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WO2017213462A1 - Matériau actif d'électrode positive pour une batterie rechargeable au sodium, et son procédé de préparation - Google Patents

Matériau actif d'électrode positive pour une batterie rechargeable au sodium, et son procédé de préparation Download PDF

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Publication number
WO2017213462A1
WO2017213462A1 PCT/KR2017/006027 KR2017006027W WO2017213462A1 WO 2017213462 A1 WO2017213462 A1 WO 2017213462A1 KR 2017006027 W KR2017006027 W KR 2017006027W WO 2017213462 A1 WO2017213462 A1 WO 2017213462A1
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Prior art keywords
sodium
active material
secondary battery
transition metal
metal oxide
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Korean (ko)
Inventor
선양국
황장연
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Industry University Cooperation Foundation IUCF HYU
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Industry University Cooperation Foundation IUCF HYU
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/04—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/80—Compounds containing nickel, with or without oxygen or hydrogen, and containing one or more other elements
    • C01G53/82—Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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 cathode active material for a sodium secondary battery, and a manufacturing method thereof, and more particularly, to improve the interfacial stability of the cathode active material against hydrogen fluoride (HF) generated during the charge and discharge of a sodium secondary battery.
  • the present invention relates to a method of manufacturing a cathode active material for a sodium secondary battery by coating a surface of a sodium transition metal oxide with a coating material through dry ball milling.
  • Lithium metal oxides are used as positive electrode active materials in lithium ion secondary batteries, which are mainly used as secondary batteries.
  • LiCoO 2 , LiMn 2 O 4 , LiNiO 2, and the like are known.
  • cobalt (Co) -based lithium oxide has been commercialized and widely used, but has a disadvantage in that the price of cobalt is high and harmful.
  • nickel-based lithium oxide is inexpensive, low in metal hazard and high in capacity, but has a disadvantage in that powder synthesis is not easy and life characteristics are not good.
  • lithium used as a main material is a rare material, and as the demand increases, the price continuously increases, so that the cost of the battery needs to be reduced in order to be applied to a large capacity storage battery for a home.
  • One technical problem to be solved by the present invention is to provide a cathode active material for sodium secondary battery with improved interfacial stability, and a manufacturing method thereof.
  • Another technical problem to be solved by the present invention is to provide a cathode active material for a sodium secondary battery with improved charge and discharge characteristics, and a manufacturing method thereof.
  • Another technical problem to be solved by the present invention is to provide a cathode active material for a sodium secondary battery with improved life characteristics, and a method of manufacturing the same.
  • Another technical problem to be solved by the present invention is to provide a cathode active material for a sodium secondary battery with improved rate characteristics, and a manufacturing method thereof.
  • Another technical problem to be solved by the present invention is to provide a cathode active material for a sodium secondary battery, and a manufacturing method thereof having reduced manufacturing costs.
  • the technical problem to be solved by the present invention is not limited to the above.
  • the present invention provides a method for producing a cathode active material for sodium secondary battery.
  • the method for manufacturing a cathode active material for a sodium secondary battery preparing a transition metal oxide containing at least two or more of nickel (Ni), cobalt (Co), or manganese (Mn), the transition metal Preparing a sodium transition metal oxide by mixing and firing a source of sodium (Na) in an oxide; and aluminum oxide (Al 2 O 3 ), zinc oxide (ZnO 2 ), and manganese oxide (MnO 2 ) in the sodium transition metal oxide.
  • the method may include preparing a cathode active material by adding a coating material including at least one of zirconium oxide (ZrO 2 ) or aluminum fluoride (AlF 3 ), followed by dry ball milling.
  • the method of manufacturing a cathode active material for a sodium secondary battery may include coating the coating material on the surface of the sodium transition metal oxide uniformly through the dry ball milling process.
  • the dry ball milling process may include being performed under an inert gas atmosphere.
  • the method for manufacturing a cathode active material for a sodium secondary battery, the chemical properties, and physical properties of the cathode active material is adjusted according to the rotational speed (rpm) and / or time of the dry ball milling process. can do.
  • the method of manufacturing a cathode active material for a sodium secondary battery may include controlling the charge and discharge characteristics of the battery according to the content of the coating material added to the sodium transition metal oxide.
  • the sodium source may include at least one of NaOH or Na 2 CO 3 .
