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WO2020060199A1 - 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 - Google Patents

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 Download PDF

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Publication number
WO2020060199A1
WO2020060199A1 PCT/KR2019/012089 KR2019012089W WO2020060199A1 WO 2020060199 A1 WO2020060199 A1 WO 2020060199A1 KR 2019012089 W KR2019012089 W KR 2019012089W WO 2020060199 A1 WO2020060199 A1 WO 2020060199A1
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Prior art keywords
secondary battery
lithium secondary
iron sulfide
fes
positive electrode
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English (en)
Korean (ko)
Inventor
예성지
한승훈
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LG Chem Ltd
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LG Chem Ltd
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Priority to JP2021500722A priority Critical patent/JP7098043B2/ja
Priority to EP19863940.3A priority patent/EP3806207A4/fr
Priority to CN201980045775.1A priority patent/CN112385061B/zh
Priority to US17/259,215 priority patent/US12155073B2/en
Priority claimed from KR1020190114771A external-priority patent/KR20200032660A/ko
Priority claimed from KR1020190114782A external-priority patent/KR102781564B1/ko
Publication of WO2020060199A1 publication Critical patent/WO2020060199A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/12—Sulfides
    • 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
    • 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
    • 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 method for manufacturing iron sulfide, a positive electrode for a lithium secondary battery including iron sulfide prepared therefrom, and a lithium secondary battery having the same, and more specifically, it is possible to manufacture selective and high purity iron sulfide by a simple process.
  • the present invention relates to a lithium secondary battery positive electrode including iron sulfide (FeS 2 ) capable of increasing charging and discharging efficiency and improving lifespan characteristics, and a lithium secondary battery having the same.
  • Secondary batteries unlike primary batteries that can only be discharged once, have been established as important parts of portable electronic devices since the 1990s as an electric storage device capable of continuous charging and discharging.
  • the lithium secondary battery was commercialized by Sony Japan in 1992, it has led the information age as a core component of portable electronic devices such as smart phones, digital cameras, and notebook computers.
  • lithium secondary batteries have expanded their application areas, and in mid-sized batteries to be used in fields such as cleaners, power tools, electric bicycles, and electric scooters, electric vehicles (EVs) and hybrid electric vehicles (hybrid electric vehicles) ; HEV), Plug-in hybrid electric vehicle (PHEV), various robots, and large-capacity batteries used in fields such as electric storage systems (ESS), demand at high speed Is increasing.
  • EVs electric vehicles
  • PHEV Plug-in hybrid electric vehicle
  • ESS electric storage systems
  • lithium secondary batteries which have the best characteristics among the secondary batteries to date, have several problems to be actively used in transportation equipment such as electric vehicles and PHEVs, and the biggest problem is the limitation of capacity.
  • the lithium secondary battery is basically composed of materials such as a positive electrode, an electrolyte, and a negative electrode, and among them, since the positive and negative electrode materials determine the capacity of the battery, the lithium secondary battery has a capacity due to the material limitations of the positive and negative electrodes. Is limited by. In particular, the secondary battery to be used in applications such as electric vehicles and PHEVs must be used for as long as possible after one charge, so its discharge capacity is very important.
  • the capacity limitation of the lithium secondary battery is difficult to completely solve due to the structure and material limitations of the lithium secondary battery despite many efforts. Therefore, in order to fundamentally solve the capacity problem of the lithium secondary battery, it is required to develop a new concept of secondary battery that goes beyond the existing secondary battery concept.
  • Lithium-sulfur secondary batteries exceed the capacity limits determined by the intercalation reaction of the lithium ion layered metal oxide and graphite into the basic principle of the existing lithium secondary battery, and replace transition metals and reduce costs. It is a new high-capacity, low-cost battery system that can be imported.
  • a lithium-sulfur secondary battery is a lithium ion and the sulfur conversion (conversion) reaction at the anode - the theoretical capacity resulting from (S 8 + 16Li + + 16e ⁇ 8Li 2 S) reached 1,675 mAh / g anode is lithium metal (theoretical capacity: 3,860 mAh / g) for ultra-high capacity of the battery system.
  • the discharge voltage is about 2.2 V, it theoretically represents an energy density of 2,600 Wh / kg based on the amount of the positive and negative electrode active materials. This is a value that is 6 to 7 times higher than the theoretical energy density of 400 Wh / kg, which is a commercial lithium secondary battery (LiCoO 2 / graphite) using a layered metal oxide and graphite.
  • Lithium-sulfur secondary batteries have been attracting attention as new high-capacity, eco-friendly, and low-cost lithium secondary batteries since it is known that the performance of batteries can be dramatically improved through the formation of nanocomposites around 2010. Is being made.
