur-carbon composite according to an embodiment of the present invention may include carbon materials having a diameter of 5 to 50 nm and a length of 500 nm to 10 ⁇ ,
  • the size of the sulfur-carbon composite may be 10 to 50 mu m.
  • the particle size of the sulfur-carbon composite is less than 10 m, there is a problem that an inter-particle resistance increases and an overvoltage occurs in the electrode of the lithium secondary battery.
  • the particle size exceeds 50 m, the surface area per unit weight becomes small, And the amount of electrons to be transferred to the composite is decreased. As a result, the discharge capacity of the resultant battery may be reduced. As a result, in the range of As appropriate.
  • the iron hydroxide (FeOOH) contained in the coating layer can reduce the lifetime of the lithium secondary battery by transferring the lithium polysulfide to the cathode by adsorbing the lithium polysulfide, , It is possible to increase the discharge capacity of the lithium secondary battery including the positive electrode and to improve the lifetime of the battery.
  • the iron hydroxide according to the present invention may preferably be one produced by the following production method.
  • the iron hydroxide can be prepared by reacting Fe (NO 3 ) 3 .9H 2 O with NaBH 4 . At this time, NaBH 4 and Fe (NO 3 ) 3 .9H 2 O can be reacted at a ratio of 3: 1 to 12: 1. Using NaBH 4 solution, iron hydroxide is naturally synthesized in aqueous solution after conversion of Fe 3 + cation to metallic Fe.
  • iron hydroxide can be prepared by reacting 0.04 to 0.08 M of Fe (NO 3 ) 3 .9H 2 O with 0.2 to 0.5 M NaBH 4 solution. At this time, Fe (NO 3 ) 3 .9H 2 O should be added to the NaBH 4 solution. If the order is reversed, pure iron hydroxide is not synthesized.
  • the reaction may be performed by mixing NaBH 4 solution and Fe (NO 3 ) 3 .9H 2 O within 10 to 120 seconds.
  • a gas is generated at one time.
  • the phase of the product in the initial stage of the reaction and the product of the latter stage of the reaction are different from each other, so that pure iron hydroxide can not be produced.
  • the reaction proceeds at 20 to 25 DEG C and the mixed solution is stirred at 300 to 500 rpm.
  • hydrogen gas H 2
  • the reaction is allowed to proceed for 40 minutes for sufficient degassing.
  • the produced iron hydroxide is filtered through a filter paper, and sufficient air is introduced into the filter, and the filter can be dried at 80 ° C. for 6 to 12 hours to produce iron hydroxide.
  • the iron hydroxide according to one embodiment of the present invention may be one prepared by the above production method, and the iron hydroxide produced by the above method may be lepidocrocite ( ⁇ -FeOOH), and the average particle diameter is 50 to 500 nm, and may be a plate-like structure.
  • the present invention also includes a step of dry-mixing the sulfur-carbon composite material and the iron hydroxide to form a coating layer containing iron hydroxide on the surface of the sulfur-carbon composite material,
  • dry mixing is a ball mill mixing or a blade mixing.
  • the method of forming the coating layer on the surface of the sulfur-carbon composite generally includes a dry mixing method and a wet mixing method.
  • a wet mixing method When the wet mixing method is used, there is an advantage that the coating layer formed on the surface of the sulfur-carbon composite material can be obtained more uniformly.
  • the sulfur-carbon composite exhibits very high hydrophobicity, Wet processes can be difficult because they do not work well.
  • an organic solvent When an organic solvent is used, a part of sulfur is dissolved in an organic solvent, and since the re-dispersed or dissolved sulfur may cover the iron hydroxide to interfere with the lithium polysulfide adsorption effect of the iron hydroxide, the present invention uses a dry mixing method .
  • the dry mixing may be performed in a weight ratio of sulfur-carbon composite material and iron hydroxide in a weight ratio of 5: 1 to 20: 1. If the content of the iron hydroxide is less than the above range, the adsorption effect of the lithium polysulfide may be insignificant. If the content exceeds the above range, the coating layer containing iron hydroxide acts as a resistor and the efficiency of the battery may decrease. .
  • the coating layer may be formed to a thickness of 500 nm to 2 ⁇ ⁇ .