  • the preparing of the sodium transition metal oxide may further include melting the sodium source before mixing the transition metal oxide and the sodium source.
  • the preparing of the sodium transition metal oxide may further include quenching after mixing and firing the transition metal oxide and the sodium source.
  • hydrogen fluoride HF
  • the manufacturing method of the cathode active material for sodium secondary battery according to the content of the coating material added to the sodium transition metal oxide
  • the permeability of hydrogen fluoride with respect to the positive electrode active material interface may be controlled.
  • the present invention provides a cathode active material for sodium secondary battery.
  • the cathode active material for a sodium secondary battery includes at least two or more transition metals of nickel, cobalt, or manganese, a sodium transition metal oxide including sodium metal, and a coating material on the surface of the sodium transition metal oxide,
  • the coating material may include at least one of aluminum oxide, zinc oxide, manganese oxide, zirconium oxide, and aluminum fluoride.
  • the cathode active material for a sodium secondary battery may include controlling charge and discharge characteristics of the battery according to the content of the coating material on the sodium transition metal oxide surface.
  • preparing a transition metal oxide comprising at least two or more of nickel, cobalt, or manganese
  • preparing a sodium transition metal oxide by mixing and calcining a sodium source with the transition metal oxide, And adding a coating material including at least one of aluminum oxide, zinc oxide, manganese oxide, zirconium oxide, or aluminum fluoride to the sodium transition metal oxide, followed by dry ball milling to prepare a cathode active material.
  • a method of manufacturing a cathode active material for a sodium secondary battery having improved instability at an interface of a cathode active material generated may be provided.
  • the instability of the interface between the positive electrode active material due to side reactions occurring between the electrolyte and the positive electrode active material in the battery during the charging and discharging process can be improved.
  • the surface of the sodium transition metal oxide with the coating material it is possible to minimize the hydrogen fluoride (HF) generated by the side reaction penetrates the positive electrode active material to reduce the charge and discharge and life characteristics of the sodium secondary battery have.
  • the rate characteristic of the battery may be improved.
  • the surface of the sodium transition metal oxide is coated using the dry ball milling process, which is a relatively simple process using sodium, which is less expensive than lithium, to produce a cathode active material for a sodium secondary battery.
  • Process time and process cost can be reduced compared to the lithium secondary battery being used. Accordingly, a cathode active material for sodium secondary battery that can be easily commercialized in various fields may be provided.
  • FIG. 1 is a flowchart illustrating a method of manufacturing a cathode active material for a sodium secondary battery according to an embodiment of the present invention.
  • FIGS. 2 and 3 are views for explaining a cathode active material for a sodium secondary battery according to an embodiment of the present invention.
  • FIG. 4 is a graph illustrating a manufacturing process of sodium transition metal oxide according to an embodiment of the present invention.
  • Example 5 is a SEM photograph of the cathode active material for sodium secondary battery according to Example 1 of the present invention.
  • FIG. 6 is a SEM photograph of a cathode active material for a sodium secondary battery different in ball milling conditions according to Examples and Comparative Examples of the present invention.
  • Example 7 and 8 are elemental analysis images using the TEM equipment of the cathode active material for sodium secondary battery according to Example 1 of the present invention.
  • Example 9 is TEM images of a cathode active material for a sodium secondary battery according to Example 1 of the present invention.
  • Example 10 is a graph of the XRD results of the cathode active material for sodium secondary battery according to Example 1 and Comparative Example 1 of the present invention.
  • Example 11 is a graph measuring discharge capacity characteristics of a sodium secondary battery including the cathode active material for sodium secondary battery according to Example 1 and Comparative Example 1 of the present invention.
  • Example 12 is a graph illustrating life characteristics of a sodium secondary battery including the cathode active material for sodium secondary battery according to Example 1 and Comparative Example 1 of the present invention.
  • Example 13 is a graph measuring rate characteristics of a sodium secondary battery including the cathode active material for sodium secondary battery according to Example 1 and Comparative Example 1 of the present invention.
  • FIG. 14 is a graph illustrating life characteristics of a sodium secondary battery including the cathode active material for sodium secondary batteries according to Examples 1 and 2 and Comparative Example 1 of the present invention.
  • Example 15 is a graph measuring rate characteristics of a sodium secondary battery including the cathode active material for sodium secondary batteries according to Examples 1 and 2 and Comparative Example 1 of the present invention.