  • the particle size is several tens of nanometers. It is necessary to reduce the size to the following and surface treatment with a conductive material. To this end, various chemicals (melt impregnation with a nano-sized porous carbon nanostructure or metal oxide structure), a physical method (high energy ball milling), etc. are reported. Is becoming.
  • Li 2 S 8 and Li 2 S 4 which are long-chain chains, have properties that are easily dissolved in a common electrolyte used in lithium ion batteries. When this reaction occurs, not only the reversible anode capacity is greatly reduced, but also the dissolved lithium polysulfide diffuses to the cathode, causing various side reactions.
  • Lithium polysulfide in particular, causes a shuttle reaction during the charging process, which causes the charging capacity to continue to increase and the charge / discharge efficiency rapidly decreases.
  • various methods have been proposed to solve these problems, and can be largely divided into a method of improving the electrolyte, a method of improving the surface of the cathode, and a method of improving the properties of the anode.
  • the method of improving the electrolyte uses a new electrolyte such as a functional liquid electrolyte, a polymer electrolyte, and an ionic liquid of a new composition to suppress the dissolution of polysulfide into the electrolyte or to control the dispersion rate to the cathode through adjustment of viscosity, etc. It is a method to suppress the shuttle reaction as much as possible by controlling.
  • a new electrolyte such as a functional liquid electrolyte, a polymer electrolyte, and an ionic liquid of a new composition to suppress the dissolution of polysulfide into the electrolyte or to control the dispersion rate to the cathode through adjustment of viscosity, etc. It is a method to suppress the shuttle reaction as much as possible by controlling.
  • Electrolyte additives such as LiNO 3 are added to the surface of the lithium anode to form oxide films such as Li x NO y and Li x SO y .
  • SEI solid-electrolyte interphase
  • a method of improving the properties of the anode includes a method of forming a coating layer on the surface of the anode particle or adding a porous material capable of catching the dissolved polysulfide to prevent the dissolution of polysulfide.
  • a method of coating the surface of a positive electrode structure containing, a method of coating the surface of a positive electrode structure with a metal oxide that conducts lithium ions, and a positive electrode having a large specific surface area and large pores capable of absorbing large amounts of lithium polysulfide.
  • the iron precursor and the sulfur precursor are mixed and heat-treated, but the high-purity iron sulfide is selectively controlled by controlling the heat treatment temperature and process time. It was confirmed that it can be produced.
  • an object of the present invention is to provide a method for manufacturing iron sulfide, which is a positive electrode additive for a lithium secondary battery of high purity through a simple process.
  • iron sulfide (FeS 2 ) produced by the above manufacturing method was introduced into the positive electrode of the lithium secondary battery. As a result, it was confirmed that the battery performance of the lithium secondary battery can be improved by solving the above problems, thereby completing the present invention.
  • another object of the present invention is to provide a positive electrode additive for a lithium secondary battery capable of solving the problem caused by lithium polysulfide.
  • Another object of the present invention is to provide a lithium secondary battery having the positive electrode having improved life characteristics of the battery.
  • the present invention (1) mixing the iron precursor and the sulfur precursor to form a mixture; And (2) heat-treating the mixture in an inert gas atmosphere; provides a method for producing iron sulfide (FeS 2 ).
  • the present invention as a positive electrode for a lithium secondary battery comprising an active material, a conductive material and a binder, the positive electrode provides a positive electrode for a lithium secondary battery containing iron sulfide (FeS 2 ).
  • FeS 2 iron sulfide
  • the lithium secondary battery positive electrode cathode; A separator interposed between the anode and the cathode; And electrolyte; provides a lithium secondary battery comprising a.
  • the lithium secondary battery provided with the positive electrode containing the iron sulfide (FeS 2 ) does not cause a reduction in the capacity of sulfur, so it is possible to implement a high-capacity battery and stably apply sulfur with high loading, thereby improving the overvoltage of the battery. And there is no problem of short circuit, heat generation, etc. of the battery, thereby improving the battery stability.
  • the lithium secondary battery has an advantage of high charging and discharging efficiency of the battery and improving life characteristics.
  • Figure 3 shows the X-ray diffraction analysis (XRD) results of iron sulfide (FeS 2 ) according to Preparation Example 1 of the present invention.
  • Figure 4 shows the X-ray diffraction analysis (XRD) results of iron sulfide (FeS 2 ) according to Preparation Example 2 of the present invention.
  • Figure 5 shows the X-ray diffraction analysis (XRD) comparison results of iron sulfide (FeS 2 ) according to Preparation Example 1 and Comparative Preparation Example 1 of the present invention.
  • composite refers to a substance that combines two or more materials to form physically and chemically different phases and express more effective functions.
  • the lithium secondary battery is manufactured by using a material capable of intercalation / deintercalation of lithium ions as a negative electrode and a positive electrode, and charging an organic electrolyte or a polymer electrolyte between the negative electrode and the positive electrode, and lithium ions are inserted at the positive and negative electrodes.