  • the thickness of the coating layer is less than 500 nm, the effect of improving the charging / discharging efficiency and lifetime characteristics of the battery may be small due to the effect of adsorption of lithium polysulfide.
  • the thickness exceeds 2 ⁇ , the electrochemical characteristics The efficiency of the battery may deteriorate, so that it is properly adjusted within the above range.
  • the coating may be a ball mill blend or blade blend in a dry blending method.
  • the sulfur contained in the sulfur-carbon composite is a highly ductile material, and may be subjected to a process in which iron hydroxide is coated on the surface of the sulfur-carbon composite by friction with iron hydroxide in the ball mill or blade mixing process as the dry mixing method. And a sulfur-carbon composite in which a coating layer containing iron hydroxide is formed is shown in FIGS.
  • the ball mill may be performed at a speed of 100 to 300 rpm for 1 to 3 hours, and the blade blending may be performed at a speed of 1000 to 3000 rpm for 30 minutes to 1 hour .
  • the iron hydroxide is not uniformly distributed on the surface of the sulfur-carbon composite, so that the lithium polysulfide adsorption effect is insignificant and the discharge capacity of the battery can be reduced.
  • - carbon composite itself has a small particle size, which causes generation of fine particles, increases resistance between particles, and generates an overvoltage on the electrode.
  • the mixing time is less than the above-mentioned time, the iron hydroxide is not uniformly distributed on the surface of the sulfur-carbon composite, so that the lithium polysulfide adsorption effect is insignificant and the discharge capacity of the battery may be reduced. If the rate is exceeded, heat is generated in a large amount during the mixing process. As a result, sulfur of the sulfur-carbon composite is melted and affects the physical properties of the anode for a lithium secondary battery.
  • the present invention provides a positive electrode for a lithium secondary battery comprising the positive electrode active material.
  • the cathode for a lithium secondary battery according to the present invention may include the above-described cathode active material for a lithium secondary battery, a binder, and a conductive material.
  • the anode may be prepared by a conventional method known in the art.
  • a slurry may be prepared by mixing and stirring a solvent, a binder, a conductive material, and a dispersant as necessary in a cathode active material, and then coating (coating) the mixture on a current collector of a metal material, have.
  • a conductive material may be added to the cathode active material.
  • the conductive material plays a role in allowing electrons to move smoothly in the anode.
  • the conductive material is not particularly limited as long as the conductive material does not cause a chemical change in the battery and can provide a large surface area. Materials are used.
  • Examples of the carbon-based material include natural graphite, artificial graphite, expanded graphite, graphite such as Graphene, active carbon, channel black, furnace black, Carbon black such as black, thermal black, contact black, lamp black, and acetylene black;
  • a carbon nano structure such as a carbon fiber, a carbon nanotube (CNT), and a fullerene, and a combination thereof may be used.
  • metallic fibers such as metal mesh may be used depending on the purpose.
  • Metallic powder such as copper (Cu), silver (Ag), nickel (Ni) and aluminum (Al);
  • an organic conductive material such as a polyphenylene derivative can also be used.
  • the conductive materials may be used alone or in combination.
  • a binder may be further included in the positive electrode composition.
  • the binder must be well dissolved in a solvent, and it should not only constitute a conductive network between the cathode active material and the conductive material, but also have an ability to impregnate the electrolyte appropriately.
  • the binder applicable to the present invention may be any binder known in the art and specifically includes a fluororesin binder containing polyvinylidene fluoride (PVdF) or polytetrafluoroethylene (PTFE) ; Rubber-based binders including styrene-butadiene rubber, acrylonitrile-butadiene rubber, and styrene-isoprene rubber; Cellulosic binders including carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, and regenerated cellulose; Polyalcohol-based binders; Polyolefin binders including polyethylene and polypropylene; But are not limited to, polyimide-based binders, polyester-based binders, and silane-based binders, or a mixture or copolymer of two or more thereof.