  • FIG. 16 is a graph illustrating microcapacity characteristics of a sodium secondary battery including the cathode active material for sodium secondary battery according to Example 1 and Comparative Example 1 of the present disclosure.
  • FIG. 17 illustrates XRD data after charge and discharge of a sodium secondary battery including the cathode active material for sodium secondary battery according to Example 1 and Comparative Example 1 of the present invention.
  • Example 18 is a graph measuring discharge capacity characteristics of a full cell including the cathode active material for sodium secondary battery according to Example 1 and Comparative Example 1 of the present invention.
  • Example 19 is a graph illustrating life characteristics of a full cell including the cathode active material for a sodium secondary battery according to Example 1 and Comparative Example 1 of the present invention.
  • Example 21 is a measurement of the impedance characteristics of the cathode active material for sodium secondary battery according to Example 1 of the present invention.
  • Example 22 is an XPS analysis data result of a cathode active material for a sodium secondary battery according to Example 1 and Comparative Example 1 of the present invention.
  • FIG. 23 is a SEM photograph of the cathode active material after charge and discharge of a pouch cell including the cathode active material for sodium secondary battery according to Example 1 and Comparative Example 1 of the present invention.
  • FIG. 24 is a photograph illustrating a measurement of sodium precipitation in a negative electrode after charge and discharge of a pouch cell including a cathode active material for sodium secondary batteries according to Example 1 and Comparative Example 1 of the present invention.
  • Example 25 is a graph illustrating the thermal stability of the cathode active material for sodium secondary batteries according to Example 1 and Comparative Example 1 of the present invention.
  • first, second, and third are used to describe various components, but these components should not be limited by these terms. These terms are only used to distinguish one component from another. Thus, what is referred to as a first component in one embodiment may be referred to as a second component in another embodiment.
  • first component in one embodiment may be referred to as a second component in another embodiment.
  • second component in another embodiment.
  • Each embodiment described and illustrated herein also includes its complementary embodiment.
  • the term 'and / or' is used herein to include at least one of the components listed before and after.
  • FIG. 1 is a flowchart illustrating a method of manufacturing a cathode active material for a sodium secondary battery according to an embodiment of the present invention
  • Figures 2 and 3 are views for explaining a cathode active material for a sodium secondary battery according to an embodiment of the present invention
  • 4 is a graph illustrating a manufacturing process of sodium transition metal oxide according to an embodiment of the present invention.
  • a transition metal oxide 200 including at least two or more of nickel (Ni), cobalt (Co), or manganese (Mn) may be prepared (S100).
  • the transition metal oxide 200 may be manufactured through a coprecipitation method.
  • the preparing of the transition metal oxide 200 may include preparing nickel sulfate, cobalt sulfate, and manganese sulfate, and co-precipitation using the nickel sulfate, cobalt sulfate, and manganese sulfate. It may include the step of manufacturing the metal oxide 200.
  • an aqueous metal solution in which the nickel sulfate, the cobalt sulfate, and the manganese sulfate is mixed at a concentration of 2.5M may be prepared.
  • the transition metal oxide 200 was prepared by adding the aqueous metal solution to a coprecipitation reactor having a capacity of 16 L and an output of 80 W or more, and then stirring at 400 rpm while supplying N 2 gas at a rate of 2 L / min at a temperature of 45 ° C. Can be.
  • 5 mol of sodium hydroxide is supplied into the coprecipitation reactor, so that the pH of the aqueous metal solution can be adjusted to 11.5.
  • the metal hydroxide precursor in the coprecipitation reactor may be dried at 110 ° C. for 12 hours after filtration and washing.
  • the transition metal oxide 200 includes at least one of a core portion 110 having a constant ratio of nickel, cobalt, and manganese, and nickel, cobalt, and manganese.
  • the composition may include a concentration gradient unit 120 is changed.
  • the step of manufacturing the transition metal oxide 200, the step of manufacturing the core portion 110 while maintaining the input amount of the nickel sulfate, the cobalt sulfate, and the manganese sulfate constant, and the nickel sulfate It may include the step of manufacturing the concentration gradient unit 120 while changing the input amount of at least one of the cobalt sulfate, and the manganese sulfate.
  • the transition metal oxide 200 has a constant ratio of nickel, cobalt, and manganese, in addition to the core portion 110 and the concentration gradient portion 120.
