WO2018236060A1 - Procédé de préparation d'hydroxyde de fer (feooh), et cathode de batterie au lithium-soufre comprenant de l'hydroxyde de fer - Google Patents

Procédé de préparation d'hydroxyde de fer (feooh), et cathode de batterie au lithium-soufre comprenant de l'hydroxyde de fer Download PDF

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WO2018236060A1
WO2018236060A1 PCT/KR2018/006003 KR2018006003W WO2018236060A1 WO 2018236060 A1 WO2018236060 A1 WO 2018236060A1 KR 2018006003 W KR2018006003 W KR 2018006003W WO 2018236060 A1 WO2018236060 A1 WO 2018236060A1
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Prior art keywords
feooh
iron hydroxide
lithium
sulfur
sulfur battery
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PCT/KR2018/006003
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English (en)
Korean (ko)
Inventor
한승훈
손권남
양두경
이동욱
문정미
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주식회사 엘지화학
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Priority claimed from KR1020180059572A external-priority patent/KR102229454B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201880003777.XA priority Critical patent/CN109792039B/zh
Priority to EP18821299.7A priority patent/EP3490038A4/fr
Priority to JP2019505215A priority patent/JP6758679B2/ja
Priority to US16/324,249 priority patent/US11038174B2/en
Publication of WO2018236060A1 publication Critical patent/WO2018236060A1/fr

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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
    • C01G49/02—Oxides; Hydroxides
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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 process for preparing iron hydroxide (FeOOH) applicable as a cathode additive for a lithium-sulfur battery, a lithium-sulfur battery anode containing iron hydroxide (FeOOH) as a cathode additive, - about sulfur cells.
  • FeOOH iron hydroxide
  • the secondary battery is an electric storage device capable of continuous charging and discharging, and has become an important electronic component of portable electronic devices since 1990's.
  • the lithium ion secondary battery was commercialized by Sony Japan in 1992, it has been leading the information age as a core component of portable electronic devices such as smart phones, digital cameras, and notebook computers.
  • a lithium ion secondary battery has been widely used as an electric vehicle (EV), hybrid electric vehicle (hybrid electric vehicle), and the like in a mid-sized battery for use in fields such as power supplies for cleaners, power tools, electric bicycles, to high-capacity batteries for applications such as HEVs, plug-in hybrid electric vehicles (PHEVs), robots and large electric power storage systems (ESS) Demand is increasing.
  • EV electric vehicle
  • hybrid electric vehicle hybrid electric vehicle
  • ESS large electric power storage systems
  • lithium secondary batteries having the most excellent characteristics among the secondary batteries described so far have some problems in being actively used in transporting apparatuses such as electric vehicles and PHEVs, and the biggest problem is capacity.
  • Lithium secondary batteries are basically composed of materials such as anodes, electrolytes, and cathodes. Among them, the anode and cathode materials determine the capacity of the battery. Therefore, the lithium ion secondary battery is limited by the material limitations of the anode and the cathode Capacity. In particular, a secondary battery to be used in applications such as electric vehicles and PHEVs must be used for as long as possible after a single charge, so that the discharge capacity of the secondary battery is very important.
  • One of the biggest constraints to the sale of electric vehicles is that the distance traveled after one charge is much shorter than that of a conventional gasoline engine.
  • Lithium-sulfur batteries surpass capacity limits determined by the intercalation reaction of lithium ions into metal oxide and graphite, which is the basic principle of existing lithium ion secondary batteries. High-capacity, low-cost battery system.
  • the lithium-sulfur cell has a theoretical capacity of 1,675 mAh / g derived from the conversion reaction of lithium ions and sulfur at the anode (S 8 + 16Li + + 16e - ⁇ 8Li 2 S) and the cathode is lithium metal (theoretical capacity: 3,860 mAh / g) can be used to increase the capacity of the battery system. Since the discharge voltage is about 2.2 V, the energy density is theoretically 2,600 Wh / kg based on the amount of the anode and the anode active material. This is 6 to 7 times higher than the energy theoretical energy density of 400 Wh / kg of commercial lithium secondary batteries (LiCoO 2 / graphite) using layered metal oxide and graphite.
  • Lithium-sulfur battery has been attracting attention as a new high-capacity, eco-friendly, low-cost lithium secondary battery since it is known that battery performance can be dramatically improved through the formation of nanocomposite around 2010, .
  • the size of the particles as in the example of LiFePO 4, which is one of other cathode active materials, (Melt impregnation into nano-sized porous carbon nanostructure or metal oxide structure) and physical methods (high energy ball milling) are reported. .
