WO2013129831A1 - Birnessite sodique turbostratique et son procédé de préparation - Google Patents

Birnessite sodique turbostratique et son procédé de préparation Download PDF

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WO2013129831A1
WO2013129831A1 PCT/KR2013/001571 KR2013001571W WO2013129831A1 WO 2013129831 A1 WO2013129831 A1 WO 2013129831A1 KR 2013001571 W KR2013001571 W KR 2013001571W WO 2013129831 A1 WO2013129831 A1 WO 2013129831A1
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Prior art keywords
birnessite
turbostratic
ray
ray diffraction
plane
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PCT/KR2013/001571
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English (en)
Inventor
Jeong Soo Kim
Hee Young Sun
Young Shol Kim
Je Hyun Chae
Kyu Tae Lee
Seung Hee Woo
Min Choi
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Sk Innovation Co.,Ltd.
Unist Academy-Industry Research Corporation
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Publication of WO2013129831A1 publication Critical patent/WO2013129831A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
    • 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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D13/00—Compounds of sodium or potassium not provided for elsewhere
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
    • 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
    • H01M4/40—Alloys based on alkali metals
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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 turbostratic Na birnessite disordered along the C axis, a cathode active material for a Na secondary battery containing the turbostratic Na birnessite, a cathode for a Na secondary battery including the cathode active material, a Na secondary battery including the cathode, and a method for preparing the turbostratic Na birnessite.
  • Sodium secondary batteries are more attractive than the existing lithium secondary battery in view of preparation of electrode materials and competitive prices of batteries since Na resources are abundant and prices thereof are low.
  • one of the serious problems of the Na secondary batteries is that since Na ions are far larger than lithium ions, volume change by several tens of percents occurs in the procedure of insertion and desertion of Na ions within a structure of the electrode material, and thus the diffusive rate of the ions becomes slow, resulting in deteriorating battery speed characteristics.
  • the large volume change of an electrode may cause electrode degradation, and thus cycle characteristics of the battery may be deteriorated.
  • Patent Document 1 Japanese Patent Laid-Open Publication No. 2007-112674
  • Patent Document 2 Japanese Patent Laid-Open Publication No. 2009-209037
  • An object of the present invention is to provide a cathode active material for a Na secondary battery, capable of having improved reversibility at the time of insertion and desertion of Na ions, achieving smooth diffusion of Na ions having a large ion diameter, suppressing decomposition of an electrolysis to thereby prevent deterioration of characteristics thereof, having stable charging and discharging cycle characteristics, and enabling high-rate charging and discharging.
  • turbostratic Na birnessite disordered along the C axis where, in an X-ray diffraction pattern of the turbostratic Na birnessite, obtained by using Cu Ka ray, a full-width half-maximum (FWHM) of diffraction peak on ⁇ 001 ⁇ plane is 0.5°to 7°.
  • FWHM full-width half-maximum
  • the diffraction peak on ⁇ 002 ⁇ plane may not be present.
  • ⁇ 002 ⁇ plane may be 0.5°to 7°.
  • turbostratic Na birnessite may satisfy Relational expressions 1 to 3 below:
  • Ir ⁇ 200 ⁇ means intensity of X-ray diffraction peak on ⁇ 200 ⁇ plane in the X-ray diffraction pattern of Na birnessite not being disordered along the C axis, obtained by using Cu Ka ray;
  • Ir ⁇ 11-1 ⁇ means intensity of X-ray diffraction peak on ⁇ 11-1 ⁇ plane in the X-ray diffraction pattern of Na birnessite not being disordered along the C axis, obtained by using Cu Ka ray;
  • turbostratic Na birnessite may satisfy Chemical Formula 1 below:
  • turbostratic Na birnessite may satisfy Chemical Formula 2 below:
  • A is at least one element selected from Li, Mg, Ca, and H; and x is a real number of 0 ⁇ x ⁇ 0.7, y is a real number of 0 ⁇ y ⁇ 0.2, and z is a real number of 0 ⁇ z ⁇ 0.7).
  • the turbostratic Na birnessite may be a cathode active material for a Na secondary battery.
  • a cathode active material for a secondary battery including the turbostratic Na birnessite as described above.