  • an electrochemical device that generates electrical energy by oxidation / reduction reaction when desorption and according to one embodiment of the present invention, the lithium secondary battery is lithium-sulfur containing 'sulfur' as an electrode active material of a positive electrode. It can be a battery.
  • the present invention relates to a method for manufacturing iron sulfide (FeS 2 ), and specifically, it can be produced as iron sulfide having a shape and physical properties that can improve the discharge capacity and life characteristics of a battery by applying it as a positive electrode additive for a lithium secondary battery. It's about how.
  • the present invention complements the disadvantages of the positive electrode for a lithium secondary battery, and provides a positive electrode for a lithium secondary battery with improved problems of continuous reactivity of an electrode due to dissolution and shuttle phenomenon of lithium polysulfide and a problem of reduction in discharge capacity.
  • the positive electrode for a lithium sulfur-cell provided in the present invention is characterized by including an active material, a conductive material, and a binder, and even iron sulfide (FeS 2 ) as a positive electrode additive.
  • the iron sulfide (FeS 2 ) is included in the positive electrode of the lithium secondary battery in the present invention, and lithium polysulfide is transferred to the negative electrode by adsorbing lithium polysulfide, thereby reducing the problem of reducing the life of the lithium secondary battery and lithium By suppressing the reduced reactivity due to polysulfide, it is possible to increase the discharge capacity of the lithium secondary battery including the positive electrode and improve the life of the battery.
  • the method for manufacturing iron sulfide (FeS 2 ) according to the present invention includes (1) mixing an iron precursor and a sulfur precursor to form a mixture, and (2) heat treating the mixture in an inert gas atmosphere.
  • the iron precursor according to the present invention means a material capable of forming iron sulfide (FeS 2 ) by reacting with a sulfur precursor, and an example of a preferred iron precursor is iron nitrate represented by Fe (NO 3 ) 3 ⁇ 9H 2 O, ⁇ It may be iron hydroxide represented by -FeOOH or a combination thereof.
  • iron nitrate Fe (NO 3 ) 3 ⁇ 9H 2 O as the iron precursor
  • the sulfur precursors include thiourea (CH 4 N 2 S), ammonium thiosulfate ((Ammonium Thiosulfate, (NH 4 ) 2 S 2 O 3 ), sulfur (S), etc., but in the case of ammonium thiosulfate, the present invention According to the manufacturing method according to the method, a side reaction may occur in which NH 4 Fe (SO 4 ) 2 and the like are generated instead of complete sulfurization, and when sulfur (S) itself is used as a sulfur precursor, iron to be described later Even when the reaction proceeds with a molar ratio of (Fe) and sulfur (S) of 1: 8 or more, iron sulfide (FeS 2 ) of uniform components may not be generated, such as Fe 7 S 8 and FeS 2 being mixed.
  • the iron precursor and the sulfur precursor may be mixed by a method known to those skilled in the art.
  • the mixing ratio of the iron precursor and the sulfur precursor may be a molar ratio of iron (Fe) and sulfur (S) contained in the iron precursor and the sulfur precursor is 1: 8 or more, preferably 1:10 or more. If the molar ratio of sulfur is less than the above range, a side reaction of Fe 7 S 8 or the like may occur through a heat treatment process to be described later due to insufficient sulfur content, which may cause a side reaction with the above-described binder, and thus the above range It is desirable to maintain the mixing ratio of sulfur.
  • the present invention includes the step of heat-treating the mixture of step (1) in an inert gas atmosphere.
  • an iron precursor and a sulfur precursor react to produce iron sulfide (FeS 2 ).
  • the heat treatment may be performed at 400 to 600 ° C, preferably 400 to 500 ° C.
  • the heating rate of the heat treatment may be controlled between 5 and 20 ° C per minute. If the temperature increase rate exceeds 20 ° C / min, the decomposition rate of the sulfur precursor, which is a reactant, is excessively high, so that the amount of sulfur reacting with the iron precursor may decrease, and as a result, Fe 7 S 8 is not the desired iron sulfide (FeS 2 ). There is a problem that can be produced in the form. In addition, if the heating rate is less than 5 ° C / min, there may be a problem that the production time of the desired product may be too long, so it is appropriately adjusted within the above range.
  • the heat treatment may be performed for 1 to 3 hours in the above temperature range, preferably 1 to 2 hours. If the heat treatment temperature is less than 400 ° C or shorter than the heat treatment time, the iron precursor and the sulfur precursor may not react sufficiently to produce desired iron sulfide (FeS 2 ). In addition, when the heat treatment temperature exceeds 600 ° C or longer than the heat treatment time, the size of the generated iron sulfide (FeS 2 ) particles may increase or, unlike the desired iron sulfide (FeS 2 ), unnecessary oxides may be generated. Therefore, since it may be difficult to synthesize iron sulfide (FeS 2 ) of desired physical properties according to the present invention, it is appropriately adjusted within the temperature and time in the above range.