  • Lithium polysulfide causes a shuttle reaction during the charging process, which causes the charging capacity to increase continuously, resulting in a drastic reduction in charge / discharge efficiency.
  • a variety of methods have been proposed to solve these problems, including a method of improving the electrolyte, a method of improving the surface of the cathode, and a method of improving the characteristics of the anode.
  • a new electrolyte such as a functional liquid electrolyte of a new composition, a polymer electrolyte, and an ionic liquid is used to suppress the dissolution of the polysulfide into an electrolyte or control the dispersion rate to the cathode To suppress the shuttle reaction as much as possible.
  • an electrolyte additive such as LiNO 3 is added to form an oxide film of Li x NO y , Li x SO y , A method of forming a thick functional SEI layer on the surface of lithium metal, and the like.
  • a method for improving the properties of the anode there is a method of forming a coating layer on the surface of the anode particles or adding a porous material capable of catching the dissolved polysulfide so as to prevent the dissolution of polysulfide.
  • a method of coating the surface of the anode structure with a metal oxide on which lithium ions are transferred a method of coating a porous metal oxide having a large specific surface area and a large pore size, which can absorb a large amount of lithium polysulfide, , A method of attaching a functional group capable of adsorbing lithium polysulfide on the surface of a carbon structure, and a method of enclosing sulfur particles using graphene or graphene oxide.
  • Patent Document 1 Korean Patent Registration No. 10-1996-0065174 (July 27, 2000), " Method for producing reedocrocite "
  • Patent Document 2 Korean Patent Laid-Open Publication No. 10-2015-0091280 (Apr. 14, 2017), " Lithium Sulfate Battery and Method for Producing the Same &
  • the inventors of the present invention have anticipated that battery performance can be improved most directly by improving the anode characteristics of the lithium-sulfur battery.
  • FeOOH was introduced into the positive electrode of a lithium-sulfur battery, it was confirmed that lithium polysulfide (LiPS) could be adsorbed, thus completing the present invention.
  • NaBH 4 is reacted with Fe (NO 3 ) 3 .9H 2 O or FeCl 3 .6H 2 O in an appropriate aqueous solution.
  • FeOOH iron hydroxide
  • ⁇ -FeOOH iron hydroxide
  • an object of the present invention is to provide a process for producing iron hydroxide of high purity through a simple process.
  • M 1 is any one selected from Li, Na, Mg, K, and Ca, and X is 1 or 2.
  • One embodiment of the present invention is an aqueous solution of 0.04 to 0.08 M of Fe (NO 3 ) 3 .9H 2 O or FeCl 3 .6H 2 O.
  • the reducing agent represented by Formula 1 is an aqueous solution of 0.2 to 0.5 M.
  • the mixing is carried out for 10 to 120 seconds.
  • the reaction temperature is 20 to 25 ⁇ ⁇ .
  • the reaction time is 10 minutes to 10 hours.
  • the reaction time is 40 minutes to 2 hours.
  • One embodiment of the present invention further comprises a step of filtration and drying after the reaction step.
  • the drying is carried out at 70 to 90 DEG C for 6 to 12 hours.
  • the iron hydroxide (FeOOH) is lepidocrocite ( ⁇ -FeOOH).
  • the iron hydroxide (FeOOH) is crystalline.
  • the iron hydroxide (FeOOH) is a plate-like type.
  • the iron hydroxide has a particle diameter of 50 to 500 nm.
  • a positive electrode for a lithium-sulfur battery including an active material, a conductive material and a binder,
  • the positive electrode provides a positive electrode for a lithium-sulfur battery including iron hydroxide (FeOOH).
  • the iron hydroxide (FeOOH) is lepidocrocite ( ⁇ -FeOOH).
  • the iron hydroxide (FeOOH) is crystalline.
  • the iron hydroxide (FeOOH) is a plate-like type.
  • the average diameter of the iron hydroxide (FeOOH) is 50 to 500 nm.
  • the amount of iron hydroxide (FeOOH) contained in the positive electrode for a lithium-sulfur battery is 0.1 to 15 parts by weight based on 100 parts by weight of the base solid content.
  • the active material is a sulfur-carbon composite.
  • the positive electrode provides the lithium-sulfur battery which is the positive electrode for the lithium-sulfur battery.
  • high purity iron hydroxide FeOOH
  • FeOOH high purity iron hydroxide
  • the shape and purity of the produced iron hydroxide (FeOOH) can be controlled by controlling the reaction temperature and the reaction time in the reaction of NaBH 4 with Fe (NO 3 ) 3 .9H 2 O or FeCl 3 .6H 2 O.