  • the cathode active material may further include carbon.
  • the cathode active material may further include 5 wt% to 25 wt of carbon.
  • a cathode for a secondary battery including the cathode active material as described above.
  • a Na secondary battery including the cathode as described above.
  • a method for preparing the turbostratic Na birnessite as described above including: a) preparing Na birnessite of Chemical Formula 3 below; and b) partially removing water molecules contained in the Na birnessite prepared in the stage a), by applying heat energy thereto:
  • A is at least one element selected from Li, Mg, Ca, and H; and x is a real number of 0 ⁇ x ⁇ 0.7, p is a real number of 0.5 ⁇ p ⁇ 2, and q is a real number of 0 ⁇ q ⁇ 0.7).
  • stage b) may be carried out by heat treatment of 100°C to 300°C in the vacuum.
  • the turbostratic Na birnessite of the present invention can have a smooth diffusion path of Na ions, improved insertion/desertion reversibility of Na ions, and a high insertion/desertion rate, and prevent deterioration of characteristics due to side reactions with an electrolyte.
  • the cathode active material, the cathode, and the secondary battery of the present invention can have excellent charging/discharging cycle characteristics, high-rate of charging/discharging characteristics, excellent lifespan, and high charging/discharging capacity.
  • FIG. 1 is a graph showing X-ray diffraction results of Na oxide, Na birnessite, and turbostratic Na birnessite, prepared in Preparative Example;
  • FIG. 2 is a scanning electron microscope (SEM) image of turbostratic Na birnessite, prepared in Preparative Example
  • FIG. 3 is a graph showing thermal analysis results of Na birnessite and turbostratic
  • FIG. 4 is a graph showing the measured charging and discharging rate characteristics of a Na secondary battery, manufactured in Manufacturing Example
  • FIG. 5 is a graph showing the measured cycle characteristics of the Na secondary battery, manufactured in Manufacturing Example.
  • FIG. 6 is a graph showing the measured charging and discharging curves by cycles, of the Na secondary battery, manufactured in Manufacturing Example.
  • turbostratic Na birnessite disordered along the C axis has improved insertion and desertion reversibility of Na ions, retains stable charging and discharging characteristics, enables high-rate of charging and discharging, and has improved stability resulting from suppressing side reactions with an electrolyte, and thus completed the present invention.
  • turbostratic Na birnessite according to the present invention
  • turbostratic Na birnessite disordered along the C axis may include Na birnessite where, crystallographically C-axial transformation occurs in a crystalline layered structure, and may be defined by X-ray diffraction pattern characteristics.
  • the embodiment of the present invention may include turbostratic Na birnessite disordered along the C axis where, in an X-ray diffraction pattern thereof obtained by using Cu Ka ray, the full- width half-maximum (FWHM) of diffraction peak on ⁇ 001 ⁇ plane is 0.5°to 7° preferably 3°to 7° and more preferably 4°to 6°.
  • FWHM full- width half-maximum
  • the position of the diffraction peak on ⁇ 001 ⁇ plane may be changed depending on the degree of C-axis disordering of turbostratic Na birnessite.
  • the diffraction peak on ⁇ 001 ⁇ plane may include peaks positioned at 12° ⁇ 2 ⁇ 9° and more substantially, the diffraction peak on ⁇ 001 ⁇ plane may include peaks positioned at 14° ⁇ 20 ⁇ 17°.
  • the embodiment of the present invention may include turbostratic Na
  • birnessite disordered along the C axis where, in the X-ray diffraction pattern thereof obtained by using Cu Ka ray, the full-width half-maximum (FWHM) of a diffraction peak positioned at 12° ⁇ 20 ⁇ 19°is 0.5°to 7° preferably 3°to 7° and more preferably 4°to 6°.
  • FWHM full-width half-maximum
  • the X-ray diffraction pattern obtained by using Cu Ka ray may include powder X- ray diffraction results, include X-ray diffraction results measured by a 2 method at room temperature and normal pressure, and include X-ray diffraction results measured at a scan rate of 2°/min.