  • the shell unit 130 may further include.
  • the step of manufacturing the transition metal oxide 200 after manufacturing the core portion 110 and the concentration gradient unit 120, the input amount of the nickel sulfate, the cobalt sulfate, and the manganese sulfate constant. It may further comprise the step of manufacturing the shell portion 130 while maintaining.
  • transition metal oxide 200 may have various structures and configurations, in addition to those shown in FIGS. 2 and 3.
  • a sodium transition metal oxide 250 may be prepared by mixing and firing a source of sodium (Na) in the transition metal oxide 200 (S200).
  • the sodium source may include at least one of NaOH or Na 2 CO 3 .
  • the sodium source before the sodium source and the transition metal oxide 200 are mixed, as shown in FIG. 4, the sodium source may be melted.
  • the sodium source when the sodium source is NaOH, the sodium source may be melted by heat treatment at 320 ° C for 4 hours.
  • the sodium source when the sodium source is Na 2 CO 3 , the sodium source may be melted by heat treatment at 870 °C for 4 hours.
  • the molten sodium source and the transition metal oxide 200 may be calcined, as shown in FIG. 4.
  • the fused sodium source and the transition metal oxide 200 may be fired at 680 ⁇ 720 °C.
  • the transition metal oxide 200 and the sodium source may be Firing efficiently, the sodium transition metal oxide 250 can be easily manufactured. Accordingly, in conditions where the nickel content in the transition metal oxide 200 is relatively high, the sodium source may include NaOH, which may be melted at a relatively low temperature.
  • the sodium transition metal oxide 250 may be easily manufactured. Accordingly, in a condition where the content of nickel in the transition metal oxide 200 is relatively low or the content of manganese is high, the sodium source may include Na 2 Co 3 which may be fused at a relatively high temperature. have.
  • the type of the sodium source may vary. Accordingly, the transition metal oxide 200 and the sodium source can be efficiently baked.
  • Electrochemical properties of the positive electrode active material 300 may be reduced.
  • a sodium source having a melting point corresponding to the content of nickel or manganese contained in the transition metal oxide 200 may be used.
  • the cathode active material 300 according to the embodiment of the present invention having improved electrical and chemical properties may be provided.
  • the manufacturing of the sodium transition metal oxide 250 may further include quenching, as illustrated in FIG. 4, after mixing and firing the transition metal oxide and the sodium source.
  • the sodium transition metal oxide 250 may be quenched in a vacuum state.
  • the transition metal oxide 200 and the sodium source may be quenched immediately after firing. For this reason, deterioration of the characteristics of the sodium transition metal oxide 250 including the sodium compound may be minimized.
  • the quenching process is not performed and the sodium transition metal oxide 250 is exposed to the atmosphere containing water, the sodium transition metal oxide ( As the structure of 250 decays, the properties of the sodium transition metal oxide 250 may deteriorate.
  • a quenching process may be performed immediately after the transition metal oxide 200 and the sodium source are fired.
  • the reaction between the moisture in the air and the sodium compound in the sodium transition metal oxide 250 is minimized, so that the cathode active material 300 according to the embodiment of the present invention having long life, high reliability, and high stability may be provided.
  • the step of quenching the sodium transition metal oxide 250 may be performed while maintaining a vacuum state in a reduction furnace immediately after firing of the transition metal oxide 200 and the sodium source. It may include rapidly lowering the temperature to room temperature for about 2-3 hours.
  • the positive electrode active material 300 may be manufactured by dry ball milling (S300).
  • the coating material 150 may be uniformly coated on the surface of the sodium transition metal oxide 250 particles.
  • the sodium transition metal oxide 250 is Na [NiCoMn] O 2 and 1 wt% Al 2 O 3 is used as the coating material, the coating material is formed on the surface of the sodium transition metal oxide 250.
  • the coating thickness formed by 150 may be about 50 to 70 nm.
  • Hydrogen fluoride may penetrate the positive electrode active material to reduce the interfacial properties of the positive electrode active material. Accordingly, the charge and discharge and lifespan characteristics of the sodium secondary battery may be reduced.
  • the sodium secondary battery is driven by coating the coating material 150 on the surface of the sodium transition metal oxide 250 through the dry ball milling process in consideration of the properties of the positive electrode active material vulnerable to moisture.