  • the present invention can selectively produce lepidocrocite ( ⁇ -FeOOH), which is also crystalline iron hydroxide. Also, when iron hydroxide (FeOOH) is applied to the anode of a lithium-sulfur battery, the reactivity of the lithium-sulfur battery anode is increased by adsorbing lithium polysulfide generated during charging and discharging, and the lithium- It is possible to exhibit an effect of increasing
  • FIG. 1 shows a scanning electron microscope (SEM) image of iron hydroxide (FeOOH) according to the production example of the present invention and the comparative preparation example.
  • FIG. 2 shows a scanning electron microscope (SEM) image of iron hydroxide (FeOOH) according to the production example of the present invention.
  • FIG. 3 shows X-ray diffraction (XRD) results of iron hydroxide (FeOOH) according to the preparation examples and comparative preparation examples of the present invention.
  • Li 2 S 6 lithium polysulfide (Li 2 S 6 ) adsorption reaction of iron hydroxide (FeOOH) according to the present invention as a result of UV absorbance measurement.
  • FIG. 8 shows the discharge capacity measurement results of a lithium-sulfur battery including a positive electrode according to Examples and Comparative Examples of the present invention.
  • FIG. 9 shows the results of measurement of lifetime characteristics of a lithium-sulfur battery including a positive electrode according to Experimental Examples and Comparative Experimental Examples of the present invention.
  • FIG. 10 shows the results of measurement of lifetime characteristics of a lithium-sulfur battery including a positive electrode 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.
  • the present invention relates to a process for producing iron hydroxide (FeOOH), and more particularly, to a process for producing iron hydroxide (FeOOH) having a shape and physical properties capable of improving the discharge capacity by applying it as a cathode material of a lithium-sulfur battery.
  • the process for producing iron hydroxide (FeOOH) according to the present invention comprises the steps of: Fe (NO 3 ) 3 .9H 2 O or FeCl 3 .6H 2 O; And
  • M 1 is any one selected from Li, Na, Mg, K, and Ca, and X is 1 or 2.
  • the Fe (NO 3) 3 ⁇ 9H 2 O or FeCl 3 ⁇ 6H 2 O and a reducing agent represented by Formula 1 may be in both the form of an aqueous solution, wherein the reducing agent aqueous solution of the formula (1) Fe (NO 3 ) 3 ⁇ 9H 2 O aqueous solution or FeCl 3 ⁇ 6H 2 O aqueous solution may be added, followed by mixing and reacting.
  • the purity of the produced iron hydroxide (FeOOH) may be lowered. That is, when the aqueous solution of the reducing agent represented by Formula 1 is added to the Fe (NO 3 ) 3 .9H 2 O aqueous solution or FeCl 3 .6H 2 O aqueous solution and mixed and reacted, the purity of the iron hydroxide (FeOOH) .
  • the Fe (NO 3 ) 3 .9H 2 O aqueous solution or FeCl 3 .6H 2 O aqueous solution may be 0.04 to 0.08 M, preferably 0.05 to 0.06 M, and if it is less than 0.04 M, the production yield of iron hydroxide (FeOOH) If it is more than 0.08 M, the physical properties of the produced iron hydroxide (FeOOH) may not be suitable as a cathode material for a lithium-sulfur battery.
  • the reducing agent aqueous solution represented by the above formula (1) may be 0.2 to 0.5 M, preferably 0.3 to 0.4 M. If it is less than 0.2 M, iron hydroxide (FeOOH) can not be produced, and if it exceeds 0.5 M, the reaction may not proceed.
  • FeOOH iron hydroxide
  • the additive represented by Formula 1 may be NaBH 4 .
  • iron hydroxide FeOOH
  • the mixing of the Fe (NO 3 ) 3 .9H 2 O or FeCl 3 .6H 2 O and the reducing agent represented by the above formula (1) may be performed within a short time, and may be performed within 10 to 120 seconds, preferably 50 to 80 seconds have. If the mixing time is less than 10 seconds, the mixing may occur excessively and the gas may be generated all at once, so that the reaction may proceed unevenly. If the mixing time is more than 120 seconds, the mixing speed is slow, The phase of the material may be different.
  • the reaction temperature may be 10 to 60 ° C, preferably 20 to 50 ° C, more preferably 20 to 25 ° C. If the reaction temperature is less than 10 ° C, the reaction may not proceed, and if it is more than 60 ° C
  • the physical properties of the produced iron hydroxide (FeOOH) may be denatured. Further, it may be preferable to conduct the reaction while maintaining the temperature at 20 to 25 DEG C for controlling the reaction rate.