  • PVdF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • Rubber-based binders including sty
  • the content of the binder resin may be 0.5-30 wt% based on the total weight of the positive electrode for a lithium secondary battery, but is not limited thereto. If 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 fall off. When the amount of the binder resin is more than 30% by weight, the ratio of the active material and the conductive material is relatively decreased The battery capacity can be reduced.
  • the solvent for preparing the cathode composition for a lithium secondary battery in a slurry state should be easy to dry and most preferably the cathode active material and the conductive material can be maintained in a dispersed state without dissolving the binder.
  • the solvent according to the present invention may be water or an organic solvent, and the organic solvent may be an organic solvent containing at least one selected from the group consisting of dimethylformamide, isopropyl alcohol, acetonitrile, methanol, ethanol and tetrahydrofuran It is possible.
  • the mixing of the cathode composition may be carried out by a conventional method using a conventional mixer such as a latex mixer, a high-speed shear mixer, a homomixer, and the like.
  • a conventional mixer such as a latex mixer, a high-speed shear mixer, a homomixer, and the like.
  • the positive electrode composition is applied to a current collector, and vacuum dried to form a positive electrode for a lithium secondary battery.
  • the slurry may be coated on the current collector with an appropriate thickness according to the viscosity of the slurry and the thickness of the anode to be formed, and may be suitably selected within the range of 10 to 300 mu m.
  • the slurry may be coated by a method such as doctor blade coating, dip coating, gravure coating, slit die coating, spin coating, Spin coating, comma coating, bar coating, reverse roll coating, screen coating, cap coating and the like.
  • the cathode current collector generally has a thickness of 3 to 500 ⁇ , 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 an aluminum current collector can be preferably used.
  • Such a positive electrode current collector may have various forms such as a film, a sheet, a foil, a net, a porous body, a foam or a nonwoven fabric.
  • the lithium secondary battery is manufactured by using a material capable of intercalation / deintercalation of lithium ions as a cathode and an anode, filling an organic electrolytic solution or a polymer electrolyte between a cathode and an anode, And an electrochemical device that generates electrical energy by an oxidation / reduction reaction when it is desorbed.
  • the lithium secondary battery includes a lithium-sulfur Battery.
  • a lithium secondary battery includes the above-described cathode for a lithium secondary battery; A negative electrode comprising 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 with the negative electrode, the positive electrode and the separator, and including a lithium salt and an organic solvent.
  • the negative electrode is a negative active material that can reversibly intercalate or deintercalate lithium ions (Li + ), a material capable of reversibly reacting with lithium ions to form a lithium-containing compound ,
  • a lithium metal or a lithium alloy can be used.
  • the material capable of reversibly intercalating or deintercalating lithium ions may be, for example, crystalline carbon, amorphous carbon, or a mixture thereof.
  • the material capable of reacting with the lithium ion 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.
  • the sulfur used as the cathode active material is changed to an inactive material and can be attached to the surface of the lithium anode.
  • Inactive sulfur is sulfur in which sulfur can not participate in the electrochemical reaction of the anode after various electrochemical or chemical reactions.
  • Inactive sulfur formed on the surface of the lithium anode is a protective film of the lithium anode layer as well. Therefore, a lithium metal and an inert sulfur formed on the lithium metal, such as lithium sulfide, may be used as the cathode.
  • the negative electrode of the present invention may further include a pretreatment layer made of a lithium ion conductive material in addition to the negative electrode active material, and a lithium metal protective layer formed on the pretreatment layer.