  • the heat treatment in step (3) may be performed in an inert gas atmosphere.
  • the inert gas atmosphere may be performed under (i) an inert gas atmosphere in which the gas inside the reactor is replaced with an inert gas, or (ii) in a state where the inert gas is continuously introduced to continuously replace the gas in the reactor.
  • the flow rate of the inert gas may be 1 to 500 mL / min, specifically 10 to 200 mL / min, and more specifically 50 to 100 mL / min.
  • the inert gas may be selected from the group consisting of nitrogen, argon, helium, and mixtures thereof, and preferably nitrogen.
  • the iron sulfide (FeS 2 ) prepared by the above-described manufacturing method may have a crystallinity of an average particle size of several hundreds nm to several ⁇ m, for example, 0.1 to 10 ⁇ m. If the average particle diameter exceeds 10 ⁇ m, it may not fit well with other electrode materials of the lithium secondary battery, and when the same amount is added, the performance improvement effect of the battery compared to iron sulfide (FeS 2 ) having a relatively small average particle diameter Can be insignificant.
  • iron hydroxide ⁇ -FeOOH
  • FeS 2 iron sulfide containing plate-shaped particles having an average particle diameter of several hundred nm to several ⁇ m may be prepared, and in this case, as described above.
  • the iron sulfide (FeS 2 ) produced by the above-described manufacturing method can effectively adsorb lithium polysulfide eluted during charging and discharging of a lithium secondary battery, and is suitable as a cathode material of a lithium secondary battery. It does not cause the performance of the battery can be improved.
  • the present invention provides an anode for a lithium secondary battery including an active material, a conductive material, and a binder, the anode comprising a lithium sulfide (FeS 2 ) produced through the above-described manufacturing method.
  • a lithium sulfide FeS 2
  • the positive electrode of the lithium secondary battery may include a current collector and an electrode active material layer formed on at least one surface of the current collector, and the electrode active material layer may include a base solid content including an active material, a conductive material, and a binder.
  • the current collector it may be preferable to use aluminum, nickel or the like having excellent conductivity.
  • the iron sulfide (FeS 2 ) may be included in an amount of 0.1 to 15 parts by weight based on 100 parts by weight of the base solid content including the active material, the conductive material, and the binder, and specifically 1 to 15 parts by weight, preferably 5 to 10 parts by weight. If it is less than the lower limit of the numerical range, the adsorption effect of polysulfide may be insignificant, and if it exceeds the upper limit, the capacity of the electrode is reduced, which is not preferable.
  • the iron sulfide (FeS 2) can be used for the iron sulfide (FeS 2) prepared by the method presented in this invention.
  • S 8 elemental sulfur
  • the positive electrode for a lithium secondary battery according to the present invention may preferably include an active material of a sulfur-carbon composite, and since the sulfur material is not electrically conductive alone, it can be used in combination with a conductive material.
  • the addition of iron sulfide (FeS 2 ) according to the present invention does not affect the maintenance of this sulfur-carbon composite structure.
  • the sulfur-carbon composite may have a sulfur content of 60 to 90 parts by weight based on 100 parts by weight of the sulfur-carbon composite, and preferably 70 to 75 parts by weight. If the content of sulfur is less than 60 parts by weight, the content of the carbon material of the sulfur-carbon composite increases relatively, and as the content of carbon increases, the specific surface area increases, so that the amount of binder added during slurry production must be increased. Increasing 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 battery performance.
  • the sulfur or sulfur compounds that are not combined with the carbon material may be difficult to directly participate in the electrode reaction due to aggregation or re-eluting to the surface of the carbon material, making it difficult to directly participate in the electrode reaction. Adjust accordingly.
  • the carbon of the sulfur-carbon composite according to the present invention 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, and its shape is spherical, rod-shaped, needle-shaped, plate-shaped, tubular or bulk-type, and can be used without limitation as long as it is commonly used in lithium secondary batteries.
  • the active material is preferably 50 to 95 parts by weight of 100 parts by weight of the base solid content, more preferably 70 parts by weight or less. If the active material is included below the above range, it is difficult to sufficiently exhibit the reaction of the electrode, and even if it is included above the above range, the amount of other conductive materials and binders is relatively insufficient, so that it is difficult to exert sufficient electrode reaction within the above range. It is desirable to determine the appropriate content.
  • the conductive material is a material that electrically connects the electrolyte and the positive electrode active material to serve as a path for electrons to move from the current collector to sulfur, and to change the battery chemically. It is not particularly limited as long as it has porosity and conductivity without causing it.