  • An unstable interface property of the positive electrode active material 300 due to the side reaction generated between the electrolyte and the positive electrode active material 300 in the battery generated at the time may be improved. Therefore, when the cathode active material 300 according to an embodiment of the present invention is applied to a sodium secondary battery at all times, a sodium secondary battery having improved charge and discharge characteristics and life characteristics as well as a rate characteristic may be provided.
  • the permeability of hydrogen fluoride with respect to the interface of the cathode active material 300 may be adjusted according to the content of the coating material added to the sodium transition metal oxide 250. Accordingly, according to the content of the coating material 150 added to the sodium transition metal oxide 250, the charge and discharge and life characteristics of the battery can be easily adjusted.
  • the positive electrode active material 300 For example, if the sodium transition after the Al 2 O 3 added in 1wt% to the coating agent to the metal oxide (250), wherein the dry ball milling process is performed in which the positive electrode active material 300 is prepared, the positive electrode active material The charge / discharge capacity value after 100 cycles of the sodium secondary battery to which 300 is applied may be about 120 / mAhg ⁇ 1 .
  • the chemical and physical properties of the cathode active material 300 to be manufactured can be adjusted depending on the rotational speed and / or time of the dry ball milling process. In addition, depending on the rotational speed and / or time of the dry ball milling process, it can be determined whether or not the cathode active material 300 to be manufactured is collapsed.
  • 2g of the sodium transition metal oxide 250 and 1wt% of the coating material 150 are added to a PP bottle made of PP, and then 100 rpm of zirconium (Zr) ball is used.
  • the dry ball milling process may be performed for about 12 hours at a rotational speed.
  • the dry ball milling process may be performed under an inert gas atmosphere.
  • the inert gas may be nitrogen (N 2 ) or argon (Ar) gas.
  • the cathode active material 300 for a sodium secondary battery may include a sodium transition metal oxide 250 and a coating material 150.
  • the sodium transition metal oxide 250 is mixed with the sodium source fused to the transition metal oxide 200 including at least two of nickel, cobalt, or manganese, as described above. After that, it can be produced by firing and quenching.
  • the coating material 150 may be located on the surface of the sodium transition metal oxide 250. According to an embodiment, the coating material 150 may include at least one of aluminum oxide, zinc oxide, manganese oxide, zirconium oxide, and aluminum fluoride.
  • Unstable interface characteristics of the cathode active material 300 may be improved. Accordingly, a sodium secondary battery having improved charge / discharge, lifespan, and rate characteristics can be provided.
  • the charge and discharge and life characteristics of the battery can be easily adjusted according to the content of the coating material 150 on the surface of the sodium transition metal oxide 250.
  • the coating material 150 on the surface of the sodium transition metal oxide 250 May be uniformly coated.
  • the dry ball milling process is performed for about 12 hours using a zirconium ball at a rotational speed of 100 rpm. This is performed to prepare a cathode active material 300 according to an embodiment of the present invention in which the coating material 150 is coated on the sodium transition metal oxide 250 surface.
  • lithium secondary batteries are already commercially available as large power sources such as small power sources such as mobile phones and laptop computers, power sources for electric vehicles, hybrid cars, and the like, or distributed power storage power supplies. Therefore, as the demand for the lithium secondary battery rapidly increases, in order to overcome and replace it, a study on a sodium secondary battery including a cathode active material having a high capacity of a lithium secondary battery, and a cathode or a cathode active material having abundant reserves It is actively underway.
  • preparing a transition metal oxide 200 including at least two of nickel, cobalt, or manganese by mixing and firing a sodium source in the transition metal oxide 200 to form a sodium transition metal
  • the cathode active material 300 may be manufactured to provide a method for manufacturing the cathode active material 300 for sodium secondary battery, in which the instability of the interface of the cathode active material generated when driving a conventional sodium secondary battery is improved.
  • the positive electrode due to side reactions occurring between the electrolyte and the positive electrode active material 300 in the battery during charging and discharging during battery operation Instability of the active material 300 interface can be improved.
  • HF hydrogen fluoride
  • the surface of the sodium transition metal oxide 250 is coated using the dry ball milling process, which is a relatively simple process using sodium, which is less expensive than lithium, thereby preparing a cathode active material 300 for sodium secondary battery.