  • the separator interposed between the anode and the cathode separates or insulates the anode and the cathode from each other and allows transport of lithium ions between the anode and the cathode, and may be made of a porous nonconductive 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 separation membrane.
  • the separator preferably has a pore diameter of 0.01 to 10 ⁇ m and a thickness of 5 to 300 ⁇ m.
  • the separator may be a glass electrolyte, a polymer electrolyte, a ceramic electrolyte, or the like.
  • olefin-based polymers such as polypropylene having chemical resistance and hydrophobicity, sheets or nonwoven fabrics made of glass fibers or polyethylene, kraft paper, and the like are used.
  • Representative examples currently on the market include the Celgard R 2400 (2300 Hoechest Celanese Corp.), polypropylene separator (Ube Industries Ltd. or Pall RAI), and polyethylene (Tonen or Entek).
  • the solid electrolyte separation membrane may contain less than about 20% by weight of a non-aqueous organic solvent, in which case it may further comprise a suitable gelling agent to reduce the fluidity of the organic solvent.
  • suitable gelling agent include polyethylene oxide, polyvinylidene fluoride, and polyacrylonitrile.
  • the electrolyte impregnated in the negative electrode, the positive electrode and the separator is a non-aqueous electrolyte containing a lithium salt.
  • the non-aqueous electrolyte is composed of a lithium salt and an electrolyte.
  • Non-aqueous organic solvents, organic solid electrolytes and inorganic solid electrolytes are used as the electrolyte.
  • the lithium salt of the present invention can be dissolved 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 3 SO 2 ) 2 , LiN (SFO 2 ) 2 , LiN (CF 3 CF 2 SO 2 ) 2 , chloroborane lithium, lower aliphatic carboxylate lithium, lithium tetraphenylborate, lithium imide and combinations thereof May be included.
  • a non-aqueous organic solvent for example, LiSCN, LiCl, LiBr, LiI, LiPF 6 , LiBF 4 , LiSbF 6
  • the concentration of the lithium salt may be in the range of 0.2 to 2 M, preferably 1 to 2 M, depending on various factors such as the precise composition of the electrolyte mixture, the solubility of the salt, the conductivity of the dissolved salt, the charging and discharging conditions of the battery, Specifically, it may be 0.6 to 2 M, more specifically 0.7 to 1.7 M. If it is used at less than 0.2 M, the conductivity of the electrolyte may be lowered and the performance of the electrolyte may be deteriorated. If it is used in excess of 2 M, the viscosity of the electrolyte may increase and the mobility of lithium ions (Li + ) may be reduced.
  • non-aqueous organic solvent of the present invention examples include N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, di Ethyl carbonate, ethyl methyl carbonate, gamma-butyrolactone, 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydroxyfuran, 2-methyltetrahydrofuran, dimethylsulfoxide, 3-dioxolane, diethyl ether, formamide, dimethyl formamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphoric acid triester, trimethylene Ethers such as ethoxymethane, dioxolane derivatives, sulfolane, methylsulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, t
  • organic solid electrolyte examples include a polymer electrolyte such as a polyethylene derivative, a polyethylene oxide derivative, a polypropylene oxide derivative, a phosphate ester polymer, an agitation lysine, a polyester sulfide, a polyvinyl alcohol, a polyvinylidene fluoride, A polymer including a group can be used.
  • a polymer electrolyte such as a polyethylene derivative, a polyethylene oxide derivative, a polypropylene oxide derivative, a phosphate ester polymer, an agitation lysine, a polyester sulfide, a polyvinyl alcohol, a polyvinylidene fluoride, A polymer including a group can be used.
  • Examples of the inorganic solid electrolyte include 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 Nitrides, halides, sulfates and the like of Li such as SiO 4 -LiI-LiOH and Li 3 PO 4 -Li 2 S-SiS 2 can be used.
  • the electrolyte of the present invention may contain at least one selected from the group consisting of pyridine, triethylphosphite, triethanolamine, cyclic ether, ethylenediamine, glyme, hexa-phosphoric triamide, Benzene derivatives, sulfur, quinone imine dyes, N-substituted oxazolidinones, N, N-substituted imidazolidines, ethylene glycol dialkyl ethers, ammonium salts, pyrrole, 2-methoxyethanol, .