  • the reaction time may be from 10 minutes to 10 hours, preferably from 40 minutes to 2 hours. If it is less than 10 minutes, iron hydroxide (FeOOH) may not be formed, and if it exceeds 20 hours, Shape may not be suitable as a cathode material of a lithium-sulfur battery. In particular, when reacting for 40 minutes to 2 hours, desired properties of FeOOH can be maintained without being lost.
  • FeOOH iron hydroxide
  • the filtration step may be performed by a filtration process commonly used in the art, for example, a filter paper may be used.
  • the drying may be carried out at 70 to 90 ° C for 6 to 12 hours.
  • the drying temperature is lower than 70 ° C or the drying time is less than 6 hours, it is not completely dried to obtain particles of iron hydroxide (FeOOH). If the drying temperature exceeds 90 ° C or exceeds 12 hours, the remaining water will boil, The physical properties may be denatured.
  • the iron hydroxide (FeOOH) produced by the method as described above may be crystalline, and specifically may be lepidocrocite ( ⁇ -FeOOH).
  • the prepared iron hydroxide (FeOOH) may be in the form of a plate, and in this case, it may be advantageous to improve the discharge capacity when applied to the cathode material of the lithium-sulfur battery.
  • the shape of the prepared iron hydroxide (FeOOH) can be controlled as needed by controlling the reaction time, and they are all applicable to the cathode material of a lithium-sulfur battery.
  • the produced iron hydroxide (FeOOH) may have a particle size of more than 0 and 500 nm or less, preferably 50 to 500 nm. As the particle size decreases within the above range, it is suitable as a cathode material for a lithium-sulfur battery. If the particle diameter is larger than the above range, the particle size is large and is not suitable as a cathode material of a lithium-sulfur battery.
  • iron hydroxide for example, crystalline lepidocrocite ( ⁇ -FeOOH) produced by the above-described method for producing iron hydroxide (FeOOH) is applied to a lithium-sulfur battery, It is possible to adsorb the polysulfide to be eluted and to improve the performance of the lithium-sulfur battery.
  • the process for producing the iron hydroxide (FeOOH) according to the present invention can selectively produce crystalline lepidocrocite (? -FeOOH) in iron hydroxide (FeOOH), and is suitable for a cathode material supply technology of a lithium-sulfur battery.
  • Figs. 1 and 2 show scanning electron microscope (SEM) images of the iron hydroxide (FeOOH) produced by the above-mentioned production method.
  • SEM scanning electron microscope
  • Fig. 4 shows the X-ray diffraction (XRD) data of the iron hydroxide (FeOOH) produced by the above-mentioned production method of reedocrocite (y-FeOOH).
  • XRD X-ray diffraction
  • a significant or effective peak in X-ray diffraction analysis means a peak that is repeatedly detected in the same pattern without being greatly affected by analysis conditions or analysts in XRD data.
  • intensity, intensity, etc. of at least 1.5 times, preferably at least 2 times, more preferably at least 2.5 times the backgound level.
  • the present invention provides a positive electrode for a lithium-sulfur battery including an active material, a conductive material and a binder, wherein the positive electrode comprises a positive electrode for a lithium-sulfur battery including iron hydroxide (FeOOH).
  • FeOOH iron hydroxide
  • the anode of the lithium-sulfur battery may have a base solid portion including an active material, a conductive material, and a binder on a current collector.
  • the current collector it is preferable to use aluminum or nickel excellent in conductivity.
  • 0.1 to 15 parts by weight, and preferably 1 to 10 parts by weight, of iron hydroxide (FeOOH) may be contained based on 100 parts by weight of base solids including the active material, the conductive material, and the binder. If it is less than the lower limit of the above-mentioned numerical range, the adsorption effect of polysulfide may be insignificant, and if it exceeds the upper limit value, the capacity of the electrode is decreased.
  • the iron hydroxide (FeOOH) may be iron hydroxide (FeOOH) produced by the production method proposed in the present invention, and preferably it may be lepidocrocite ( ⁇ -FeOOH).
  • the iron hydroxide (FeOOH) may be crystalline and may be in the form of a plate having an average particle size of 50 to 500 nm.
  • the positive electrode for a lithium-sulfur battery according to the present invention may include an active material of a sulfur-carbon composite. Since the sulfur material alone does not have electrical conductivity, it can be used in combination with a conductive material. The addition of iron hydroxide (FeOOH) according to the present invention does not affect the structure maintenance of this sulfur-carbon complex.
  • FeOOH iron hydroxide
  • the active material is composed of 50 to 95 parts by weight, more preferably 70 parts by weight, of 100 parts by weight of the base solid content. If the active material is contained in an amount less than the above range, it is difficult to sufficiently exert the reaction of the electrode. Even if the active material is contained in an amount exceeding the above range, the amount of other conductive materials and binders is relatively insufficient, It is desirable to determine the titratable content.
