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WO2014077663A1 - Matériau actif d'anode pour pile secondaire au sodium et son procédé de fabrication - Google Patents

Matériau actif d'anode pour pile secondaire au sodium et son procédé de fabrication Download PDF

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Publication number
WO2014077663A1
WO2014077663A1 PCT/KR2013/010521 KR2013010521W WO2014077663A1 WO 2014077663 A1 WO2014077663 A1 WO 2014077663A1 KR 2013010521 W KR2013010521 W KR 2013010521W WO 2014077663 A1 WO2014077663 A1 WO 2014077663A1
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WO
WIPO (PCT)
Prior art keywords
secondary battery
active material
sodium
sodium secondary
cathode active
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2013/010521
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English (en)
Korean (ko)
Inventor
선양국
오승민
장민우
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Industry University Cooperation Foundation IUCF HYU
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Industry University Cooperation Foundation IUCF HYU
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Publication date
Application filed by Industry University Cooperation Foundation IUCF HYU filed Critical Industry University Cooperation Foundation IUCF HYU
Priority to CN201380068762.9A priority Critical patent/CN104904047A/zh
Priority claimed from KR1020130140911A external-priority patent/KR20140064681A/ko
Publication of WO2014077663A1 publication Critical patent/WO2014077663A1/fr
Priority to US14/716,362 priority patent/US20150333325A1/en
Anticipated expiration legal-status Critical
Priority to US15/993,174 priority patent/US10781110B2/en
Ceased legal-status Critical Current

