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WO2020235909A1 - Matériau actif de cathode pour batterie secondaire au sodium dopé au calcium, et batterie secondaire au sodium le comprenant - Google Patents

Matériau actif de cathode pour batterie secondaire au sodium dopé au calcium, et batterie secondaire au sodium le comprenant Download PDF

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WO2020235909A1
WO2020235909A1 PCT/KR2020/006510 KR2020006510W WO2020235909A1 WO 2020235909 A1 WO2020235909 A1 WO 2020235909A1 KR 2020006510 W KR2020006510 W KR 2020006510W WO 2020235909 A1 WO2020235909 A1 WO 2020235909A1
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active material
secondary battery
sodium
sodium secondary
cathode active
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Korean (ko)
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선양국
유태연
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Industry University Cooperation Foundation IUCF HYU
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Industry University Cooperation Foundation IUCF HYU
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Priority claimed from KR1020200058855A external-priority patent/KR102466222B1/ko
Publication of WO2020235909A1 publication Critical patent/WO2020235909A1/fr
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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 secondary battery, and more particularly, to a sodium secondary battery.
  • a secondary battery refers to a battery that can be used repeatedly because it can be charged as well as discharged.
  • lithium ions contained in the positive electrode active material are transferred to the negative electrode through the electrolyte and then inserted into the layered structure of the negative electrode active material (charging), and then the lithium ions inserted into the layered structure of the negative electrode active material are again It works through the principle of returning to the anode (discharge).
  • These lithium secondary batteries are currently commercialized and used as small power sources such as mobile phones and notebook computers, and are predicted to be usable as large power sources such as hybrid vehicles, and their demand is expected to increase.
  • the composite metal oxide which is mainly used as a cathode active material in lithium secondary batteries, contains rare metal elements such as lithium, and thus there is a fear that it cannot meet the increasing demand. Accordingly, research on a sodium secondary battery in which the supply amount is abundant and cheap sodium is used as a cathode active material is being conducted.
  • the problem to be solved by the present invention is to improve the cycle characteristics through improvement of the positive electrode active material used in the sodium secondary battery.
  • an aspect of the present invention provides a cathode active material for a sodium secondary battery.
  • the positive electrode active material for a sodium secondary battery may be represented by Formula 1 below.
  • M includes at least one of Co and Fe
  • x may have a value of 0.003 or more and 0.05 or less.
  • the positive electrode active material may have an O3 structure.
  • y may have a value of 0.4 or more.
  • y may have a value of 0.4 or more and 0.8 or less.
  • the Ca element may be doped in the sodium layer.
  • the positive electrode active material may maintain its structure at a voltage exceeding 4.0V.
  • the positive electrode active material may maintain its structure at a voltage of more than 4.0V and less than 4.3.
  • another aspect of the present invention provides a method of manufacturing the positive electrode active material.
  • the method of preparing the positive electrode active material is to supply and mix a metal mixed aqueous solution containing nickel salt and manganese salt and an aqueous solution containing an ammonium ion supply to a reaction tank, and supply a caustic alkali aqueous solution for coprecipitation to produce a metal complex hydroxide.
  • Step (first step) And mixing sodium salt and calcium salt with the metal composite hydroxide and heat-treating to prepare a positive electrode active material (second step).
  • the metal mixed solution may further include at least one of a cobalt salt and an iron salt.
  • the ammonium ion supply may be at least one of ammonia, ammonium sulfate, or ammonium chloride.
  • the caustic alkaline aqueous solution may be an aqueous sodium hydroxide or potassium hydroxide solution.
  • the sodium salt may be sodium hydroxide or sodium carbonate.
  • the calcium salt may be calcium hydroxide.
  • the mixing ratio of the metal complex hydroxide, sodium salt and calcium salt may be 1:1 to 1.1:0.005 to 0.03 in molar ratio.
  • the sodium secondary battery may include a positive electrode including the positive electrode active material; A negative electrode positioned opposite to the positive electrode; And an electrolyte positioned between the positive electrode and the negative electrode.
  • the sodium secondary battery may be driven at a voltage of more than 4.0V and less than 4.3.
  • the positive electrode active material has 03 crystal structure, and calcium is doped in the sodium layer of sodium transition metal oxide to stabilize the structure in the charging/discharging process, thereby improving battery performance, and driving even at a high voltage exceeding 4.0V This is possible.