  • the conductive material is a material that electrically connects the electrolyte and the cathode active material and serves as a path through which electrons move from the current collector to the sulfur. And is not particularly limited as long as it has porosity and conductivity.
  • a graphite-based material such as KS6; Carbon black such as 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 fiber and metal fiber; Metal powders such as carbon fluoride, aluminum, and nickel powder; Or conductive polymers such as polyaniline, polythiophene, polyacetylene, and polypyrrole may be used alone or in combination.
  • the conductive material may preferably be 1 to 10 parts by weight, preferably 5 parts by weight, based on 100 parts by weight of the base solid content. If the content of the conductive material contained in the electrode is less than the above range, the portion of the electrode in which sulfur does not react increases and eventually the capacity is reduced. If the content exceeds the above range, the high efficiency discharge characteristic and the charge and discharge cycle life are adversely affected It is preferable to determine the optimum content within the above-mentioned range.
  • the binder is a material that contains a base solids slurry composition that forms the anode to adhere well to the current collector, and is a material that is well dissolved in the solvent and can well constitute the conductive network of the cathode active material and the conductive material use.
  • binders known in the art can be used and are preferably selected from the group consisting of poly (vinyl) acetate, polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, alkylated polyethylene oxide, crosslinked polyethylene oxide , Copolymers of polyvinyl ether, poly (methyl methacrylate), polyvinylidene fluoride (PVdF), polyhexafluoropropylene, polyvinylidene fluoride (trade name: Kynar), poly (ethyl acrylate) Siloxane series such as tetrafluoroethylene polyvinyl chloride, polytetrafluoroethylene, polyacrylonitrile, polyvinylpyridine, polystyrene, carboxymethylcellulose, polydimethylsiloxane, styrene-butadiene rubber, acrylonitrile-butadiene Rubber, a rubber-based binder including a styrene-isoprene rubber,
  • the binder may comprise 1 to 10 parts by weight, preferably 5 parts by weight, of 100 parts by weight of the base composition contained in the electrode. 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 fall off. If the amount exceeds the above range, the ratio of the active material and the conductive material may be relatively decreased, Therefore, it is desirable to determine the optimum content within the above-mentioned range.
  • the positive electrode containing the iron hydroxide (FeOOH) and the base solid can be produced by a conventional method.
  • iron hydroxide FeOOH
  • a solvent for preparing an organic compound
  • an active material for forming an organic compound
  • a conductive material for forming an organic compound
  • a binder for forming an organic compound
  • This slurry composition is then coated on a current collector and dried to complete the anode. At this time, if necessary, it can be manufactured by compression-molding the current collector to improve the electrode density.
  • a cathode active material, a binder, and a conductive material can be uniformly dispersed and a material capable of easily dissolving iron hydroxide (FeOOH) is used.
  • a solvent water is most preferable as an aqueous solvent, and the water may be distilled water (DW) or deionized water (DIW), which is a third distillation.
  • DW distilled water
  • DIW deionized water
  • a lower alcohol which can be easily mixed with water may be used. Examples of the lower alcohol include methanol, ethanol, propanol, isopropanol, butanol, etc., and they can be used in combination with water.
  • the present invention provides a lithium-sulfur battery having an anode, a cathode, a separator interposed therebetween, and an electrolyte, wherein the anode is the anode as described above.
  • the cathode, the separator, and the electrolyte may be composed of conventional materials that can be used in a lithium-sulfur battery.
  • the negative electrode may include 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, Or a lithium alloy may be used.
  • the material capable of reversibly storing or releasing lithium ions may be, for example, crystalline carbon, amorphous carbon, or a mixture thereof.
  • the material capable of reacting with the lithium ion (Li + ) to reversibly form a lithium-containing compound 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 optionally in combination with the negative electrode active material.
  • the binder acts as a paste for the anode active material, mutual adhesion between the active materials, adhesion between the active material and the current collector, buffering effect on expansion and contraction of the active material, and the like. Specifically, 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 the negative electrode active material and the 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.
  • fired carbon, a nonconductive 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 separation membrane is made of a material capable of separating or inserting the positive electrode and the negative electrode from each other while allowing the lithium ion to be transported therebetween, and can be used without any particular limitation as long as it is used as a separation membrane in a lithium-sulfur battery. Particularly, It is preferable that the electrolyte has a low resistance to migration and an excellent ability to hinder the electrolyte.
  • the separation membrane material may be a porous, nonconductive or insulating material, such as an independent member such as a film, or a coating layer added to the anode and / or the cathode.