  • the turbostratic Na birnessite according to the embodiment of the present invention has a layered structure, and has the following advantages: the interlay er distance in the layered structure is wide so that the diffusion path of Na ions having a relatively large ion diameter can be effectively provided, which allows high-rate insertion and desertion of Na ions; the layered structure is a turbostratic structure so that the volume change occurring in the insertion and desertion procedure of Na ions can be minimized; and deterioration in diffusion of Na ions and decomposition of the electrolyte due to water molecules can be prevented even while wide interlayer distances due to the water molecules are maintained.
  • the meaning that diffraction peaks on a specific plane or specific planes family are not present in the X-ray diffraction pattern obtained by using Cu Ka ray is that only intensities corresponding to noise levels are detected in the X-ray diffraction pattern.
  • the position (2) and/or intensity of the diffraction peak on ⁇ 002 ⁇ plane may be changed depending on the degree of C-axis disordering of Na birnessite.
  • the change of intensity include a case where the diffraction peak on ⁇ 002 ⁇ plane is not present.
  • the turbostratic Na birnessite according to the embodiment of the present invention may include Na birnessite where the diffraction peak on ⁇ 002 ⁇ plane is not present in the X-ray diffraction pattern thereof obtained by using Cu Ka ray.
  • the turbostratic Na birnessite according to the embodiment of the present invention may include, substantially Na birnessite where the diffraction peak is not detected at 12° ⁇ 20 ⁇ 19° and more substantially Na birnessite where the diffraction peak is not detected at 14° ⁇ 20 ⁇ 17° in the X-ray diffraction pattern thereof obtained by using Cu Ka ray.
  • the turbostratic Na birnessite according to the embodiment of the present invention may include Na birnessite where the full-width half-maximum (FWHM) of diffraction peak on ⁇ 002 ⁇ plane is 0.5°to 7° preferably 3°to 7° and more preferably 4°to 6° in the X-ray diffraction pattern thereof obtained by using Cu Ka ray.
  • FWHM full-width half-maximum
  • Turbostratic Na birnessite may include Na birnessite where the full-width half-maximum (FWHM) of diffraction peak at substantially 12° ⁇ 2 ⁇ 19° and more substantially 14° ⁇ 20 ⁇ 17°is 0.5°to 7° preferably 3°to 7° and more preferably 4°to 6° in the X-ray diffraction pattern thereof obtained by using Cu Ka ray.
  • FWHM full-width half-maximum
  • the turbostratic Na birnessite according to the embodiment of the present invention may include Na birnessite satisfying Relational Expressions 1 to 3.
  • It ⁇ 11-1 ⁇ means intensity of X-ray diffraction peak on ⁇ 11-1 ⁇ plane in the X-ray diffraction pattern of turbostratic Na birnessite obtained by using Cu Ka ray
  • Ir ⁇ 11-1 ⁇ means intensity of X-ray diffraction peak on ⁇ 11-1 ⁇ plane in the X-ray diffraction pattern of Na birnessite not being disordered along the C axis, obtained by using Cu Ka ray.
  • It ⁇ 310 ⁇ means intensity of X-ray diffraction peak on ⁇ 310 ⁇ plane in the X-ray diffraction pattern of turbostratic Na birnessite obtained by using Cu ⁇ ray
  • Ir ⁇ 310 ⁇ means intensity of X-ray diffraction peak on ⁇ 310 ⁇ plane in the X-ray diffraction pattern of Na birnessite not being disordered along the C axis, obtained by using Cu Ka ray.
  • the Na birnessite not being disordered along the C axis contains 0.5 mole or more, and substantially, substantially 0.5 to 2 mole of moisture based on 1 mole of Na-Mn based oxide.
  • the Na birnessite not being disordered along the C axis may include Na
  • birnessite of Na x MnA k 0 2 ⁇ pH 2 0 (0 ⁇ x ⁇ 0.7, 0 ⁇ k ⁇ 0.7, 0.5 ⁇ p ⁇ 2, A at least one selected from Li, Mg, Ca and H), and the Na birnessite not being disordered along the C axis may include Na x Mn0 2 ⁇ pH 2 0 or Na x A z Mn0 2 ⁇ pH 2 0, when compared with Chemical Formula 1 or 2 below.