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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
    • 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
    • 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
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
    • 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 cathode active material for a sodium secondary battery and a method for manufacturing the same, and more particularly, to a cathode active material for a sodium secondary battery having a new O 3 structure and a method for manufacturing the same.
  • a lithium ion secondary battery using a nonaqueous electrolyte solution in which an electrolyte salt is dissolved in a nonaqueous solvent and moving lithium ions between a positive electrode and a negative electrode so that charge and discharge is performed is widely used.
  • Lithium ion batteries using an intercalation reaction of lithium ions using lithium transition metal oxides are commercially available as positive electrode materials.
  • lithium included in the lithium ion battery is expensive, there is a need for a battery having a lower cost and a higher capacity.
  • Japanese Unexamined Patent Application Publication No. 2007-287661 has a positive electrode made of a composite metal oxide obtained by firing a raw material having a composition ratio of Na, Mn and Co (Na: Mn: Co) of 0.7: 0.5: 0.5 and a negative electrode made of sodium metal. Secondary batteries are described in detail. Further, Japanese Patent Laid-Open No. 2005-317511 discloses ⁇ -NaFeO 2 having a hexagonal crystal (layered rock salt) crystal structure as a sum metal oxide, specifically, by mixing Na 2 O 2 and Fe 3 O 4 . This composite metal oxide was obtained by baking at 600-700 degreeC in air. However, the conventional sodium secondary battery cannot be said to have sufficient lifespan characteristics, that is, a discharge capacity retention rate when repeated charging and discharging.
  • An object of the present invention is to provide a cathode active material for a sodium secondary battery of a novel composition with improved life characteristics and a method of manufacturing the same in order to solve the problems of the prior art as described above.
  • the present invention to solve the above problems Na x [Ni y Fe z Mn 1-yz ] O 2 (0.8 ⁇ x ⁇ 1.2, 0.05 ⁇ y ⁇ 0.9, 0.05 ⁇ z ⁇ 0.9, 0.05 ⁇ 1-yz ⁇ 0.9), which provides a cathode active material for a sodium secondary battery having an O 3 crystal structure.
  • the cathode active material for sodium secondary battery according to the present invention is a spherical particle having a particle size of 5 to 15 ⁇ m, and the particle size distribution is monodisperse.
  • the cathode active material for sodium secondary battery according to the present invention is characterized in that 2 ⁇ in XRD shows three peaks in a range of 30 ° to 40 °.
  • the cathode active material for a sodium secondary battery according to the present invention is characterized in that the peak (104) having a main peak in the range of 2 ⁇ in the range of 40 ° to 45 ° in XRD.
  • the cathode active material for sodium secondary battery according to the present invention is characterized in that the tap density is 1.0 to 2.4 g / cc.
  • the present invention also provides
  • It provides a method for producing a cathode active material for sodium secondary battery according to the present invention comprising a heat treatment step.
  • the cathode active material precursor for sodium secondary battery is characterized in that represented by any one of the following formulas (1) to (3).
  • the cathode active material precursor for sodium secondary battery is preferably prepared by the co-precipitation method, such as the application No. 10-2012-0130824 of the inventors filed on November 19, 2012.
  • the second pH adjusting agent in the step (b) is characterized in that selected from the group consisting of ammonium oxalate, NaOH and KOH.
  • the pH in the reactor is adjusted to 9 to 11, and the ammonium oxalate is used as the second pH adjusting agent.
  • the pH in the reactor is characterized in that to adjust to 6.5 to 11.
  • the nickel salt in the step (c) is selected from the group consisting of nickel sulfate, nickel nitrate, nickel chloride, and nickel fluoride, and the iron salt is iron sulfate, It is selected from iron nitrate, iron chloride, iron fluoride, and the manganese salt is characterized in that it is selected from manganese sulfate, manganese nitrate, manganese chloride, manganese fluoride.
  • the complexing agent in the step (c) is an aqueous ammonia solution (NH 4 OH), ammonium sulfate ((NH 4 ) 2 SO 4 ), ammonium nitrate (NH 4 NO 3 ) and first ammonium phosphate ((NH 4 ) 2 HPO 4 ).
  • the ratio of the concentration of the complexing agent and the concentration of the aqueous solution of the transition metal compound in the step (c) is 0.8 to 1.2.