  • the cathode active material 300 for sodium secondary battery which can be easily commercialized in various fields, may be provided.
  • Example 2 the ball milling conditions were performed for 24 hours at 100rpm and 12 hours at 50rpm, to prepare a cathode active material for sodium secondary battery according to Examples 1-1 and 1-2.
  • the positive electrode active material was prepared the positive electrode active material, the dry ball of Na [Ni by milling to the sodium transfer omitted coating process for the metal oxide wherein the sodium transition metal oxides 0.6 Co 0.2 Mn 0.2 ] O 2 was prepared.
  • Example 1 100 rpm 12 hours
  • Example 1-1 100 rpm 24 hours
  • FIG. 5 is a SEM picture of a cathode active material for a sodium secondary battery according to Example 1 of the present invention
  • FIG. 6 is a SEM picture of a cathode active material for a sodium secondary battery different in ball milling conditions according to an embodiment and a comparative example of the present invention.
  • FIG. 7 and 8 are elemental analysis images using the TEM equipment of the cathode active material for sodium secondary battery according to Example 1 of the present invention. Specifically, (a) of FIG. 7 is a TEM element analysis image of the cathode active material for sodium secondary battery according to Example 1 of the present invention, and FIG. 7 (b) shows the cathode active material for sodium secondary battery according to Example 1 of the present invention. TEM images for each element.
  • the sodium transition metal oxide contains nickel (Ni), cobalt (Co), and manganese (Mn), and it was confirmed that an aluminum oxide component was present on the sodium transition metal oxide surface. From this, it was found that Al 2 O 3 , the coating material, was evenly coated on the surface of Na [Ni 0.6 Co 0.2 Mn 0.2 ] O 2 , which is the sodium transition metal oxide.
  • Example 9 is TEM images of a cathode active material for a sodium secondary battery according to Example 1 of the present invention.
  • a sodium secondary battery positive electrode according to Example 2 of 1 wt% of the coating material Al 2 O 3 coated on a surface of Na [Ni 0.6 Co 0.2 Mn 0.2 ] O 2 , which is the sodium transition metal oxide, may be used.
  • TEM transmission electron microscope
  • the coating material was uniformly coated on the sodium transition metal oxide surface, and the coating thickness was about 50 to 70 nm.
  • FIG. 10 is a graph of the XRD results of the cathode active material for sodium secondary battery according to Example 1 and Comparative Example 1 of the present invention. Specifically, (a) of FIG. 10 is an XRD result graph of the cathode active material for sodium secondary battery according to Comparative Example 1, and FIG. 10 (b) is an XRD result graph of the cathode active material for sodium secondary battery according to Example 1.
  • FIG. 10 is a graph of the XRD results of the cathode active material for sodium secondary battery according to Example 1 and Comparative Example 1 of the present invention. Specifically, (a) of FIG. 10 is an XRD result graph of the cathode active material for sodium secondary battery according to Comparative Example 1, and FIG. 10 (b) is an XRD result graph of the cathode active material for sodium secondary battery according to Example 1.
  • FIG. 10 is a graph of the XRD results of the cathode active material for sodium secondary battery according to Example 1 and Comparative Example 1 of the present invention. Specifically,
  • the intensity of X-rays diffracted and emitted according to the measurement angles of the cathode active material for sodium secondary battery according to Example 2 and Comparative Example 1 of the present invention was measured using an X-ray diffraction (XRD) device. .
  • XRD X-ray diffraction
  • the weight ratio of the positive electrode active material according to the first and second embodiments prepared according to the method for manufacturing a cathode active material for a sodium secondary battery according to the embodiment, super-p and KS-6 as a conductive material, and PVDF (polyvinylidene fluoride) as a binder is 85
  • a slurry was prepared by mixing at 10: 5. The slurry was uniformly coated on aluminum foil, which is a cathode material of a sodium secondary battery, and then vacuum dried at a temperature of 80 ° C. to prepare a cathode of the sodium secondary battery.
  • a coin type sodium secondary battery was manufactured using a glass fiber filter (advanced) as a separator and using a PC liquid electrolyte.
  • the coating material Al 2 O 3 is not coated Na [Ni 0.6 Co 0.2 Mn 0.2 ] O 2 , that is, according to the comparative example Using a cathode active material, a sodium secondary battery according to a comparative example of the coin type was prepared.