  • the Na birnessite not being disordered along the C axis may substantially include Na
  • the turbostratic Na birnessite according to the embodiment of the present invention may include turbostratic Na birnessite of Chemical Formula 1 below or Chemical Formula 2 below.
  • A is at least one element selected from Li, Mg, Ca and H; and x is a real number of 0 ⁇ x ⁇ 0.7, y is a real number of 0 ⁇ y ⁇ 0.2, and z is a real number of 0 ⁇ z ⁇ 0.7.
  • the turbostratic Na birnessite according to the embodiment of the present invention may be a cathode active material for a Na secondary battery.
  • the turbostratic Na birnessite according to the embodiment of the present invention can have excellent charging and discharging cycle characteristics as well as high-rate charging and dis- charging characteristics, and prevent deterioration of characteristics due to repetitive charging and discharging and deterioration of characteristics due to side reactions with the electrolyte contacted with the cathode active material.
  • the present invention may include a cathode active material for a secondary battery containing the turbostratic Na birnessite as described above.
  • the cathode active material according to the embodiment of the present invention may include a cathode active material for a Na secondary battery.
  • the cathode active material according to the embodiment of the present invention contains turbostratic Na birnessite, and thus can have excellent charging and discharging cycle characteristics as well as high-rate charging and discharging characteristics, suppress volume change due to charging and discharging, and prevent deterioration of characteristics due to repetitive charging and discharging and deterioration of characteristics due to side reactions with the electrolyte contacted with the cathode active material.
  • the cathode active material according to the embodiment of the present invention can have significantly excellent cycle stability and high-rate charging and discharging characteristics since, under the charging and discharging conditions of 0.5C and 2.0 ⁇ 4.0(V) voltage range, the change of specific capacity (mAh/g) at the time of repetition of 30 cycles of charging and discharging (SC30) based on specific capacity (mAh/g) at the time of repetition of 5 cycles of charging and discharging (SC5) ((SC5-SC30)/SC5*100 ) is within 99%.
  • the cathode active material according to the embodiment of the present invention has specific capacity of 50 mAh/g or higher under the charging and discharging conditions of 2.0 ⁇ 4.0(V) voltage range and high-rate current density of 2C rate.
  • the cathode active material according to the embodiment of the present invention may further contain carbon together with the turbostratic Na birnessite as described above, and specifically, the cathode active material may further contain 5 to 25 wt% of carbon. For this reason, electrical conductivity of electrodes and output characteristics of the battery can improved.
  • the present invention may include a cathode for a secondary battery containing the cathode active material as described above.
  • the cathode according to the embodiment of the present invention may include a cathode for a Na secondary battery.
  • the cathode according to the embodiment of the present invention may include the cathode active material as described above and current collectors.
  • a cathode active material layer may be formed by applying or coating a cathode active material on at least one surface of the current collector.
  • the present invention may include a Na secondary battery including the cathode as described above.
  • the Na secondary battery according to the embodiment of the present invention may include an anode containing Na, a cathode including a cathode active material containing the turbostratic Na birnessite as described above, and an electrolyte provided between the anode and the cathode, the electrolyte having ion conductivity with respect to Na ions.
  • the Na secondary battery according to the embodiment of the present invention may include an all-solid-state Na secondary battery where an anode containing Na, a cathode containing the above cathode active material, and an electrolyte are all solid states; may include a Na secondary battery including a liquid phase electrolyte; and may include a Na secondary battery including a cathode electrolytic liquid as well as an electrolyte.
  • the Na secondary battery according to the embodiment of the present invention may further include a separator, as necessary.
  • a cathode and/or an anode may be positioned within the electrolytic liquid so that Na ions conducted from a solid electrolyte can be effectively transferred to the active material.
  • the anode includes an anode active material containing Na
  • the electrolyte includes an organic solvent containing Na salt.
  • the anode may be Na metal
  • the Na salt contained in the electrolyte may be NaAsF 6 , NaPF 6 , NaC10 4 , NaB(Q H 5 ), NaAlCU, NaBr, NaBF 4 , or a mixture thereof
  • the organic solvent may be ethylene carbonate, dimethyl carbonate, methylethyl carbonate, propylene carbonate, or a mixture thereof.