  • a halogen-containing solvent such as carbon tetrachloride, ethylene trifluoride or the like may be further added to impart nonflammability.
  • carbon dioxide gas may be further added.
  • the electrolyte may be used as a liquid electrolyte or as a solid electrolyte separator.
  • the separator When used as a liquid electrolyte, the separator further includes a separation membrane made of porous glass, plastic, ceramic, or polymer as a physical separation membrane having a function of physically separating the electrode.
  • the shape of the above-described lithium secondary battery is not particularly limited and may be, for example, a jelly-roll type, a stack type, a stack-folding type (including a stack-Z-folding type), or a lamination- Stack-folding type.
  • An electrode assembly in which the positive electrode, the separator, and the negative electrode are sequentially stacked is prepared, and then inserted into a battery case. Then, an electrolyte is injected into the upper part of the case and sealed with a cap plate and a gasket to assemble a lithium secondary battery .
  • the lithium secondary battery may be classified into a cylindrical type, a square type, a coin type, a pouch type, and the like depending on the form, and may be divided into a bulk type and a thin type depending on the size.
  • the structure and the manufacturing method of these cells are well known in the art, and detailed description thereof will be omitted.
  • the slurry composition prepared above was coated on a collector (Al Foil) and dried at 50 ° C for 12 hours to prepare a positive electrode for a lithium-sulfur battery.
  • the loading amount was 3.5 mAh / cm 2
  • the porosity of the electrode was 60%.
  • the slurry composition prepared above was coated on a collector (Al Foil) and dried at 50 ° C for 12 hours to prepare a positive electrode for a lithium-sulfur battery.
  • the loading amount was 3.5 mAh / cm 2
  • the porosity of the electrode was 60%.
  • the slurry composition prepared above was coated on a collector (Al Foil) and dried at 50 ° C for 12 hours to prepare a positive electrode for a lithium-sulfur battery.
  • the loading amount was 3.5 mAh / cm 2
  • the porosity of the electrode was 60%.
  • the slurry composition prepared above was coated on a collector (Al Foil) and dried at 50 DEG C for 12 hours to prepare a positive electrode.
  • the loading amount was 3.5 mAh / cm 2
  • the porosity of the electrode was 60%.
  • the coin cell of the lithium-sulfur battery including the positive electrode, separator, negative electrode and electrolyte prepared in Examples 1 to 2 and Comparative Examples 1 and 2 was prepared as follows. Specifically, the anode was used as a 14-phi circular electrode, and a polyethylene (PE) membrane was used at 19 phi and a 150- ⁇ m lithium metal was used at 16 phi as a cathode.
  • PE polyethylene
  • the discharge capacity of the prepared coin cell was measured at a charging current of 0.1 C and a voltage of 1.6 to 2.8 V, and it was shown in FIG. 1, and the nominal voltage was measured and shown in Table 1 below.
  • iron hydroxide is randomly distributed in the anode for a lithium-sulfur battery.
  • iron hydroxide not located on the surface of the sulfur-carbon composite, It acts as a resistance component of the battery, and when the resistance is increased, an overvoltage is applied to the battery and the nominal voltage is reduced.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne un matériau actif d'électrode positive pour batterie secondaire au lithium, où le matériau actif d'électrode positive comprend : un composite soufre-carbone ; et une couche de revêtement comprenant de l'hydroxyde de fer (FeOOH) et formée sur la surface du composite soufre-carbone. Un procédé de fabrication d'un matériau actif d'électrode positive pour batterie secondaire au lithium, le procédé comprenant une étape de formation d'une couche de revêtement comprenant de l'hydroxyde de fer sur la surface d'un composite soufre-carbone par mélange à sec du composite soufre-carbone avec l'hydroxyde de fer, où le mélange à sec est un mélange à boulets ou un mélange à lames est en outre décrit.
PCT/KR2018/012795 2017-11-30 2018-10-26 Composite soufre-carbone, son procédé de préparation et batterie secondaire au lithium le comprenant WO2019107752A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020170162671A KR102268182B1 (ko) 2017-11-30 2017-11-30 황-탄소 복합체, 그의 제조방법 및 이를 포함하는 리튬 이차전지
KR10-2017-0162671 2017-11-30

