WO2020059902A1 - Matériau de cathode ayant une couche de revêtement d'oxyde de silicium formée sur celui-ci, cathode le comprenant, batterie au sodium-ion et son procédé de fabrication - Google Patents

Matériau de cathode ayant une couche de revêtement d'oxyde de silicium formée sur celui-ci, cathode le comprenant, batterie au sodium-ion et son procédé de fabrication Download PDF

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Publication number
WO2020059902A1
WO2020059902A1 PCT/KR2018/011046 KR2018011046W WO2020059902A1 WO 2020059902 A1 WO2020059902 A1 WO 2020059902A1 KR 2018011046 W KR2018011046 W KR 2018011046W WO 2020059902 A1 WO2020059902 A1 WO 2020059902A1
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WO
WIPO (PCT)
Prior art keywords
sodium ion
ion battery
silicon oxide
metal oxide
positive electrode
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Ceased
Application number
PCT/KR2018/011046
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English (en)
Korean (ko)
Inventor
조우석
김경수
정구진
유지상
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Korea Electronics Technology Institute
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Korea Electronics Technology Institute
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Priority to PCT/KR2018/011046 priority Critical patent/WO2020059902A1/fr
Publication of WO2020059902A1 publication Critical patent/WO2020059902A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a sodium ion battery and a method for manufacturing the same, and more specifically, a positive electrode material having a silicon oxide coating layer on which the silicon oxide is coated on the surface of the positive electrode material to improve battery characteristics, the positive electrode and the sodium ion battery comprising the same, and It relates to a manufacturing method.
  • Lithium secondary batteries have been put into practical use as batteries that can be charged and discharged in a compact, lightweight and high capacity, and are used in portable electronic and communication devices such as small video cameras, mobile phones, and notebook computers.
  • the lithium secondary battery is composed of a positive electrode, a negative electrode, and an electrolyte, and it charges and discharges because lithium ions from the positive electrode material are inserted into the negative electrode material by charging and resorption when discharged. This is possible.
  • sodium ion battery a sodium-based secondary battery (hereinafter referred to as “sodium ion battery”) using sodium instead of lithium. Since sodium has a rich resource reserve, if a secondary battery using sodium instead of lithium can be manufactured, the secondary battery can be manufactured at a low cost.
  • the Ni-Fe-Mn-based positive electrode material that does not contain expensive Co has an O 3 structure and is known to be capable of securing a high reversible capacity.
  • the Ni-Fe-Mn-based positive electrode material has a disadvantage in that battery characteristics related to output and life characteristics are significantly reduced.
  • Ni-Fe-Mn-based positive electrode material The disadvantage of the Ni-Fe-Mn-based positive electrode material is that a sodium residue is present on the surface of the positive electrode material, and when exposed to the atmosphere, the amount is significantly increased, thereby acting as a factor that deteriorates battery characteristics.
  • an object of the present invention is to reduce the resistance by surface by-products such as sodium residue through surface modification of the positive electrode material to secure a stable lifespan characteristic, thereby forming a positive electrode material having a silicon oxide coating layer capable of improving battery characteristics, and a positive electrode comprising the same. And a sodium ion battery and a method for manufacturing the same.
  • the present invention provides a positive electrode material having a silicon oxide coating layer formed on its surface, a positive electrode and a sodium ion battery comprising the same, and a method for manufacturing the same.
  • the forming step may include adding tetraethyl orthosilicate (TEOS) to the metal oxide; Converting the TEOS into silicon oxide by heat treatment; And forming the silicon oxide coating layer by coating the silicon oxide on the surface of the metal oxide.
  • TEOS tetraethyl orthosilicate
  • the TEOS 0.5 to 5 wt% may be added to the metal oxide 95 to 99.5 wt%.
  • the present invention also provides a positive electrode for a sodium ion battery comprising the positive electrode material.
  • the present invention provides a sodium ion battery comprising the positive electrode.
  • the present invention by forming a silicon oxide coating layer on the surface of the metal oxide having the O 3 layered structure, reducing the resistance by surface by-products such as sodium residue that may be present on the surface of the anode material to secure a stable life characteristics Battery characteristics can be improved.
  • FIG. 1 is a flow chart according to a method of manufacturing a positive electrode material for a sodium ion battery according to the present invention.
  • FIG. 2 is a detailed flow chart showing the steps of forming the silicon oxide coating layer of FIG. 1.
  • FIG. 3 is a photograph showing a cathode material for a sodium ion battery according to a comparative example.
  • FIG. 4 is a photograph showing a cathode material for a sodium ion battery according to an embodiment.
  • FIG. 5 is a photograph showing the results of SEM-EDS analysis of the positive electrode material for a sodium ion battery according to the embodiment.
  • FIG. 6 is a graph showing charge and discharge characteristics of a sodium ion battery using a cathode material according to Comparative Examples and Examples.