  • FIG. 11 is a graph illustrating discharge capacity characteristics of a sodium secondary battery including the cathode active material for sodium secondary battery according to Example 1 and Comparative Example 1 of the present invention
  • FIG. It is a graph measuring the life characteristics of a sodium secondary battery comprising a cathode active material for sodium secondary battery according to the present invention
  • Figure 13 is a rate characteristic of a sodium secondary battery comprising a cathode active material for sodium secondary battery according to Example 1 and Comparative Example 1 of the present invention Is a graph measured.
  • the coating material is Al 2 O 3 is compared with the sodium secondary battery, the positive electrode active material is not coated, Al 2 O 3 is the discharge capacity characteristics of the secondary battery comprising the coated sodium secondary battery, the positive electrode active material It can be seen that the life characteristics, and the rate characteristics are improved.
  • FIG. 14 is a graph illustrating life characteristics of a sodium secondary battery including the cathode active material for sodium secondary battery according to Examples 1 to 3 and Comparative Example 1 of the present invention
  • FIG. 15 illustrates Examples 1 and 2 of the present invention. It is a graph which measured the rate characteristic of the sodium secondary battery containing the positive electrode active material for sodium secondary batteries which concerns on Example 1.
  • the positive electrode active material is not coated, life characteristics of secondary batteries including a sodium secondary battery, the positive electrode active material is Al 2 O 3 coating, And it can be seen that the rate characteristic is improved.
  • the life characteristics and capacity characteristics are controlled according to the content of Al 2 O 3 as the coating material. Specifically, when the content of Al 2 O 3 as the coating material exceeds 1wt%, specifically when the content of Al 2 O 3 is 3wt%, it can be seen that the life characteristics and discharge capacity characteristics are rather reduced. In other words, it can be confirmed that it is an efficient method of improving the life characteristics and the discharge capacity characteristics of controlling the content of Al 2 O 3 of the coating material to 1wt% or less.
  • FIG. 16 is a graph illustrating microcapacity characteristics of a sodium secondary battery including the cathode active material for sodium secondary battery according to Example 1 and Comparative Example 1 of the present disclosure.
  • the cathode active material for a sodium secondary battery according to Example 1 and Comparative Example 1 is Hex.O 3 + Mon. O'3 phase, Hex. P3 phase, Mon. P'3 phase, Hex. O3 + Mon. It can be seen that the O'3 phase has sequentially.
  • Hex.O3 phase means that the cathode active material for a sodium secondary battery has a hexagonal O3-type crystal structure, and Hex.
  • the P3 phase means that the cathode active material for a sodium secondary battery has a hexagonal O3-type crystal structure.
  • the O'3 phase means that the cathode active material for a sodium secondary battery has a monoclinic O'3 type crystal structure, and the Mon.
  • P'3 phase means that the cathode active material for a sodium secondary battery has a monoclinic P3 type crystal structure.
  • the positive electrode active material according to Comparative Example 1 and compare the sodium secondary battery the positive electrode active material is Al 2 O 3 is not coated, Hex .O3 + Mon. O'3 phase, Hex. P3 phase, Mon. P'3 phase, Hex. O3 + Mon. It can be seen that the O'3 phase value is not substantially shifted. In other words, in the case of the cathode active material for a sodium secondary battery coated with Al 2 O 3 , it can be confirmed that the reversibility of sodium ions in the charging and discharging process is high.
  • FIG. 17 illustrates XRD data after charge and discharge of a sodium secondary battery including the cathode active material for sodium secondary battery according to Example 1 and Comparative Example 1 of the present invention.
  • FIG. 18 is a graph illustrating discharge capacity characteristics of a full cell including a cathode active material for a sodium secondary battery according to Example 1 and Comparative Example 1 of the present invention
  • FIG. 19 is a view illustrating Example 1 and Comparative Example 1 of the present invention It is a graph measuring the life characteristics of a full cell containing a cathode active material for sodium secondary battery.
  • Example 18 and 19 a full cell was prepared using the cathode active material and the hard carbon anode for a sodium secondary battery according to Example 1 and Comparative Example 1, and discharge capacity characteristics and lifetime characteristics were measured.
  • Figure 21 is a measurement of the impedance characteristics of the cathode active material for sodium secondary battery according to the first embodiment of the present invention.