  • the present invention is, of course, not limited by the kind of anode, the kind of electrolyte, or the structure of the battery.
  • the present invention provides a method for preparing the turbostratic Na birnessite as described above, the method including: a) preparing Na birnessite of Chemical Formula 3; and b) partially removing water molecules contained in the Na birnessite prepared in the stage a), by applying heat thereto.
  • A is at least one element selected from Li, Mg, Ca and H; and x is a real number of 0 ⁇ x ⁇ 0.7, p is a real number of 0.5 ⁇ p ⁇ 2, and q is a real number of 0 ⁇ q ⁇ 0.7.
  • Na birnessite not being disordered along the C axis which has the desired composition thereof (Na, A, Mn)
  • the prepared Na birnessite not being disordered along the C axis is made to be disordered along the C axis.
  • layer-structured Na birnessite having a predetermined interlayer distance is prepared, and through the stage b), the water molecules contained in the Na birnessite prepared in the stage a) are partially removed by using heat energy to prepare turbostratic Na birnessite disordered along the C axis.
  • the partially removing of the water molecules in the stage b) may include a case where, in the X-ray diffraction pattern obtained by using Cu Ka ray, the full-width half-maximum
  • the stage a) may be carried out by using a known method for preparing Na birnessite not being disordered along the C axis.
  • the stage a) may include: al) preparing Na-Mn complex oxide by using a precipitation method and heat treatment; and a2) mixing the complex oxide obtained in the stage al) and a solution containing Na salt to thereby prepare Na birnessite not being disordered along the C axis.
  • A is at least one element selected from Li, Mg, Ca and H; and x is a real number of 0 ⁇ x ⁇ 0.7, p is a real number of 0.5 ⁇ p ⁇ 2, and q is a real number of 0 ⁇ q ⁇ 0.7. )
  • the stage al) may be carried out by using a precipitation method.
  • a precipitation method using a precursor solution has advantages of easily preparing Na birnessite having desired materials and composition and easily and precisely controlling the composition of desired materials by regulation a mixing ratio of raw materials.
  • Na-Mn complex oxide may be prepared by weighting precursor materials including a Mn precursor and a Na precursor so as to satisfy the composition of Na birnessite to be prepared, mixing the precursor materials in a solvent to obtain a precipitate, and then performing heat treatment on the dried precipitate.
  • the heat treatment of powder may be carried out at 300°C to 500°C.
  • hydroxides hydroxides, halides, nitrogen compounds containing nitric acid, or a mixture thereof may be used.
  • Na birnessite is prepared by using the prepared complex oxide.
  • a Na precursor and/or a precursor of at least one element selected from Li, Mg, Ca and H (hereinafter, a metal precursor) are dissolved in a solvent, and then the complex oxide obtained in the stage al) is added to, stirred in, and allowed to react with the solution at a temperature of 10°C to 50°C, thereby preparing Na birnessite of Chemical Formula 3 by ion exchange between the existing Na and the desired composition, which are present in the complex oxide.
  • the source of heat energy in the stage b) may be at least one selected from electrical joule heat, heat by heat radiation, and heat from physical vibration, and as a non-limited example, electrical joule heat using a heating material having high electrical resistance may be used.
  • the partially removing of the water molecules in the stage b) may be carried out by performing heat treatment on the Na birnessite (Chemical Formula 3) of the stage a) at a temperature of 100°C to 300°C in the vacuum condition.
  • the vacuum in the stage b) may include a pressure of substantially 0.1 to 0.01 atm.
  • the stage b) is carried out in the vacuum so that the water molecules can be more partially and homogeneously removed in a short time.
  • the temperature for partially removing the water molecules may include 100°C to 300°C, as described above. If the temperature is too low, the time necessary for diffusing and emitting the water molecules out of Na birnessite particles may be increased, resulting in decreasing productivity, and water molecules may be non-homogeneously removed between a region neighboring Na birnessite surface and an inner center region of Na birnessite. If the temperature is too high, Na-Mn oxide may be partially formed instead of the Na birnessite disordered along the C axis, and also, the water molecules may be non-homogeneously removed between a region neighboring Na birnessite surface and an inner center region of Na birnessite.