  • Graphite-based materials such as KS6; Carbon blacks such as super P (Super-P), carbon black, denka black, acetylene black, ketjen black, channel black, furnace black, lamp black, and summer black; Carbon derivatives such as fullerene; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder, and nickel powder; Alternatively, conductive polymers such as polyaniline, polythiophene, polyacetylene, and polypyrrole may be used alone or in combination.
  • the conductive material is preferably configured to constitute 1 to 10 parts by weight of 100 parts by weight of the base solid content, preferably 5 parts by weight or less. If the content of the conductive material included in the electrode is less than the above range, a portion of the electrode that does not react increases in the sulfur, and eventually, a capacity decrease occurs, and if it exceeds the above range, high efficiency discharge characteristics and charge and discharge cycle life are adversely affected. It is desirable to determine the appropriate content within the above-described range.
  • the binder is a material containing a slurry composition of a base solid that forms a positive electrode to adhere well to a current collector, and is a material that is well soluble in a solvent and can well constitute a conductive network between a positive electrode active material and a conductive material. use.
  • binder any binder known in the art can be used, unless otherwise specified, preferably poly (vinyl) acetate, polyvinyl alcohol, polyethylene oxide, polyvinyl pyrrolidone, alkylated polyethylene oxide, crosslinked polyethylene oxide , Polyvinyl ether, poly (methyl methacrylate), polyvinylidene fluoride (PVdF), polyhexafluoropropylene, copolymer of polyvinylidene fluoride (trade name: Kynar), poly (ethyl acrylate), poly Siloxane groups such as tetrafluoroethylene polyvinyl chloride, polytetrafluoroethylene, polyacrylonitrile, polyvinylpyridine, polystyrene, carboxymethyl cellulose, polydimethylsiloxane, styrene-butadiene rubber, acrylonitrile-butadiene Rubber, rubber-based binder containing styrene-isoprene rubber, polyester
  • the binder is made to constitute 1 to 10 parts by weight of 100 parts by weight of the base composition included in the electrode, preferably 5 parts by weight. If the content of the binder resin is less than the above range, the physical properties of the positive electrode may deteriorate and the positive electrode active material and the conductive material may drop off. If the content exceeds the above range, the ratio of the active material and the conductive material in the positive electrode may be relatively reduced to decrease the battery capacity. Therefore, it is preferable to determine an appropriate content within the above-described range.
  • the anode including iron sulfide (FeS 2 ) and the base solid content may be prepared according to a conventional method.
  • a mixture of a solvent, a binder, a conductive material, and a dispersant may be mixed with a positive electrode active material, if necessary, to prepare a slurry, and then coated (coated) on a current collector of a metal material, compressed, and dried to produce a positive electrode.
  • iron sulfide FeS 2
  • the obtained solution is mixed with an active material, a conductive material, and a binder to obtain a slurry composition for positive electrode formation.
  • the slurry composition is coated on a current collector and then dried to complete an anode.
  • compression molding may be performed on the current collector.
  • the method for coating the slurry for example, doctor blade coating, dip coating, gravure coating, slit die coating, spin coating coating, comma coating, bar coating, reverse roll coating, screen coating, and cap coating.
  • the solvent one capable of uniformly dispersing the positive electrode active material, the binder, and the conductive material, as well as those capable of easily dissolving iron sulfide (FeS 2 ) are used.
  • water is most preferable as the water-based solvent, and the water may be DW (Distilled Water) distilled second, or DIW (Deionzied Water) distilled third.
  • the present invention is not limited thereto, and if necessary, a lower alcohol that can be easily mixed with water may be used. Examples of the lower alcohol include methanol, ethanol, propanol, isopropanol, and butanol. Preferably, they can be used by mixing with water.
  • the positive electrode includes a current collector and an electrode active material layer formed on at least one surface of the current collector, and the electrode active material layer includes an active material, a conductive material, a binder, and iron sulfide (FeS 2 ) according to the present invention
  • the porosity of the electrode active material layer may be 60 to 75%, specifically 60 to 70%, preferably 60 to 65%.
  • porosity refers to the ratio of the volume occupied by the pores to the total volume in a certain structure, uses% as its unit, is used interchangeably with terms such as porosity, porosity, etc. You can.
  • the measurement of the porosity is not particularly limited, and according to an embodiment of the present invention, for example, the size (micro) by BET (Brunauer-Emmett-Teller) measurement method or mercury penetration method (Hg porosimeter) And meso pore volume.
  • the porosity of the electrode active material layer is less than 60%, the filling degree of the base solids containing the active material, the conductive material, and the binder is too high, and sufficient electrolyte solution capable of exhibiting ionic conductivity and / or electrical conduction between the active materials is obtained. Since it cannot be maintained, the output characteristics or cycle characteristics of the battery may be deteriorated, and the overvoltage and discharge capacity of the battery are severely reduced, so that the effect of including iron sulfide (FeS 2 ) according to the present invention may not be properly expressed. There is.