  • a porous polymer film made of a polyolefin-based polymer such as an ethylene homopolymer, a propylene homopolymer, an ethylene / butene copolymer, an ethylene / hexene copolymer and an ethylene / methacrylate copolymer may be used alone Or they may be laminated.
  • a nonwoven fabric made of a conventional porous nonwoven fabric for example, glass fiber of high melting point, polyethylene terephthalate fiber or the like may be used, but not always limited thereto.
  • the electrolyte is a non-aqueous electrolyte containing a lithium salt, and 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 is a material that can easily be dissolved in 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 Lithium tetraborate, lithium tetraborate, lithium tetraborate, lithium tetraborate, lithium tetraborate, and imide.
  • the concentration of the lithium salt may be in the range of 0.2 to 2 M, preferably in the range of 0.2 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, Preferably 0.6 to 2 M, and more preferably 0.7 to 1.7 M. If the concentration of the lithium salt is less than the above range, the conductivity of the electrolyte may be lowered and the performance of the electrolyte may be deteriorated. If the concentration exceeds the above range, the viscosity of the electrolyte may increase and the mobility of lithium ions (Li + ) may decrease. It is preferable to select an appropriate concentration.
  • the non-aqueous organic solvent is a substance capable of dissolving a lithium salt well, preferably 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane, Dioxolane, DOL ), 1,4-dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), methyl propyl carbonate (EP), toluene, xylene, dimethyl ether (DME), diethyl ether, triethylene glycol monomethyl ether (TEGME), dipropyl carbonate, butyl ethyl carbonate, ethyl propanoate Hexamethylphosphoric triamide, gamma butyrolactone (GBL), acetonitrile, propionitrile, ethylene carbonate (EC), propylene carbonate (PC), N-methylpiperaz
  • the organic solid electrolyte is selected from the group consisting of 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 dissociation group, and the like may be used.
  • the inorganic solid electrolytes of the present invention are preferably 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 PO 4 -Li 2 S-SiS 2, and the like can be used.
  • the shape of the above-described lithium-sulfur 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- May be a stack-folding type.
  • An electrode assembly in which the positive electrode, the separator, and the negative electrode are sequentially stacked is manufactured, and the electrode assembly is inserted into a battery case. Then, an electrolyte is injected into the upper portion of the case, and the assembly is sealed with a cap plate and a gasket. do.
  • the lithium-sulfur battery may be classified into a cylindrical type, a rectangular type, a coin type, a pouch type, and the like depending on the type, 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.
  • iron hydroxide for example, crystalline lepidocrocite ( ⁇ -FeOOH) produced by the above-described method for producing iron hydroxide (FeOOH) is applied to a lithium-sulfur battery
  • ⁇ -FeOOH crystalline lepidocrocite
  • the reactivity of the lithium-sulfur battery is increased by adsorbing the polysulfide to be eluted, and the lithium-sulfur battery to which the lithium-sulfur battery is applied has the effect of improving the discharge capacity and the life characteristic.
  • NaBH 4 is a product of TCI, having a purity of> 95%
  • Fe (NO 3 ) 3 .9H 2 O is a product of Aldrich, having a purity of 98%.
  • Ferric hydroxide was prepared by adding 10 L of an aqueous solution of sodium hydroxide having a concentration of 1.6 M / L to 40 L of an aqueous ferrous chloride solution having a concentration of 0.8 M / L, and then subjected to an oxidation reaction at a reaction temperature of 25 ° C. At this time, the seed crystal formation reaction was proceeded at different oxidation rates of the ferrous hydroxide.
  • the reaction rate of ferrous hydroxide is less than 0.15 mol / min, the reaction rate is slowed down and the goethite is incorporated.
  • the ferrous hydroxide can be sludged without being oxidized. If the oxidation rate is more than 0.4 mol / min, The grown lepidocrocite is formed into an unstable particle and may be redissolved as Fe 2 + and OH - .
  • iron hydroxide FeOOH
  • solid base material active material, conductive material and binder
  • iron hydroxide (FeOOH) prepared in Production Example 1 was added as a solvent, based on the total solid weight (100 parts by weight) Lt; / RTI >
  • 90 parts by weight of the sulfur-carbon composite (S / C 7: 3) as the active material 5 parts by weight of the conductive black rode black, and 5 parts by weight of the styrene butadiene rubber / And 5 parts by weight of carboxymethylcellulose (SBR / CMC 7: 3) were added and mixed to prepare a positive electrode slurry composition.