  • the sodium compound is characterized in that one of sodium carbonate, sodium nitrate, sodium acetate, sodium hydroxide, sodium hydroxide hydrate, sodium oxide or a combination thereof.
  • the sodium compound per 1 mol of the cathode active material precursor for sodium secondary battery is mixed in a ratio of 1.0 to 1.5 mol It is characterized by.
  • the heat treatment step is characterized in that the heat treatment at 800 °C to 1000 °C.
  • the sodium secondary battery positive electrode active material according to the present invention is structurally stable in the O 3 structure unlike the prior art, and thus the sodium battery including the sodium secondary battery positive electrode active material according to the present invention exhibits excellent life characteristics.
  • 1 to 4 show SEM pictures of the precursor prepared in the embodiment of the present invention.
  • 5 to 8 show the results of measuring the particle size distribution of the precursor prepared in the embodiment of the present invention.
  • Figure 9 shows the results of measuring the XRD of the precursor prepared in the embodiment of the present invention.
  • Figure 10 shows the results of measuring the particle size distribution of the precursor prepared in the embodiment of the present invention.
  • the reactor was charged with 4 L of distilled water and stirred at 1000 rpm while adding ammonia to maintain the reactor internal pH at 7 and the internal temperature at 50 ° C. 4 M NaOH solution was added as a second pH adjusting agent to adjust the pH inside the reactor to 10.2 and maintained for 30 minutes.
  • NiSO 4 ⁇ 6H 2 O, FeSO 4 ⁇ 7H 2 O, MnSO 4 ⁇ 5H 2 O as an aqueous solution of a transition metal compound were mixed in an equivalent ratio, and introduced into the reactor together with NH 4 OH as a complexing agent, A precursor was prepared.
  • Example 2 Except for adjusting the mixing ratio of the transition metal compound aqueous solution in Example 1 as shown in Table 1 below as shown in Table 1 Ni 0.25 Fe 0.35 Mn 0.4 (OH) 2 , Ni 0.25 Fe 0.5 Mn The precursors of Examples 2-4 were prepared, represented by 0.25 (OH) 2 and Ni 0.15 Fe 0.35 Mn 0.5 (OH) 2 .
  • Example 1 Ni 0.25 Fe 0.25 Mn 0.5 (OH) 2
  • Example 2 Ni 0.25 Fe 0.35 Mn 0.4 (OH) 2
  • Example 3 Ni 0.25 Fe 0.5 Mn 0.25 (OH) 2
  • Example 4 Ni 0.15 Fe 0.35 Mn 0.5 (OH) 2
  • Example 5 Ni 0.25 Fe 0.5 Mn 0.25 C 2 O 4
  • Example 6 Ni 0.2 Fe 0.6 Mn 0.2 C 2 O 4
  • Example 7 Ni 0.17 Fe 0.66 Mn 0.17 C 2 O 4
  • Example 8 Ni 0.2 Fe 0.55 Mn 0.25 C 2 O 4
  • Example 9 Ni 0.3 Fe 0.45 Mn 0.25 C 2 O 4
  • Example 10 Ni 0.35 Fe 0.4 Mn 0.25 C 2 O 4
  • Example 11 Ni 0.25 Fe 0.5 Mn 0.25 ) 3 O 4
  • Example 12 (Ni 0.25 Fe 0.25 Mn 0.5 ) 3 O 4
  • the particle size distribution of the precursors prepared in Examples 1 to 4 was measured and shown in FIGS. 5 to 8. 5 to 8, it can be seen that the particle size of the precursor particles is monodisperse.
  • Example 5 In the same manner as in Example 1 except that the pH inside the reactor was adjusted to 7 using ammonia as the first pH regulator, and the pH inside the reactor was adjusted to 7 using an aqueous 0.5M ammonium oxalate solution as the second pH regulator.
  • the precursors of Examples 5 to 10 of the composition as shown in Table 1 were prepared.
  • the internal pH of the reactor was adjusted to 7 using ammonia as the first pH regulator, and the internal pH of the reactor was adjusted to 9.2 by adding 4 M NaOH as the second pH regulator (Ni).
  • Particle size distributions of the precursors prepared in Examples 11 and 12 were measured and shown in FIGS. 13 and 14. It can be seen from FIG. 13 and FIG. 14 that the particle size distribution is monodisperse.
  • the results of measuring XRD of the cathode active materials of Examples 13 to 16 are shown in FIGS. 15 to 18, and the results of XRD measurement of the cathode active materials of Examples 17 to 19 are shown in FIG. 19.
  • the results of measuring XRD with respect to the positive electrode active materials of 20 to 22 are shown in FIG. 20, and the results of measuring XRD with respect to the positive electrode active materials of Examples 23 and 24 are shown in FIGS. 21 and 22.
  • the cathode active material for the sodium secondary battery prepared in Examples of the present invention exhibits three peaks in a range of 30 ° to 40 ° in 2RD in XRD, and O 3 in a range of 40 ° to 45 ° in 2 ⁇ . It can be seen that the (104) main peak, which is characteristic of the crystal structure, appears.
  • Composite metal oxide E1 acetylene black (manufactured by Denki Chemical Co., Ltd.) as a conductive material, and PVDF (PolyVinylidene DiFluoride Polyflon) as a binder are used as the composite metal oxide E1.
  • Conductive material: Binder 85: 10: 5 (weight ratio), each weighed so as to have a composition.
  • the composite metal oxide and acetylene black are sufficiently mixed with an agate mortar, and N-methyl-2-pyrrolidone (NMP: manufactured by Tokyo Kasei Kogyo Co., Ltd.) is appropriately added to the mixture, followed by addition.