  • FIG. 1 is a schematic diagram of a sodium secondary battery according to an embodiment of the present invention.
  • FIG. 2 shows an X-ray diffraction spectrum of the positive electrode active material prepared in any one of Preparation Examples 1A, 1B, and 1C of the positive electrode active material of the present invention, and Comparative Example 1 of the positive electrode active material.
  • FIG 3 is a graph showing changes in lattice parameters and volumes according to the Ca doping concentration of the positive electrode active material prepared in any one of Preparation Examples 1A, 1B, and 1C of the positive electrode active material of the present invention.
  • Example 4 is a graph showing initial charge/discharge characteristics of half-cells according to Example 1A, 1B, and 1C of half-cells of the present invention, and Comparative Example 1 of half-cells.
  • Example 5 is a graph showing discharge capacity and coulomb efficiency according to the number of cycles of half-cells according to Example 1A, 1B, and 1C of half-cells of the present invention and Comparative Example 1 of half-cells.
  • FIG. 6 shows an X-ray diffraction spectrum of an anode after driving the half cells according to the half cell Preparation Example 1A and the half cell Comparative Example 1 at a rate of 0.5C for 100 cycles.
  • FIG. 7 is a graph showing initial charge/discharge characteristics of half cells according to Manufacturing Example 2 and Comparative Example 2 of the half cell of the present invention.
  • FIG. 8 is a graph showing discharge capacity according to the number of cycles of the half cells according to Manufacturing Example 2 and Comparative Example 2 of the half cell of the present invention.
  • FIG. 9 is a graph showing initial charge/discharge characteristics of half cells according to Manufacturing Example 3 and Comparative Example 3 of half cells of the present invention.
  • FIG 10 is a graph showing discharge capacity according to the number of cycles of the half cells according to Manufacturing Example 3 and Comparative Example 3 of the half cell of the present invention.
  • FIG. 11 is a graph showing initial charging and discharging characteristics of half cells according to Manufacturing Example 4 and Comparative Example 4 of half cells of the present invention.
  • FIG. 12 is a graph showing the discharge capacity according to the number of cycles of the half cells according to Manufacturing Example 4 and Comparative Example 4 of the half cell of the present invention.
  • FIG. 13 is a graph showing initial charging and discharging characteristics of half cells according to Manufacturing Example 5 and Comparative Example 5 of half cells of the present invention.
  • the cathode active material for a sodium secondary battery according to an embodiment of the present invention may be represented by the following Formula 1.
  • M includes at least one of Co and Fe
  • the cathode active material for a sodium secondary battery has a crystal structure of O3 structure, specifically a hexagonal O3 structure, and a Ca element may be doped in the sodium layer.
  • the doping content (x) of Ca may be 0.003 to 0.05 in molar ratio, specifically 0.005 to 0.03, and more specifically 0.007 to 0.015, and in the above range, the crystal structure of the active material is stably maintained during the charging/discharging process. The characteristics and rate control characteristics are excellent at the same time.
  • y can have a value of 0.4 or more.
  • the content of nickel among the transition metals Ni, Mn, Co, and Fe may be 40% or more, and in this case, an increase in the capacity of the active material can be expected.
  • the crystal structure may become somewhat unstable during the charging and discharging process.
  • the sodium layer is doped with Ca, it is possible to suppress the crystal structure from becoming unstable. As a result, it is possible to obtain an increase in capacity and an improvement in life characteristics at the same time.
  • y may have a value of 0.4 or more and 0.8 or less.
  • Fe 3 + may be oxidized to Fe 4 + at high voltage, resulting in unstable crystal structure.
  • the crystal structure is doped with Ca in the sodium layer. It can suppress becoming unstable.
  • another aspect of the present invention provides a method of manufacturing the cathode active material for the sodium secondary battery.
  • a metal mixed aqueous solution containing nickel salt and manganese salt and an aqueous solution containing an ammonium ion supply are supplied to a reaction tank and mixed, and a caustic alkaline aqueous solution is mixed. Supplying a co-precipitation reaction to prepare a metal composite hydroxide (first step); And
  • It may include a step (second step) of preparing a positive electrode active material by mixing sodium salt and calcium salt with the metal complex hydroxide and heat treatment.