  • the porosity may be performed by a method selected from the group consisting of a hot press method, a roll press method, a plate press method and a roll laminate method.
  • the positive electrode may have a loading amount of sulfur per unit area of 3 to 7 mAh / cm 2 , preferably 4 to 6 mAh / cm 2 .
  • the present invention includes a high loading amount of 4 to 6 mAh / cm 2 including iron sulfide (FeS 2 ) at the positive electrode.
  • FeS 2 iron sulfide
  • the present invention provides a lithium secondary battery including a positive electrode for a lithium secondary battery, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte.
  • the negative electrode, the separator and the electrolyte may be composed of common materials that can be used in lithium secondary batteries.
  • the negative electrode is a material capable of reversibly intercalating or deintercalating lithium ions (Li + ) as an active material, a material capable of reversibly forming a lithium-containing compound by reacting with lithium ions, lithium metal Alternatively, a lithium alloy can be used.
  • the material capable of reversibly occluding or releasing the lithium ion (Li + ) 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 (Li + ) 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 negative electrode may further include a binder selectively together with the negative electrode active material.
  • the binder plays the role of pasting the negative electrode active material, mutual adhesion between the active materials, adhesion between the active material and the current collector, and buffering effects for expansion and contraction of the active material.
  • the binder is the same as described above.
  • the negative electrode may further include a current collector for supporting the negative electrode active layer including a negative electrode active material and a binder.
  • the current collector may be specifically selected from the group consisting of copper, aluminum, stainless steel, titanium, silver, palladium, nickel, alloys thereof, and combinations thereof.
  • the stainless steel may be surface treated with carbon, nickel, titanium or silver, and an aluminum-cadmium alloy may be used as the alloy.
  • calcined carbon, a non-conductive polymer surface-treated with a conductive agent, or a conductive polymer may be used.
  • the negative electrode may be a thin film of lithium metal.
  • the separator uses a material that allows lithium ions to be transported between the positive electrode and the negative electrode while insulating or insulating them from each other, but can be used without particular limitation as long as it is used as a separator in a lithium secondary battery. It is preferable to have a low resistance and excellent electrolyte-moisturizing ability.
  • a porous, non-conductive or insulating material may be used, such as an independent member such as a film, or a coating layer added to the positive electrode and / or the negative electrode.
  • a porous polymer film made of a polyolefin-based polymer such as ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymer, and ethylene / methacrylate copolymer is used alone. It may be used as or by laminating them, or a conventional porous non-woven fabric, for example, a high-melting point glass fiber, a polyethylene terephthalate fiber, or the like may be used, but is not limited thereto.
  • a polyolefin-based polymer such as ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymer, and ethylene / methacrylate copolymer is used alone. It may be used as or by laminating them, or a conventional porous non-woven fabric, for example, a high-melting point glass fiber, a polyethylene
  • the electrolyte is a non-aqueous electrolyte containing a lithium salt, and is composed of a lithium salt and an electrolyte.
  • a non-aqueous organic solvent, an organic solid electrolyte, and an inorganic solid electrolyte are used.
  • the lithium salt is a material that can be easily dissolved in a non-aqueous organic solvent, for example, LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiB (Ph) 4, LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2, LiAsF 6, LiSbF 6, LiAlCl 4, LiSO 3 CH 3, LiSO 3 CF 3, LiSCN, LiC (CF 3 SO 2) 3, LiN (CF 3 SO 2) 2, chloroborane lithium, lower aliphatic It may be one or more selected from the group consisting of lithium carboxylate, lithium 4-phenyl borate and imide.
  • the concentration of the lithium salt is preferably 0.2 to 2M, 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 field of lithium batteries. It may be 0.6 to 2M, and more preferably 0.7 to 1.7M. If the concentration of the lithium salt is less than the above range, the conductivity of the electrolyte may be lowered to degrade the electrolyte performance, and if it exceeds the above range, the viscosity of the electrolyte may increase and mobility of lithium ions (Li + ) may be reduced, so within the above range. It is desirable to select an appropriate concentration.
  • the non-aqueous organic solvent is a material capable of dissolving the lithium salt well, and preferably 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane, and dioxolane (Dioxolane, DOL) ), 1,4-dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), methylpropyl carbonate (MPC), ethyl propyl carbonate , Dipropyl carbonate, butyl ethyl carbonate, ethyl propanoate (EP), toluene, xylene, dimethyl ether (DME), diethyl ether, triethylene glycol monomethyl ether (TEGME), Diglyme, tetraglyme, hexamethyl phosphoric triamide, gamma-buty
  • the organic solid electrolyte is a polyethylene derivative, a polyethylene oxide derivative, a polypropylene oxide derivative, a phosphoric acid ester polymer, a poly edgeation lysine, polyester sulfide, polyvinyl alcohol, polyvinylidene fluoride, ionic Polymers containing dissociation groups and the like can be used.