  • SBR / CMC 7: 3 carboxymethylcellulose
  • 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 according to the above 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 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 according to the above 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
  • FeOOH / Co prepared by mixing Fe (NO 3 ) 3 / CoCl 2 and NaBH 4 in place of iron hydroxide (FeOOH).
  • Example 1 The procedure of Example 1 was repeated, except that Fe (OH) 3 was used in place of iron hydroxide (FeOOH).
  • FIG. 3 is a graph showing the results of XRD analysis of the lepidocrocite prepared in Production Example 1 and Comparative Production Example 1, respectively.
  • the lithium-sulfur battery prepared in Examples 1 and 2 and Comparative Examples 1 to 3 was used to measure the discharge capacity according to the type of cathode material.
  • the positive electrode of Example 1 contains 10 parts by weight of sulfur-carbon composite and iron hydroxide (FeOOH), and the positive electrode of Example 2 contains 5 parts by weight of sulfur-carbon composite and iron hydroxide (FeOOH).
  • the positive electrode of Comparative Example 1 was comprised of a sulfur-carbon composite, and the positive electrode of Comparative Example 2 was composed of a sulfur-carbon composite and 10 parts by weight of gamma-FeOOH / Co.
  • the positive electrode of Comparative Example 3 was composed of a sulfur- And 10 parts by weight of (OH) 3 . At this time, the measurement current was 0.1 C and the voltage range was 1.8 to 2.5 V.
  • the measured discharge capacity data are shown in Table 1 and FIG.
  • Example 1 Metallic lithium Sulfur-carbon composite + FeOOH (10 parts by weight) of Production Example 1 1222
  • Example 2 Metallic lithium Sulfur-carbon composite + FeOOH (5 parts by weight) of Production Example 1 1165
  • Comparative Example 1 Metallic lithium Sulfur-carbon complex 1073
  • Comparative Example 2 Metallic lithium Sulfur-carbon composite + ⁇ -FeOOH / Co (10 parts by weight) 1160
  • Comparative Example 3 Metallic lithium Sulfur-carbon composite + Fe (OH) 3 (10 parts by weight) 1118
  • the positive electrode of Experimental Example (1) includes a sulfur-carbon composite, and the positive electrode of Experimental Example (1) contains a sulfur-carbon composite and the iron hydroxide of Production Example 1 (FeOOH) (FeOOH) of Comparative Production Example 1 and discharged at a rate of 0.1 C, and the results are shown in Table 2 and FIG.
  • Example 1 The lithium-sulfur battery according to Example 1, Example 2, and Comparative Example 1 was used to measure the change pattern of the discharge capacity according to the cycle of the battery and charge / discharge efficiency at 90 cycles. At this time, the initial discharge / charge proceeded to 0.1 C / 0.1 C for 2.5 cycles, and then to 0.5 C / 0.3 C thereafter. The voltage range was set to 1.8 to 2.5V.
  • the discharge capacity reduction rate during the course of the battery cycle is significantly smaller than that of Comparative Example 1 which does not contain iron hydroxide (FeOOH) in the anode. Further, it is confirmed that the decrease of the discharge capacity is smaller as the content of iron hydroxide (FeOOH) is further decreased.
  • Comparative Example 1 the battery is degenerated from 60 cycles, but in Example 1, the degeneration of the battery starts after 70 cycles .
  • the anode and anode of the lithium-sulfur battery were constituted as shown in Table 3 below, and the discharge capacity was measured.
  • the positive electrode of Comparative Experiment Example (1) was composed of a sulfur-carbon composite, and the positive electrode of Experimental Example (1) was composed of sulfur-carbon composite material and iron hydroxide of Production Example 1 (FeOOH) 0.3 C / 0.5 C 10 cycles were repeated to evaluate the lifetime characteristics.
  • the results are shown in Table 3 and FIG.
  • the Coulombic Efficiency which represents the ratio of the charging capacity to the discharging capacity, is also maintained at 100%.
  • the adsorption capacity of lithium polysulfide was visually checked through the change of chromaticity. As a result, it was confirmed that the red color of lithium polysulfide (FIG. 5, blank) reacted with iron hydroxide (FeOOH) , And iron hydroxide (FeOOH) were excellent in the adsorption performance of lithium polysulfide.

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Abstract

La présente invention concerne un procédé de préparation d'hydroxyde de fer (FeOOH), et une cathode de batterie au lithium-soufre comprenant de l'hydroxyde de fer. Plus précisément, l'hydroxyde de fer cristallin, notamment la lépidocrocite (γ-FeOOH), peut être préparé en régulant un temps de réaction et une température de réaction, et la capacité de décharge et les caractéristiques de durée de vie d'une batterie peuvent être améliorées en appliquant l'hydroxyde de fer à pureté élevée préparé à une cathode de batterie au lithium-soufre.