  • Example 22 is an XPS analysis data result of a cathode active material for a sodium secondary battery according to Example 1 and Comparative Example 1 of the present invention.
  • FIG. 23 is a SEM photograph of the cathode active material after charge and discharge of a pouch cell including the cathode active material for sodium secondary battery according to Example 1 and Comparative Example 1 of the present invention. Specifically, (a) of FIG. 23 is an SEM photograph of the cathode active material according to Comparative Example 1, and FIG. 23 (b) is an SEM photograph of the cathode active material according to Example 2.
  • a pouch cell was prepared using the cathode active material for sodium secondary battery according to Example 1 and Comparative Example 1, and SEM images were taken of the cathode active material after charge and discharge.
  • Comparative Example 1 in the case of the cathode active material for sodium secondary battery Al 2 O 3 is not coated, it can be confirmed that a large number of particles collapsed.
  • Example 1 in the case of the cathode active material for Al 2 O 3 coated sodium secondary battery, it can be seen that the particle shape is maintained stably.
  • FIG. 24 is a photograph illustrating a measurement of sodium precipitation in a negative electrode after charge and discharge of a pouch cell including a cathode active material for sodium secondary batteries according to Example 1 and Comparative Example 1 of the present invention.
  • the amount of sodium precipitated at the cathode was measured.
  • Comparative Example 1 in the case of the pouch cell including the cathode active material for sodium secondary battery not coated with Al 2 O 3 (c, c-1, c-2 of FIG. 24), a large amount of sodium was deposited on the surface of the negative electrode. You can see that.
  • the pouch cell including the positive electrode active material for Al 2 O 3 coated sodium secondary battery according to Example 1 (d, d-1, d-2 in Figure 24)
  • the high for the insertion and desorption of sodium ions Reversible it can be seen that a significant amount of sodium precipitated on the cathode.
  • Example 25 is a graph illustrating the thermal stability of the cathode active material for sodium secondary batteries according to Example 1 and Comparative Example 1 of the present invention.
  • thermal stability of the cathode active material for a sodium secondary battery according to Example 1 and Comparative Example 1 of the present invention was evaluated by differential scanning calorimetry.
  • the coating material may be uniformly coated on the sodium transition metal oxide surface.
  • the charge and discharge characteristics of the battery may be superior to when the coating material is not coated on the surface of the sodium transition metal oxide.
  • a cathode active material for a sodium secondary battery having improved battery charging and discharging characteristics, battery life, rate characteristics, and thermal stability may be provided.
  • a cathode active material for a sodium secondary battery and a secondary battery including the same may be used in various industrial fields such as a portable electronic device, an electric vehicle, and an energy storage device.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

L'invention porte également sur un procédé de préparation d'un matériau actif d'électrode positive pour une batterie rechargeable au sodium, le procédé comprenant les étapes consistant à : préparer un oxyde de métal de transition contenant au moins deux éléments parmi le nickel (Ni), le cobalt (Co), ou le manganèse (Mn); préparer un oxyde de métal de transition de sodium (250) en mélangeant une source de sodium (Na) avec l'oxyde de métal de transition, puis brûler; et préparer un matériau actif d'électrode positive en ajoutant un matériau de revêtement, qui contient au moins un élément parmi l'oxyde d'aluminium (Al2O3), l'oxyde de zinc (ZnO2), l'oxyde de manganèse (MnO2), l'oxyde de zirconium (ZrO2), ou le fluorure d'aluminium (AlF3), à l'oxyde de métal de transition de sodium (250), puis réaliser un broyage à sec.
PCT/KR2017/006027 2016-06-09 2017-06-09 Matériau actif d'électrode positive pour une batterie rechargeable au sodium, et son procédé de préparation Ceased WO2017213462A1 (fr)

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CN112436116A (zh) * 2020-11-18 2021-03-02 合肥国轩高科动力能源有限公司 一种铝掺杂ZnO膜包覆三元正极@C复合微球及其制备方法和应用
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CN115966701A (zh) * 2023-01-29 2023-04-14 上海轩邑新能源发展有限公司 金属氟化物改性正极材料及制备方法、正极及钠离子电池

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CN112436116A (zh) * 2020-11-18 2021-03-02 合肥国轩高科动力能源有限公司 一种铝掺杂ZnO膜包覆三元正极@C复合微球及其制备方法和应用
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