  • 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 SiO 4 -LiI-LiOH, Li 3 PO4-Li 2 S-SiS 2 and other nitrides of Li, halide, sulfate, and the like can be used.
  • the shape of the lithium secondary battery as described above 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 type, preferably It may be a stack-folding type.
  • the electrode assembly After preparing the electrode assembly in which the positive electrode, the separator, and the negative electrode are sequentially stacked, they are placed in a battery case, and then an electrolyte is injected into the upper portion of the case and sealed with a cap plate and gasket to assemble to produce a lithium secondary battery. .
  • the lithium secondary battery may be classified into a cylindrical shape, a square shape, a coin shape, a pouch shape, and the like, and may be divided into a bulk type and a thin film type according to the size.
  • the structure and manufacturing method of these batteries are well known in the art, so detailed descriptions thereof are omitted.
  • the lithium secondary battery according to the present invention configured as described above, contains iron sulfide (FeS 2 ) to adsorb lithium polysulfide generated during charging and discharging of the lithium secondary battery, thereby increasing the reactivity of the anode of the lithium secondary battery and applying it
  • the lithium secondary battery has an effect of increasing discharge capacity and life.
  • the iron sulfide (FeS 2 ) according to the present invention is included, there is an advantage that the overload is improved and the discharge capacity is improved even in the electrode having high loading and low porosity.
  • Iron nitrate hydrate Fe (NO 3 ) 3 ⁇ 9H 2 O
  • Sigma-Aldrich Iron nitrate hydrate (Fe (NO 3 ) 3 ⁇ 9H 2 O)
  • the mixture was treated with argon gas at a flow rate of 100 mL / min and heat-treated at 400 ° C for 1.5 hours. At this time, the rate of temperature increase for heat treatment was 10 ° C per minute.
  • Iron sulfide (FeS 2 ) was prepared through the heat treatment.
  • Iron sulfide with plate-like particles was performed in the same manner as in Preparation Example 1, except that 0.42 g of iron hydroxide ( ⁇ -FeOOH) was used instead of iron nitrate hydrate (Fe (NO 3 ) 3 ⁇ 9H 2 O) as an iron precursor ( FeS 2 ) was prepared.
  • FIG. 4 is a graph showing the results of XRD analysis for iron sulfide (FeS 2 ) prepared in Preparation Example 2.
  • iron nitrate hydrates Fe (NO 3 ) 3 ⁇ 9H 2 O
  • iron hydroxides ⁇ -FeOOH
  • FeS 2 iron sulfide
  • the prepared slurry composition was coated on a current collector (Al Foil), dried at 50 ° C. for 12 hours, and pressed with a roll press machine to prepare a positive electrode. At this time, the loading amount was 5.3 mAh / cm 2 , and the porosity of the electrode was set to 68%.
  • a coin cell of a lithium secondary battery including an anode, a cathode, a separator, and an electrolyte prepared according to the above was prepared as follows. Specifically, the positive electrode was punched and used as a 14 phi circular electrode, and a polyethylene (PE) separator was punched to 19 phi, and a 150 um lithium metal was punched to 16 phi as the negative electrode.
  • PE polyethylene
  • the lithium secondary battery was performed in the same manner as in Example 1, except that iron sulfide (FeS 2 ) having plate-like particles prepared in Preparation Example 2 was used instead of iron sulfide (FeS 2 ) prepared in Preparation Example 1. It was prepared (ie, electrode porosity is 68%).
  • FeS 2 iron-carbon composite
  • the prepared slurry composition was coated on a current collector (Al Foil) and dried at 50 ° C. for 12 hours to prepare a positive electrode.
  • the loading amount was 5.3 mAh / cm 2
  • the porosity of the electrode was 68%.
  • a coin cell of a lithium secondary battery including an anode, a cathode, a separator, and an electrolyte prepared according to the above was prepared as follows. Specifically, the positive electrode was punched and used as a 14 phi circular electrode, and a polyethylene (PE) separator was punched to 19 phi, and a 150 um lithium metal was punched to 16 phi as the negative electrode.
  • PE polyethylene
  • a lithium secondary battery was manufactured in the same manner as in Comparative Example 2, except that the porosity of the electrode was changed from 68% to 62% by rolling the electrode.
  • FIG. 8 and 9 is a graph showing the discharge capacity measurement results of the lithium secondary battery prepared according to an embodiment and a comparative example of the present invention.