  • the first step is a step of preparing a metal composite hydroxide.
  • the preparation of the metal composite hydroxide may be performed by a coprecipitation process commonly used in the art.
  • a metal mixed aqueous solution containing nickel salt and manganese salt and an aqueous solution containing an ammonium ion supply are supplied to the reaction tank and mixed, and the pH is maintained in the range of 11 to 13 based on a liquid temperature of 25°C.
  • a caustic aqueous alkali solution is supplied to form a reaction solution, and the metal composite hydroxide particles are co-precipitated in the reaction solution while maintaining the oxygen concentration of the atmosphere in contact with the open surface of the reaction solution in the reaction tank at 0.2 vol% or less.
  • at least one of a cobalt salt and an iron salt may be further added to the metal mixed aqueous solution.
  • the metal composite hydroxide obtained in the co-precipitation step is represented by the following formula (2), and almost matches the atomic ratio of the supplied metal mixed aqueous solution.
  • M includes at least one of Co and Fe
  • the atomic ratio of nickel, cobalt, manganese, and iron can be in the range of formula (2).
  • the salt concentration of the metal mixed aqueous solution may be 1 mol/L to 2.2 mol/L in total of each salt. If the salt concentration of the metal mixed aqueous solution is less than 1 mol/L, the salt concentration is low, and the crystal of the metal complex hydroxide may not grow sufficiently. If it exceeds 2.2 mol/L, the saturation concentration at room temperature is exceeded. , There is a problem in that it is impossible to form particles of a desired size because there are many fine particles due to the large number of crystal nuclei.
  • the nickel salt, manganese salt, cobalt salt and iron salt that can be used are not particularly limited, but at least one of sulfate, nitrate, and chloride is preferable.
  • the pH of the reaction solution can be controlled in the range of 11 to 13, specifically 11 to 12 based on the liquid temperature of 25°C.
  • the pH is less than 11, the particles of the metal composite hydroxide become coarse, and when the pH exceeds 13, the coprecipitation rate of the metal composite hydroxide becomes slow, and fine particles increase. If there are too many fine particles, the specific surface area increases, and there is a problem that they are sintered to generate agglomerated powder during the production of the positive electrode active material.
  • the pH of the reaction solution can be controlled by supplying a caustic alkaline aqueous solution.
  • the caustic alkaline aqueous solution is not particularly limited, and for example, an aqueous alkali metal hydroxide solution such as sodium hydroxide and potassium hydroxide can be used.
  • the alkali metal hydroxide may be added directly to the reaction solution, but it is preferable to add it as an aqueous solution from the viewpoint of easy pH control.
  • the method of adding the aqueous caustic alkali solution is also not particularly limited, and the reaction solution can be added so that the pH is in the range of 11 to 13 with a pump capable of controlling a flow rate such as a metering pump while sufficiently stirring.
  • the ammonium ion concentration in the reaction solution is preferably in the range of 5 to 20 g/L.
  • the ammonium ion concentration is less than 5 g/L, the solubility of nickel, cobalt, and manganese in the reaction solution is low, and there is a problem that crystal growth of the hydroxide particles is not sufficient.
  • the ammonium ion concentration exceeds 20 g/L, there is a problem in that the coprecipitation rate decreases and productivity deteriorates.
  • the ammonium ion concentration can be controlled by adding an ammonium ion supply to the reaction solution.
  • the ammonium ion supply body is not particularly limited, but is preferably at least one of ammonia, ammonium sulfate, and ammonium chloride.
  • the oxygen concentration of the atmosphere in the reaction tank in contact with the open surface of the reaction solution to 0.2 vol% or less.
  • the oxygen concentration in the reaction tank can be controlled by, for example, supplying an inert gas such as nitrogen gas (N 2 ) into the reaction tank.
  • the temperature of the reaction solution it is preferable to maintain the temperature of the reaction solution at 20°C to 70°C. Thereby, crystals of the metal composite hydroxide can be grown.
  • the prepared metal composite hydroxide may be further subjected to subsequent washing, filtering, and drying processes.
  • the second step is a step of preparing a positive electrode active material by mixing sodium salt and calcium salt with the metal complex hydroxide and heat treatment.