  • the removing degree of water molecules may be controlled by using at least one factor selected from temperature, pressure, and time for carrying out the stage b ⁇ .
  • the Na birnessite (Chemical Formula 3) is subjected to heat treatment at the foregoing temperature and pressure ranges for 1 to 12 hours, thereby preparing tur- bostratic Na birnessite disordered along the C axis due to the partial removal of water molecules, where, in an X-ray diffraction pattern obtained by using Cu Ka ray, the full- width half-maximum (FWHM) of diffraction peak on (001) plane has a value of 0.5°to 7°
  • the prepared Na oxide (NaMn0 2 ) and NaN0 3 were input in the distilled water at a mole ratio of 1 :20 (150ml of distilled water per 0.3g of Na oxide), followed by stirring for 10 hours. After stirring, particles were separated and obtained by using filtering, and the obtained particles were dried at a temperature of 30°C for 1 hour, thereby preparing Na birnessite, Nao. 44 Mn0 2 ⁇ 0.7H 2 O.
  • the prepared Na birnessite (Nao. 44 Mn0 2 ⁇ 0.7H 2 O) was inserted into a vacuum oven, and then subjected to heat treatment at a pressure of O.Olatm and a temperature of 120°C for 10 hours, thereby preparing turbostratic Na birnessite, Nao .44 Mn0 2 ⁇ 0.05H 2 O.
  • NaMn0 2 having crystallinity was prepared by a precipitating method, and Na birnessite having a uniform interlayer distance, that is, Na birnessite not being disordered along the C axis was manufactured by mixing with a sodium nitrate solution.
  • FIG. 2 is a scanning electron microscope (SEM) image of the prepared turbostratic Na birnessite, and it can be confirmed that the particle size was about 200-300 nm.
  • FIG. 3 shows residual amounts of water remaining in respective structures of the Na birnessite and the turbostratic Na birnessite prepared in the preparative example, which are measured through heat analysis (TGA). It can be confirmed that the water in the structure was rapidly removed at a temperature of about 100°C, and 10wt% of water (corresponding to 0.7H 2 O) remained in the structure in the case where heat treatment was not carried out in the vacuum and lwt% of (corresponding to 0.05H 2 O) water remained in the structure in the case where heat treatment was carried out.
  • TGA heat analysis
  • An active material, a conducting material (carbon black (super P)), and a binder (polyvinylidene fluoride; PVdF) were mixed at a weight ratio of 8:1 : 1, and then the mixture was dissolved in an N-methyl pyrrolidone (NMP), to thereby prepare a slurry.
  • NMP N-methyl pyrrolidone
  • the prepared slurry was coated on an aluminum foil, and then dried in a vacuum oven at 120°C for 10 hours, to form an electrode.
  • the thus formed electrode, Na metal as a counter electrode, and 0.8M NaOCViethylene carbonate + diethylene carbonate, 1: 1 vol. ratio) as an electrolyte were placed in a glove box, to manufacture a battery.
  • FIG. 4 shows evaluation results on rate characteristics of the manufactured Na secondary battery. 4V-2V of charging and discharging was performed at C/20 to 20C. As shown in FIG. 4, the Na secondary battery exhibited reversible capacity of 145 mAh/g or higher at current density of C/20, reversible capacity of 90 mAh/g or higher at 1C, and reversible capacity of 50 mAh/g or higher at current density of 2C. Therefore, it was confirmed that high reversible capacity was maintained even at high current density.
  • FIG. 5 shows measurement results of cycle characteristics where 4V-2V of charging and discharging was performed at C/20 or C/2. It was confirmed that the change of specific capacity (mAh/g) at the time of repetition of 30 cycles of charging and discharging (SC30) based on specific capacity (mAh/g) at the time of repetition of 5 cycles of charging and discharging (SC5) at C/2 ((SC5-SC30)/SC5*100%) was 99%. In the case where charging and discharging was performed at C/2, Coulomb efficiency after 5 cycles of charging and discharging was stabilized to about 97%, and this high Coulomb efficiency confirmed that Na ions were reversibly inserted into or deserted from the structure.