  • PVDF was added to the mixture to make it uniform and slurryed.
  • An anode prepared with aluminum foil facing downward was placed in the recess of the lower part of the coin cell (manufactured by Hosen Kabushiki Co., Ltd.), followed by 1 M NaClO 4 / propylene carbonate + 2 vol% fluoroethylene carbonate as a nonaqueous electrolyte.
  • a sodium secondary battery was produced by combining (FEC, Fluoro Ethylene Carbonate), a polypropylene porous membrane (thickness 20 ⁇ m) as a separator, and sodium metal as a negative electrode.
  • the charge and discharge characteristics of the sodium secondary battery including the active materials of Examples 13 to 19 and 23 made of the precursors of Examples 1 to 7 and 11 were measured and the results are shown in Table 2 below.
  • Example 13 Ni 0.25 Fe 0.25 Mn 0.5 (OH) 2 precursor / Na 95%, sintered at 970 ° C / 24h, 4.3V 155.5 mAh / g 94.1%
  • Example 2 Ni 0.25 Fe 0.35 Mn 0.4 (OH) 2 Precursor / Na 98%, 900 ° C / 24h Sintered, 4.3V 180.1 mAh / g 101.2% Ni 0.25 Fe 0.35 Mn 0.4 (OH) 2 precursor / Na 98%, sintered at 930 ° C / 24h, 4.3V 176.3 mAh / g 100.9% Ni 0.25 Fe 0.35 Mn 0.4 (OH) 2 Precursor / Na 98%, 970 ° C / 24h Sintered, 4.3V 166.2 mAh / g 95.4%
  • Example 3 Example 15 Ni 0.25 Fe 0.5 Mn 0.25 (OH) 2 / Na 98%,
  • Example 13 155.5 mAh / g 130.2 mAh / g 83.7% 106.9 mAh / g 96.0 mAh / g 89.8%
  • Example 2 Example 14 180.1 mAh / g 141.3 mAh / g 78.5% 125.6 mAh / g 117.5 mAh / g 93.6% 176.3 mAh / g 140.5 mAh / g 76.7% 125.9 mAh / g 117.8 mAh / g 93.6% 166.2 mAh / g 124.6 mAh / g 75.0% 107.7 mAh / g 95.1 mAh / g 88.3%
  • Example 3 Example 15 130.7 mAh / g 122.0 mAh / g 93.3% 114.3 mAh / g 105.4 mAh / g 92
  • the sodium secondary battery including the active material having the O 3 crystal structure according to the present invention shows that the charge and discharge efficiency up to 20 cycles has a very high lifespan characteristic of about 90%.
  • the charge and discharge characteristics of the sodium secondary battery including the active material prepared in Examples 13 to 16 are measured in FIGS. 23 to 26, and the charge and discharge characteristics and lifetime characteristics of the sodium secondary batteries of Examples 17 to 19 were measured.
  • the results are shown in FIGS. 27 and 28, and the results of measuring charge and discharge characteristics and life characteristics of the sodium secondary battery including the active materials prepared in Examples 17 and 20 to 22 are shown in FIGS. 29 to 31.
  • 32 and 33 show the results of measuring charge and discharge characteristics and lifespan characteristics of a sodium secondary battery including an active material having an O 3 crystal structure formed at 23 and 24.
  • the sodium secondary battery positive electrode active material according to the present invention is structurally stable in the O 3 structure unlike the prior art, and thus the sodium battery including the sodium secondary battery positive electrode active material according to the present invention exhibits excellent life characteristics.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention concerne un matériau actif d'anode pour une pile secondaire au sodium ainsi que son procédé de fabrication. Elle concerne, plus précisément, un matériau actif d'anode doté d'une nouvelle structure O3 et destiné à une pile secondaire au sodium, ainsi que son procédé de fabrication. Le matériau actif d'anode pour pile secondaire au sodium selon la présente invention présente une structure O3, il est donc structurellement stable contrairement aux matériaux actifs d'anode classiques. Par voie de conséquence, une pile au sodium comprenant le matériau actif d'anode pour pile secondaire au sodium selon la présente invention présente d'excellentes caractéristiques de durabilité.
PCT/KR2013/010521 2012-11-19 2013-11-19 Matériau actif d'anode pour pile secondaire au sodium et son procédé de fabrication Ceased WO2014077663A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201380068762.9A CN104904047A (zh) 2012-11-19 2013-11-19 钠二次电池用正极活性材料及其制备方法
US14/716,362 US20150333325A1 (en) 2012-11-19 2015-05-19 Manufacturing method of positive active material precursor for sodium rechargeable batteries, positive active material precursor for sodium rechargeable batteries made by the same, and manufacturing method of positive active material for sodium rechargeable batteries, positive active material for sodium rechargeable batteries made by the same
US15/993,174 US10781110B2 (en) 2012-11-19 2018-05-30 Manufacturing method of positive active material precursor for sodium rechargeable batteries, positive active material precursor for sodium rechargeable batteries made by the same, and manufacturing method of positive active material for sodium rechargeable batteries, positive active material for sodium rechargeable batteries made by the same