  • the prepared metal composite hydroxide may be mixed with sodium salt and calcium salt, followed by heat treatment, thereby preparing the positive electrode active material of Formula 1 above.
  • sodium hydroxide or sodium carbonate may be used as the sodium salt
  • calcium hydroxide may be used as the calcium salt
  • the mixing ratio of the metal complex hydroxide, sodium salt, and calcium salt may be 1:1 to 1.1:0.005 to 0.03 in a molar ratio, and specifically 1:1 to 1.05:0.01 to 0.03.
  • the heat treatment may be performed at 600 to 850°C for 20 to 30 hours.
  • another aspect of the present invention provides a sodium secondary battery including the positive electrode active material.
  • FIG. 1 is a schematic diagram of a sodium secondary battery according to an embodiment of the present invention.
  • the sodium secondary battery includes a positive electrode 10 including a positive electrode active material; A cathode 20 positioned opposite to the anode; And an electrolyte 30 positioned between the anode 10 and the cathode 20.
  • a cathode material can be obtained by mixing a cathode active material, a conductive material, and a binder.
  • the positive electrode active material may have a composition represented by Formula 1 described above.
  • the conductive material may be a carbon material such as natural graphite, artificial graphite, coke, carbon black, carbon nanotubes, and graphene.
  • the conductive material may be contained in an amount of 2 to 15 parts by weight, specifically 8 to 12 parts by weight or 5 to 6 parts by weight, based on 100 parts by weight of the positive electrode active material.
  • the binder is a thermoplastic resin such as polyvinylidene fluoride, polytetrafluoroethylene, tetrafluoroethylene, vinylidene fluoride copolymer, fluorine resin such as propylene hexafluoride, and/or polyolefin resin such as polyethylene and polypropylene. Can include.
  • the binder may be contained in an amount of 2 to 9 parts by weight, specifically 4 to 7 parts by weight, and more specifically 5 to 6 parts by weight, based on 100 parts by weight of the positive electrode active material.
  • the positive electrode 10 may be formed by applying a positive electrode material on the positive electrode current collector.
  • the positive electrode current collector may be a conductor such as Al, Ni, or stainless steel. Applying the positive electrode material on the positive electrode current collector may be performed by pressure molding or a method of making a paste using an organic solvent, etc., and then applying the paste onto the current collector and pressing to fix it.
  • organic solvent examples include amines such as N,N-dimethylaminopropylamine and diethyltriamine; Ethers such as ethylene oxide and tetrahydrofuran; Ketone systems such as methyl ethyl ketone; Esters such as methyl acetate; It may be an aprotic polar solvent such as dimethylacetamide and N-methyl-2-pyrrolidone.
  • Applying the paste onto the positive electrode current collector may be performed using, for example, a gravure coating method, a slit die coating method, a knife coating method, or a spray coating method.
  • Anode active materials include metals, metal alloys, metal oxides, metal fluorides, metal sulfides, and natural graphite, artificial graphite, coke, carbon black, carbon nanotubes, and graphite that can de-insert Na ions or cause conversion reactions. It can also be formed using carbon materials such as fins.
  • a negative electrode material can be obtained by mixing a negative electrode active material, a conductive material, and a binder.
  • the conductive material may be a carbon material such as natural graphite, artificial graphite, coke, carbon black, carbon nanotubes, and graphene.
  • the binder is a thermoplastic resin such as polyvinylidene fluoride, polytetrafluoroethylene, tetrafluoroethylene, vinylidene fluoride copolymer, fluorine resin such as propylene hexafluoride, and/or polyolefin resin such as polyethylene and polypropylene.
  • a negative electrode material may be applied on the negative electrode current collector to form the negative electrode 20.
  • the negative electrode current collector may be a conductor such as Al, Ni, or stainless steel. Applying the negative electrode material on the positive electrode current collector may be performed by pressure molding or a method of making a paste using an organic solvent, etc., and then applying the paste onto the current collector and pressing to fix it.
  • organic solvent examples include amines such as N,N-dimethylaminopropylamine and diethyltriamine; Ethers such as ethylene oxide and tetrahydrofuran; Ketone systems such as methyl ethyl ketone; Esters such as methyl acetate; It may be an aprotic polar solvent such as dimethylacetamide and N-methyl-2-pyrrolidone.