  • FIG. 6 shows charging and discharging curves by cycles where 4V-2V charging and discharging was carried out at C/20.
  • the first cycle of discharging with respect to Nao. 4 Mn0 2 ⁇ 0.05H 2 O, since the oxidation number of Mn is 4 + , a Na ion is additively inserted by an electrochemical reaction, and therefore, the oxidation number of each Mn becomes 3 + .
  • 0.44Na present in the existing birnessite structure as well as the electrochemically inserted Na ion come out together, and thus in the case of the first cycle, the charging capacity is higher than the discharging capacity.
  • an electrochemical reaction where all Na ions are reversibly inserted or deserted occurred.

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  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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Abstract

L'invention porte sur une birnessite sodique turbostratique désordonnée le long de l'axe C, caractérisée en ce que, dans un diagramme de diffraction des rayons X de la birnessite sodique turbostratique, obtenu à l'aide du rayonnement Cu-Kα, la largeur totale à mi-hauteur (LTMH) du pic de diffraction sur le plan {001} est de 0,5° à 7°.
PCT/KR2013/001571 2012-02-27 2013-02-27 Birnessite sodique turbostratique et son procédé de préparation WO2013129831A1 (fr)

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JP2013230965A (ja) * 2012-04-02 2013-11-14 Toray Fine Chemicals Co Ltd 二酸化マンガンおよびそれを含む硬化型組成物
WO2020227927A1 (fr) * 2019-05-14 2020-11-19 浙江裕源储能科技有限公司 Matériau actif d'électrode positive pour batterie aqueuse, son procédé de préparation et batterie zinc-ion en solution aqueuse
CN116565183A (zh) * 2023-07-06 2023-08-08 宁德时代新能源科技股份有限公司 正极活性材料及其制备方法、正极极片、电池和用电装置

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KR102586288B1 (ko) * 2021-01-08 2023-10-18 고려대학교 산학협력단 양극 활물질
KR102536228B1 (ko) * 2021-01-08 2023-05-23 고려대학교 산학협력단 양극 활물질

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JP2001332258A (ja) * 2000-05-22 2001-11-30 Nippon Telegr & Teleph Corp <Ntt> 複酸化物電極材料、その製造方法及びそれを用いた電池
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JP2009206085A (ja) * 2008-01-28 2009-09-10 Sumitomo Chemical Co Ltd 正極活物質およびナトリウム二次電池、ならびにオリビン型リン酸塩の製造方法
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JP2001332256A (ja) * 2000-05-22 2001-11-30 Nippon Telegr & Teleph Corp <Ntt> 電極材料、その製造方法及びそれを用いた電池
JP2001332258A (ja) * 2000-05-22 2001-11-30 Nippon Telegr & Teleph Corp <Ntt> 複酸化物電極材料、その製造方法及びそれを用いた電池
KR20070100918A (ko) * 2005-02-07 2007-10-12 산요덴키가부시키가이샤 정극 및 비수 전해질 이차 전지
JP2009206085A (ja) * 2008-01-28 2009-09-10 Sumitomo Chemical Co Ltd 正極活物質およびナトリウム二次電池、ならびにオリビン型リン酸塩の製造方法
KR20110017850A (ko) * 2008-04-07 2011-02-22 카네기 멜론 유니버시티 나트륨 이온계 수성 전해질 전기화학 2차 에너지 저장 장치

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013230965A (ja) * 2012-04-02 2013-11-14 Toray Fine Chemicals Co Ltd 二酸化マンガンおよびそれを含む硬化型組成物
WO2020227927A1 (fr) * 2019-05-14 2020-11-19 浙江裕源储能科技有限公司 Matériau actif d'électrode positive pour batterie aqueuse, son procédé de préparation et batterie zinc-ion en solution aqueuse
CN116565183A (zh) * 2023-07-06 2023-08-08 宁德时代新能源科技股份有限公司 正极活性材料及其制备方法、正极极片、电池和用电装置
CN116565183B (zh) * 2023-07-06 2023-11-17 宁德时代新能源科技股份有限公司 正极活性材料及其制备方法、正极极片、电池和用电装置

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