Publications (1)

Publication Number Publication Date
WO2019107752A1 true WO2019107752A1 (fr) 2019-06-06

Family

ID=66664528

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2018/012795 WO2019107752A1 (fr) 2017-11-30 2018-10-26 Composite soufre-carbone, son procédé de préparation et batterie secondaire au lithium le comprenant

Country Status (2)

Country Link
KR (1) KR102268182B1 (fr)
WO (1) WO2019107752A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110492071A (zh) * 2019-08-19 2019-11-22 西京学院 内壁载有氢氧化镍和硫的空心碳球及制备方法和用途
EP3490038A4 (fr) * 2017-06-20 2020-02-12 LG Chem, Ltd. Procédé de préparation d'hydroxyde de fer (feooh), et cathode de batterie au lithium-soufre comprenant de l'hydroxyde de fer
CN116885146A (zh) * 2023-08-22 2023-10-13 大连交通大学 一种电池负极活性材料、制备方法及其应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20230072616A (ko) * 2021-11-18 2023-05-25 주식회사 엘지에너지솔루션 리튬 이차전지용 양극 및 이를 포함하는 리튬 이차전지

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005281128A (ja) * 2004-03-01 2005-10-13 Japan Storage Battery Co Ltd リチウム含有オキシ水酸化鉄の製造方法およびその製造方法で得られたリチウム含有オキシ水酸化鉄を含む電極を用いた非水電解質電気化学セル
JP2008176981A (ja) * 2007-01-17 2008-07-31 Toyota Motor Corp 全固体リチウム二次電池用電極および全固体リチウム二次電池
KR20150135961A (ko) * 2014-05-26 2015-12-04 현대자동차주식회사 이중 건식 복합화를 통한 황-탄소 복합체 제조 방법
KR20170032190A (ko) * 2015-09-14 2017-03-22 주식회사 엘지화학 리튬 황 전지용 양극, 이의 제조방법 및 이를 포함하는 리튬 황 전지
WO2017109014A1 (fr) * 2015-12-22 2017-06-29 Rhodia Operations Matière active positive pour batterie rechargeable au lithium-soufre

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101764455B1 (ko) * 2013-11-28 2017-08-03 주식회사 엘지화학 리튬-황 전지용 양극 및 이의 제조방법
KR101737217B1 (ko) 2014-09-26 2017-05-18 주식회사 엘지화학 황-탄소나노튜브 복합체, 이의 제조방법, 이를 포함하는 리튬-황 전지용 캐소드 활물질 및 이를 포함한 리튬-황 전지

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005281128A (ja) * 2004-03-01 2005-10-13 Japan Storage Battery Co Ltd リチウム含有オキシ水酸化鉄の製造方法およびその製造方法で得られたリチウム含有オキシ水酸化鉄を含む電極を用いた非水電解質電気化学セル
JP2008176981A (ja) * 2007-01-17 2008-07-31 Toyota Motor Corp 全固体リチウム二次電池用電極および全固体リチウム二次電池
KR20150135961A (ko) * 2014-05-26 2015-12-04 현대자동차주식회사 이중 건식 복합화를 통한 황-탄소 복합체 제조 방법
KR20170032190A (ko) * 2015-09-14 2017-03-22 주식회사 엘지화학 리튬 황 전지용 양극, 이의 제조방법 및 이를 포함하는 리튬 황 전지
WO2017109014A1 (fr) * 2015-12-22 2017-06-29 Rhodia Operations Matière active positive pour batterie rechargeable au lithium-soufre

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3490038A4 (fr) * 2017-06-20 2020-02-12 LG Chem, Ltd. Procédé de préparation d'hydroxyde de fer (feooh), et cathode de batterie au lithium-soufre comprenant de l'hydroxyde de fer
US11038174B2 (en) 2017-06-20 2021-06-15 Lg Chem, Ltd. Method for preparing iron oxide-hydroxide (FeOOH) and positive electrode for lithium-sulfur battery comprising iron oxide-hydroxide
CN110492071A (zh) * 2019-08-19 2019-11-22 西京学院 内壁载有氢氧化镍和硫的空心碳球及制备方法和用途
CN116885146A (zh) * 2023-08-22 2023-10-13 大连交通大学 一种电池负极活性材料、制备方法及其应用
CN116885146B (zh) * 2023-08-22 2024-02-20 大连交通大学 一种电池负极活性材料、制备方法及其应用