  • Example 1 in which iron sulfide (FeS 2 ) prepared in Preparation Example 1 was added to the positive electrode
  • Example 2 in which iron sulfide (FeS 2 ) prepared in Preparation Example 2 was added to the positive electrode. It was confirmed that the overvoltage of the battery was improved and the initial discharge capacity was further increased as compared with the conventional comparative example 1. Therefore, it was found that the iron sulfide according to the present invention has an effect of increasing the initial discharge capacity and improving the overvoltage of the lithium secondary battery.
  • Example 2 using iron hydroxide ( ⁇ -FeOOH) as an iron precursor of iron sulfide as shown in FIG. 8, using iron nitrate hydrate (Fe (NO 3 ) 3 ⁇ 9H 2 O) as an iron precursor of iron sulfide
  • iron nitrate hydrate Fe (NO 3 ) 3 ⁇ 9H 2 O
  • iron sulfide FeS 2
  • FeS 2 iron sulfide
  • ⁇ -FeOOH iron sulfide
  • Fe (NO 3 ) 3 ⁇ 9H 2 O iron precursor

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Abstract

L'invention concerne : un procédé de préparation de sulfure de fer (FeS2), qui est sélectif pour du sulfure de fer de haute pureté et qui permet de le préparer dans un processus simple ; une cathode contenant du sulfure de fer (FeS2) pour une batterie secondaire au lithium, le sulfure de fer (FeS2) adsorbant du polysulfure de lithium généré pendant les processus de charge et de décharge de la batterie secondaire au lithium, ce qui permet à la batterie d'augmenter son efficacité de charge et de décharge et d'améliorer ses caractéristiques de durée de vie ; ainsi qu'une batterie secondaire au lithium la comprenant.
PCT/KR2019/012089 2018-09-18 2019-09-18 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 Ceased WO2020060199A1 (fr)

Priority Applications (4)

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JP2021500722A JP7098043B2 (ja) 2018-09-18 2019-09-18 硫化鉄の製造方法、これより製造された硫化鉄を含むリチウム二次電池用正極及びこれを備えたリチウム二次電池
EP19863940.3A EP3806207A4 (fr) 2018-09-18 2019-09-18 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
CN201980045775.1A CN112385061B (zh) 2018-09-18 2019-09-18 硫化铁的制备方法、包含由其制备的硫化铁的锂二次电池用正极、和包含所述正极的锂二次电池
US17/259,215 US12155073B2 (en) 2018-09-18 2019-09-18 Method for preparing iron sulfide, cathode comprising iron sulfide prepared thereby for lithium secondary battery, and lithium secondary battery comprising same

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KR20180111788 2018-09-18
KR10-2018-0111792 2018-09-18
KR20180111792 2018-09-18
KR10-2018-0111788 2018-09-18
KR1020190114771A KR20200032660A (ko) 2018-09-18 2019-09-18 황화철의 제조방법
KR1020190114782A KR102781564B1 (ko) 2018-09-18 2019-09-18 황화철을 포함하는 리튬 이차전지용 양극 및 이를 구비한 리튬 이차전지
KR10-2019-0114782 2019-09-18
KR10-2019-0114771 2019-09-18

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JPWO2022254962A1 (fr) * 2021-06-02 2022-12-08
JP2023542192A (ja) * 2021-06-15 2023-10-05 エルジー エナジー ソリューション リミテッド リチウム－硫黄電池用正極及びこれを含むリチウム－硫黄電池
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
CN118743058A (zh) * 2022-03-31 2024-10-01 住友橡胶工业株式会社 硫系活性材料、电极、锂离子二次电池及其制备方法
CN118811779A (zh) * 2024-09-19 2024-10-22 洛阳理工学院 一种单相三元铁基硫硒化物复合材料及其制备方法和应用

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2022254962A1 (fr) * 2021-06-02 2022-12-08
WO2022254962A1 (fr) * 2021-06-02 2022-12-08 住友ゴム工業株式会社 Matériau actif à base de soufre, électrode, batterie rechargeable au lithium-ion et procédé de production
JP2023542192A (ja) * 2021-06-15 2023-10-05 エルジー エナジー ソリューション リミテッド リチウム－硫黄電池用正極及びこれを含むリチウム－硫黄電池
JP7589339B2 (ja) 2021-06-15 2024-11-25 エルジー エナジー ソリューション リミテッド リチウム－硫黄電池用正極及びこれを含むリチウム－硫黄電池
CN118743058A (zh) * 2022-03-31 2024-10-01 住友橡胶工业株式会社 硫系活性材料、电极、锂离子二次电池及其制备方法
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
CN118811779A (zh) * 2024-09-19 2024-10-22 洛阳理工学院 一种单相三元铁基硫硒化物复合材料及其制备方法和应用

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