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2012-0131027 2012-11-19
KR20120131027 2012-11-19
KR1020130140911A KR20140064681A (ko) 2012-11-19 2013-11-19 나트륨 이차전지용 양극활물질 및 이의 제조 방법
KR10-2013-0140911 2013-11-19

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Cited By (8)

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Publication number Priority date Publication date Assignee Title
CN104953172A (zh) * 2015-07-24 2015-09-30 上海中聚佳华电池科技有限公司 一类钠离子电池正极材料及其制备方法、钠离子电池
US10196280B2 (en) 2014-05-22 2019-02-05 Faradion Limited Compositions containing doped nickelate compounds
CN111628164A (zh) * 2020-05-22 2020-09-04 兰州理工大学 一种钠离子电池正极材料及制备方法
US10781110B2 (en) 2012-11-19 2020-09-22 Iucf-Hyu(Industry-University Cooperation Foundation Hanyang University) Manufacturing method of positive active material precursor for sodium rechargeable batteries, positive active material precursor for sodium rechargeable batteries made by the same, and manufacturing method of positive active material for sodium rechargeable batteries, positive active material for sodium rechargeable batteries made by the same
US10978708B2 (en) 2014-01-09 2021-04-13 Faradion Limited Doped nickelate compounds
CN114920306A (zh) * 2022-06-29 2022-08-19 荆门市格林美新材料有限公司 正极材料前驱体、正极材料、其制备方法和钠离子电池
CN115000399A (zh) * 2022-05-25 2022-09-02 西安交通大学 一种类球状钠离子电池正极材料及其制备方法和钠离子电池
EP4545484A1 (fr) * 2023-10-24 2025-04-30 Hubei Rt Advanced Materials Group Company Limited Matériau de cathode de batterie sodium-ion et son procédé de préparation et son application

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WO2012060295A1 (fr) * 2010-11-05 2012-05-10 学校法人東京理科大学 Oxyde métallique composite, procédé de fabrication de l'oxyde métallique composite, matière active positive pour une batterie secondaire au sodium, électrode positive pour une batterie secondaire au sodium et batterie secondaire au sodium

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10781110B2 (en) 2012-11-19 2020-09-22 Iucf-Hyu(Industry-University Cooperation Foundation Hanyang University) Manufacturing method of positive active material precursor for sodium rechargeable batteries, positive active material precursor for sodium rechargeable batteries made by the same, and manufacturing method of positive active material for sodium rechargeable batteries, positive active material for sodium rechargeable batteries made by the same
US10978708B2 (en) 2014-01-09 2021-04-13 Faradion Limited Doped nickelate compounds
US10196280B2 (en) 2014-05-22 2019-02-05 Faradion Limited Compositions containing doped nickelate compounds
US10399863B2 (en) 2014-05-22 2019-09-03 Faradion Limited Doped nickelate materials
US10550007B2 (en) 2014-05-22 2020-02-04 Faradion Limited Compositions containing doped nickelate compounds
CN104953172A (zh) * 2015-07-24 2015-09-30 上海中聚佳华电池科技有限公司 一类钠离子电池正极材料及其制备方法、钠离子电池
CN111628164A (zh) * 2020-05-22 2020-09-04 兰州理工大学 一种钠离子电池正极材料及制备方法
CN115000399A (zh) * 2022-05-25 2022-09-02 西安交通大学 一种类球状钠离子电池正极材料及其制备方法和钠离子电池
CN114920306A (zh) * 2022-06-29 2022-08-19 荆门市格林美新材料有限公司 正极材料前驱体、正极材料、其制备方法和钠离子电池
CN114920306B (zh) * 2022-06-29 2024-03-26 荆门市格林美新材料有限公司 正极材料前驱体、正极材料、其制备方法和钠离子电池
EP4545484A1 (fr) * 2023-10-24 2025-04-30 Hubei Rt Advanced Materials Group Company Limited Matériau de cathode de batterie sodium-ion et son procédé de préparation et son application

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