Also Published As

Publication number Publication date
KR102268182B1 (ko) 2021-06-22
KR20190063699A (ko) 2019-06-10

Similar Documents

Publication Publication Date Title
WO2018030616A1 (fr) Composite soufre-carbone, son procédé de préparation et batterie au lithium-soufre comprenant celui-ci
WO2020045854A1 (fr) Procédé permettant de préparer une nanostructure de carbone comprenant du disulfure de molybdène, cathode de batterie rechargeable au lithium comprenant une nanostructure de carbone comprenant du disulfure de molybdène, préparée au moyen de ce procédé, et batterie rechargeable au lithium comprenant ladite cathode
WO2019066369A2 (fr) Composite carbone-soufre, son procédé de préparation et batterie secondaire au lithium le comprenant
WO2019103326A2 (fr) Composite soufre-carbone, son procédé de préparation et batterie secondaire au lithium le comprenant
WO2019107752A1 (fr) Composite soufre-carbone, son procédé de préparation et batterie secondaire au lithium le comprenant
WO2019066366A1 (fr) Composite de titane-nanotube de carbone-soufre (tio2-x-cnt-s) et son procédé de préparation
WO2020040446A1 (fr) Matériau actif de cathode destiné à une batterie rechargeable au lithium, son procédé de fabrication et batterie rechargeable au lithium le comprenant
WO2019103409A1 (fr) Méthode de fabrication d'un composite soufre-carbone
WO2019088628A2 (fr) Composite soufre-carbone, son procédé de préparation et batterie rechargeable au lithium le comprenant
WO2019177355A1 (fr) Composite oxyde de cérium-carbone-soufre, son procédé de préparation, et électrode positive et batterie au lithium-soufre comprenant ladite électrode positive
WO2019212162A1 (fr) Liant pour batterie secondaire au lithium-soufre et batterie secondaire au lithium-soufre le comprenant
WO2019088630A2 (fr) Composite soufre-carbone et son procédé de préparation
WO2021025349A1 (fr) Anode, son procédé de fabrication et batterie secondaire la comprenant
WO2019107815A1 (fr) Liant pour la fabrication d'une électrode positive de batterie secondaire au lithium et procédé de fabrication d'électrode positive à l'aide de celui-ci
WO2020166871A1 (fr) Materiau actif cathodique pour batterie de secours au lithium
WO2021251663A1 (fr) Anode et batterie secondaire la comprenant
WO2018097695A1 (fr) Matériau actif de cathode pour pile lithium-soufre, comportant des nanoparticules de sulfure métallique, et son procédé de fabrication
WO2019083257A1 (fr) Séparateur pour batterie au lithium-soufre et batterie au lithium-soufre comprenant celui-ci
WO2019098733A1 (fr) Composite soufre-carbone, son procédé de préparation et batterie secondaire au lithium le comprenant
WO2018236060A1 (fr) Procédé de préparation d'hydroxyde de fer (feooh), et cathode de batterie au lithium-soufre comprenant de l'hydroxyde de fer
WO2020009332A1 (fr) Composite soufre-carbone, son procédé de production, et électrode positive de batterie au lithium-soufre et batterie au lithium-soufre le comprenant
WO2020067793A1 (fr) Composite soufre-carbone et son procédé de fabrication
WO2020060199A1 (fr) Procédé de préparation de sulfure de fer, cathode contenant du sulfure de fer ainsi préparé pour batterie secondaire au lithium, et batterie secondaire au lithium la comprenant
WO2019212161A1 (fr) Matériau actif de cathode pour batterie lithium-soufre et son procédé de fabrication
WO2018236046A1 (fr) Batterie au lithium-soufre

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18882706

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18882706

Country of ref document: EP

Kind code of ref document: A1