  • Applying the paste onto the negative electrode current collector may be performed using, for example, a gravure coating method, a slit die coating method, a knife coating method, or a spray coating method.
  • Electrolyte 30 may be NaClO 4 , NaPF 6 , NaAsF 6 , NaSbF 6 , NaBF 4 , NaCF 3 SO 3 , NaN(SO 2 CF 3 ) 2 , lower aliphatic sodium carboxylate, NaAlCl 4 , and the like, It is also possible to use a mixture of two or more. Among these, it is preferable to use an electrolyte containing fluorine. Further, the electrolyte can be dissolved in an organic solvent and used as a non-aqueous electrolyte.
  • organic solvent for example, propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, isopropyl methyl carbonate, vinylene carbonate, 4- Carbonates such as trifluoromethyl-1,3-dioxolan-2-one and 1,2-di(methoxycarbonyloxy)ethane; 1,2-dimethoxyethane, 1,3-dimethoxypropane, pentafluoropropylmethylether, 2,2,3,3-tetrafluoropropyldifluoromethylether, tetrahydrofuran, 2-methyltetrahydro Ethers such as furan; Esters such as methyl formate, methyl acetate, and ⁇ -butyrolactone; Nitriles such as acetonitrile and butyronitrile; Amides such as N,N-dimethylformamide and N,N-dimethylacetamide; Carbamates such as 3-methyl-2-o
  • a solid electrolyte may be used.
  • the solid electrolyte may be an organic solid electrolyte such as a polyethylene oxide polymer compound, a polymer compound including at least one of a polyorganosiloxane chain, or a polyoxyalkylene chain.
  • a so-called gel-type electrolyte in which a non-aqueous electrolyte is supported on a polymer compound can also be used.
  • an inorganic solid electrolyte it is also possible to use an inorganic solid electrolyte. In some cases, the safety of a sodium secondary battery can be further improved by using these solid electrolytes.
  • the solid electrolyte may serve as a separator to be described later, and in that case, a separator may not be required.
  • a separator 40 may be disposed between the anode and the cathode.
  • a separator may be a material having a form such as a porous film, a nonwoven fabric, or a woven fabric made of a material such as a polyolefin resin such as polyethylene or polypropylene, a fluorine resin, or a nitrogen-containing aromatic polymer.
  • the thickness of the separator is preferably thinner as long as the mechanical strength is maintained from the viewpoint that the bulk energy density of the battery is increased and the internal resistance is decreased.
  • the thickness of the separator may be generally 5 to 200 ⁇ m, and more specifically 5 to 40 ⁇ m.
  • the electrode group After forming an electrode group by sequentially stacking a positive electrode, a separator, and a negative electrode, if necessary, the electrode group is rolled up and stored in a battery can, and a sodium secondary battery can be manufactured by impregnating the electrode group with a non-aqueous electrolyte.
  • the electrode group after forming an electrode group by stacking a positive electrode, a solid electrolyte, and a negative electrode, if necessary, the electrode group may be rolled up and stored in a battery can to manufacture a sodium secondary battery.
  • the thus manufactured sodium secondary battery maintains the structure of the positive electrode active material even at a high voltage of more than 4.0V, specifically more than 4.0V and less than 4.3V, so that high-speed charging of a large-capacity battery is possible.
  • a metal aqueous solution having a concentration of 2 M with a molar ratio of nickel sulfate and manganese sulfate of 50:50 is 0.187 liters/hour
  • an ammonia solution having a concentration of 10.5 M is 0.043 liters/hour
  • a sodium hydroxide solution having a concentration of 4 M is 0.196 liters/hour [Ni 0 . 5 Mn 0 . 5 ](OH) 2
  • a metal composite hydroxide was prepared.
  • the prepared [Ni 0 . 5 Mn 0 . 5 ](OH) 2 The metal composite hydroxide was washed with water, filtered, and dried in a vacuum dryer at 110° C. for 12 hours.
  • the metal complex hydroxide and sodium carbonate (Na 2 CO 3 ) were mixed at a molar ratio of 1:1.05, heated at a temperature increase rate of 2°C/min, and fired at 800°C for 24 hours to Na[Ni 0.5 Mn 0.5 ]O 2 anode
  • An active material powder was obtained.