PCT/KR2018/006003 2017-06-20 2018-05-28 Procédé de préparation d'hydroxyde de fer (feooh), et cathode de batterie au lithium-soufre comprenant de l'hydroxyde de fer WO2018236060A1 (fr)

Priority Applications (4)

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CN201880003777.XA CN109792039B (zh) 2017-06-20 2018-05-28 制备羟基氧化铁(FeOOH)的方法和包含羟基氧化铁的锂硫电池正极
EP18821299.7A EP3490038A4 (fr) 2017-06-20 2018-05-28 Procédé de préparation d'hydroxyde de fer (feooh), et cathode de batterie au lithium-soufre comprenant de l'hydroxyde de fer
JP2019505215A JP6758679B2 (ja) 2017-06-20 2018-05-28 水酸化鉄（ＦｅＯＯＨ）の製造方法及び水酸化鉄を含むリチウム−硫黄電池用正極
US16/324,249 US11038174B2 (en) 2017-06-20 2018-05-28 Method for preparing iron oxide-hydroxide (FeOOH) and positive electrode for lithium-sulfur battery comprising iron oxide-hydroxide

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KR20170078017 2017-06-20
KR10-2017-0078017 2017-06-20
KR10-2017-0089104 2017-07-13
KR20170089104 2017-07-13
KR10-2018-0059572 2018-05-25
KR1020180059572A KR102229454B1 (ko) 2017-06-20 2018-05-25 수산화철(FeOOH)의 제조방법 및 수산화철을 포함하는 리튬-황 전지용 양극

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111547831A (zh) * 2020-05-19 2020-08-18 常熟理工学院 一种绿锈掺纳米银颗粒脱氯剂及其制备方法和应用
EP3954655A4 (fr) * 2019-08-13 2022-07-27 LG Energy Solution, Ltd. Oxyhydroxynitrate de fer ayant une surface adsorbée par anion d'acide phosphorique, son procédé de préparation, cathode comprenant de l'oxyhydroxynitrate de fer ayant une surface adsorbée par anion d'acide phosphorique pour pile secondaire au lithium et pile secondaire au lithium comprenant celui-ci
CN116605916A (zh) * 2023-05-31 2023-08-18 湖北虹润高科新材料有限公司 一种α-FeOOH的制备方法和磷酸铁的制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19755351A1 (de) * 1997-12-12 1999-06-17 Walter Prof Dr Jansen Niedertemperatur-Metall-Schwefel-Batterie
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
KR20090120058A (ko) * 2008-05-19 2009-11-24 포항공과대학교 산학협력단 카르보닐계 용매를 이용한 나노 철의 제조방법 및 이로부터제조된 나노 철
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

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19755351A1 (de) * 1997-12-12 1999-06-17 Walter Prof Dr Jansen Niedertemperatur-Metall-Schwefel-Batterie
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
KR20090120058A (ko) * 2008-05-19 2009-11-24 포항공과대학교 산학협력단 카르보닐계 용매를 이용한 나노 철의 제조방법 및 이로부터제조된 나노 철
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

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
AGARWAL. ASHUTOSH ET AL.: "Synthesis, Characterization and Application of Nano Lepidocrocite and Magnetite in the Degradation of Carbon Tetrachloride", SOUTH AFRICAN JOURNAL OF CHEMISTRY, vol. 64, 2011, pages 218 - 224, XP055574521 *
See also references of EP3490038A4 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3954655A4 (fr) * 2019-08-13 2022-07-27 LG Energy Solution, Ltd. Oxyhydroxynitrate de fer ayant une surface adsorbée par anion d'acide phosphorique, son procédé de préparation, cathode comprenant de l'oxyhydroxynitrate de fer ayant une surface adsorbée par anion d'acide phosphorique pour pile secondaire au lithium et pile secondaire au lithium comprenant celui-ci
CN111547831A (zh) * 2020-05-19 2020-08-18 常熟理工学院 一种绿锈掺纳米银颗粒脱氯剂及其制备方法和应用
CN111547831B (zh) * 2020-05-19 2022-03-29 常熟理工学院 一种绿锈掺纳米银颗粒脱氯剂及其制备方法和应用
CN116605916A (zh) * 2023-05-31 2023-08-18 湖北虹润高科新材料有限公司 一种α-FeOOH的制备方法和磷酸铁的制备方法
CN116605916B (zh) * 2023-05-31 2024-02-20 湖北虹润高科新材料有限公司 一种α-FeOOH的制备方法和磷酸铁的制备方法

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