  • N 2 gas is supplied to the reactor at a rate of 5 liters/minute and stirred at 350 rpm while maintaining the temperature of the reactor at 45 °C.
  • a metal composite hydroxide was prepared.
  • the prepared [Ni 0 . 6 Co 0 . 2 Mn 0 . 2 ](OH) 2 The metal complex hydroxide was washed with water, filtered, and dried in a vacuum dryer at 110° C. for 12 hours. After mixing the metal complex hydroxide and sodium hydroxide (NaOH) at a molar ratio of 1:1.05, heating at a temperature increase rate of 2°C/min and firing at 660°C for 24 hours, Na[Ni 0.6 Co 0.2 Mn 0.2 ]O 2 positive electrode An active material powder was obtained.
  • N 2 gas is supplied to the reactor at a rate of 5 liters/minute and stirred at 350 rpm while maintaining the temperature of the reactor at 45 °C. I did.
  • the prepared [Ni 0 . 7 Co 0 . 1 Mn 0 . 2 ](OH) 2 The metal complex hydroxide was washed with water, filtered, and dried in a vacuum dryer at 110° C. for 12 hours. After mixing the metal complex hydroxide and sodium hydroxide (NaOH) at a molar ratio of 1:1.05, heating at a temperature increase rate of 2°C/min and firing at 660°C for 24 hours, Na[Ni 0.7 Co 0.1 Mn 0.2 ]O 2 positive electrode An active material powder was obtained.
  • N 2 gas is supplied to the reactor at a rate of 5 liters/minute and stirred at 350 rpm while maintaining the temperature of the reactor at 45 °C. I did.
  • the prepared [Ni 0 . 8 Co 0 . 1 Mn 0 . 1 ](OH) 2 The metal composite hydroxide was washed with water, filtered, and dried in a vacuum dryer at 110° C. for 12 hours. After mixing the metal complex hydroxide and sodium hydroxide (NaOH) at a molar ratio of 1:1.05, heating at a temperature increase rate of 2°C/min and firing at 660°C for 24 hours, Na[Ni 0.8 Co 0.1 Mn 0.1 ]O 2 positive electrode An active material powder was obtained.
  • N 2 gas is supplied to the reactor at a rate of 5 liters/minute and stirred at 350 rpm while maintaining the temperature of the reactor at 45 °C. I did.
  • the prepared [Ni 0 . 4 Fe 0 . 2 Mn 0 . 4 ](OH) 2 The metal complex hydroxide was washed with water, filtered, and dried in a vacuum dryer at 110° C. for 12 hours.
  • the metal complex hydroxide and sodium carbonate (Na 2 CO 3 ) were mixed at a molar ratio of 1:1.05, heated at a temperature increase rate of 2 °C/min, and fired at 800 °C for 24 hours to Na[Ni 0.4 Fe 0.2 Mn 0.4 ]O 2
  • a cathode active material powder was obtained.
  • FIG. 2 shows an X-ray diffraction spectrum of the positive electrode active material prepared in any one of Preparation Examples 1A, 1B, and 1C of the positive electrode active material, and Comparative Example 1 of the positive electrode active material.
  • FIG. 3 is a graph showing changes in lattice parameters and volumes according to the Ca doping concentration of the positive electrode active material prepared in any one of the positive electrode active material Preparation Examples 1A, 1B, and 1C, and the positive electrode active material Comparative Example 1.
  • FIG. 3 is a graph showing changes in lattice parameters and volumes according to the Ca doping concentration of the positive electrode active material prepared in any one of the positive electrode active material Preparation Examples 1A, 1B, and 1C, and the positive electrode active material Comparative Example 1.
  • NMP N-Methyl-2-Pyrrolidone
  • a half-cell was prepared using a non-aqueous electrolyte containing electrolyte NaPF 6 (0.5M) in a mixed organic solvent.
  • the half cells using the positive electrode active materials obtained in Preparation Examples 1A, 1B, 1C, 2, 3, 4 and 5 of the positive electrode active material are named as Half Cell Preparation Examples 1A, 1B, 1C, 2, 3, 4 and 5, respectively ,
  • Positive electrode active material The half cells using the positive electrode active materials obtained in Comparative Examples 1 to 5 were respectively named as half cell Comparative Examples 1 to 5.
  • FIG. 4 is a graph showing the initial charge/discharge characteristics of half cells according to half-cell Preparation Examples 1A, 1B, and 1C, and half-cell Comparative Example 1
  • FIG. 5 is a graph showing half-cell Preparation Examples 1A, 1B, and 1C, And a graph showing discharge capacity and coulomb efficiency according to the number of cycles of half cells according to Comparative Example 1 of half cells.
  • the initial discharge capacity is slightly lower than when it is not doped, but even if the number of cycles increases, the discharge capacity retention rate is more excellent.
  • the initial discharge capacity was somewhat lower, but the discharge capacity retention rate was more excellent when the number of cycles increased.
  • FIG. 6 shows an X-ray diffraction spectrum of an anode after driving the half cells according to the half cell Preparation Example 1A and the half cell Comparative Example 1 at a rate of 0.5C for 100 cycles.
  • FIG. 7 is a graph showing the initial charge/discharge characteristics of half cells according to Preparation Example 2 and Comparative Example 2 of half cells
  • FIG. 8 is a graph showing the number of cycles of the half cells according to Preparation Example 2 and Comparative Example 2 of half cells. It is a graph showing the discharge capacity according to the.
  • FIG. 9 is a graph showing the initial charge/discharge characteristics of half cells according to Preparation Example 3 and Comparative Example 3 of half cells
  • FIG. 10 is a graph showing the number of cycles of the half cells according to Preparation Example 3 and Comparative Example 3 of half cells. It is a graph showing the discharge capacity according to.
  • FIG. 11 is a graph showing the initial charging and discharging characteristics of half-cells according to half-cell Preparation Example 4 and half-cell Comparative Example 4
  • FIG. 12 is a graph showing the number of cycles of half-cells according to half-cell Preparation Example 4 and half-cell Comparative Example 4 It is a graph showing the discharge capacity according to.
  • FIG. 13 is a graph showing initial charging and discharging characteristics of half-cells according to half-cell Preparation Example 5 and half-cell Comparative Example 5
  • FIG. 14 is a graph showing the number of cycles of half-cells according to half-cell Preparation Example 5 and half-cell Comparative Example 5 It is a graph showing the discharge capacity according to.

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Abstract

La présente invention concerne un matériau actif de cathode pour une batterie secondaire au sodium, le matériau actif de cathode ayant une structure cristalline de 03, et du calcium est dopé sur une couche de sodium d'un oxyde de métal de transition de sodium de façon à stabiliser une structure pendant un processus de charge/décharge, et ainsi la performance de la batterie est améliorée et la conduite est possible même avec une tension élevée supérieure à 4,0 V.
PCT/KR2020/006510 2019-05-17 2020-05-18 Matériau actif de cathode pour batterie secondaire au sodium dopé au calcium, et batterie secondaire au sodium le comprenant Ceased WO2020235909A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20190057777 2019-05-17
KR10-2019-0057777 2019-05-17
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CN114005969A (zh) * 2021-09-29 2022-02-01 浙江钠创新能源有限公司 一种金属离子掺杂的改性钠离子材料及其制备方法与应用
CN114005969B (zh) * 2021-09-29 2023-09-15 浙江钠创新能源有限公司 一种金属离子掺杂的改性钠离子材料及其制备方法与应用
CN115986106A (zh) * 2023-02-09 2023-04-18 广东凯金新能源科技股份有限公司 正极材料及其制备方法和钠离子电池
CN116646514A (zh) * 2023-04-23 2023-08-25 湖南钠能时代科技发展有限公司 一种惰性金属离子掺杂镍铁锰酸钠三元正极材料及其制备方法
CN116544417A (zh) * 2023-07-06 2023-08-04 宁波容百新能源科技股份有限公司 正极活性材料及其制备方法、正极片和钠离子电池
CN116544417B (zh) * 2023-07-06 2024-03-19 宁波容百新能源科技股份有限公司 正极活性材料及其制备方法、正极片和钠离子电池
WO2025007779A1 (fr) * 2023-07-06 2025-01-09 宁波容百新能源科技股份有限公司 Matériau actif d'électrode positive et son procédé de préparation, feuille d'électrode positive et batterie sodium-ion

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