  • FIG. 7 is a graph showing output characteristics of a sodium ion battery using a positive electrode material according to Comparative Examples and Examples.
  • FIG. 8 is a graph showing the life characteristics of a sodium ion battery using a cathode material according to Comparative Examples and Examples.
  • FIG. 1 is a flow chart according to a method of manufacturing a positive electrode material for a sodium ion battery according to the present invention.
  • FIG. 2 is a detailed flow chart showing the steps of forming the silicon oxide coating layer of FIG. 1.
  • Step S10 will be described in detail as follows.
  • the metal oxide is manufactured in powder form.
  • the precursor mixture is fired to prepare a metal oxide having an O 3 layered structure.
  • the firing may be performed at 760 to 960 ° C for 14 to 34 hours.
  • the input amount of Na 2 CO 3 may be adjusted so that the sodium content of the metal oxide is less than one.
  • Step S30 will be described in detail as follows.
  • TEOS tetraethyl orthosilicate
  • step S31 proceeds as a solution process, and after preparing a mixed solution in which metal oxide and TEOS are added, the mixture is stirred for a certain time at room temperature so that the metal oxide and TEOS can be uniformly mixed. Then, the mixture is filtered and dried to remove the solvent, whereby TEOS adsorbed powder can be obtained on the surface of the metal oxide.
  • step S35 the silicon oxide is coated on the surface of the metal oxide to form a silicon oxide coating layer. That is, the TEOS adsorbed on the surface of the metal oxide is converted into silicon oxide and formed into a silicon oxide coating layer by putting the powder adsorbed on the surface of the metal oxide into the heat treatment facility and then heat treating it in an air atmosphere.
  • a positive electrode material according to Examples and Comparative Examples was prepared as follows.
  • the positive electrode material according to the comparative example is Na 0 having a Na content of 0.9 . 9 (Ni 0.25 Fe 0.25 Mn 0.5 ) O 2 was used. Synthesis of positive electrode material according to a comparative example was prepared by precursor (Ni 0. 25 Fe 0. 25 Mn 0. 5) After mixing ratio quantitative with OH 2 and Na 2 CO 3, 24 sigan baked at 860 °C.
  • the positive electrode material according to the embodiment was prepared by additionally performing a process of forming a silicon oxide coating layer as follows for the positive electrode material according to the comparative example.
  • TEOS 1 wt% was added to 70 mL of absolute ethanol to the weight of the metal oxide, followed by stirring for about 10 minutes to prepare a coating solution. After stirring the prepared coating solution for 1 hour at room temperature, the solvent was dried at 80 degrees after filtering to prepare a powder with TEOS adsorbed on the surface of the metal oxide.
  • the powder adsorbed on the surface of the metal oxide was heat-treated in a tube electric furnace to prepare a positive electrode material according to an embodiment.
  • the heat treatment was performed in an air atmosphere at 700 degrees for 4 hours.
  • TEOS adsorbed on the surface of the metal oxide is converted to silicon oxide to form a silicon oxide coating layer.
  • CR2032 coin cells were prepared. At this time, Na: metal as the cathode, glass fiber (glass fiber) as the separator, and electrolyte: 1 M of NaClO 4 dissolved in EC: PC (1: 1) was used.
  • 3 is a photograph showing a cathode material for a sodium ion battery according to a comparative example.
  • 4 is a photograph showing a cathode material for a sodium ion battery according to an embodiment.
  • 3 and 4 are SEM pictures, and (b) is an enlarged picture of (a).
  • FIG. 5 is a photograph showing the results of SEM-EDS analysis of the positive electrode material for a sodium ion battery according to the embodiment.
  • the positive electrode material according to the embodiment includes Na, Ni, Fe, Mn, and Si, and Si is uniformly distributed on the surface of the positive electrode material.
  • the positive electrode material according to the embodiment can be confirmed that a silicon oxide coating layer of a silicon oxide material is formed on the surface.
  • FIG. 6 is a graph showing charge and discharge characteristics of a sodium ion battery using a cathode material according to Comparative Examples and Examples.
  • the discharge capacity of the sodium ion battery according to the comparative example is 161 mAh / g, it can be seen that the discharge capacity of the sodium ion battery according to the embodiment is improved to 175 mAh / g.
  • Table 1 is a measurement value of the output characteristics at 0.1C to 5C of a sodium ion battery using a cathode material according to Comparative Examples and Examples.
  • Na 0.9. represents a comparative example
  • H.TEOS represents an example.
  • FIG. 7 is a graph showing output characteristics of a sodium ion battery using a positive electrode material according to Comparative Examples and Examples.
  • the embodiment shows excellent output characteristics.
  • the overvoltage of the sodium ion battery according to the embodiment is significantly improved and the capacity is increased. This means that the sodium ion battery according to the embodiment exhibits better properties in terms of energy density (Wh).
  • Table 2 is a value obtained by measuring the capacity retention rate after one, 50, and 100 cycles of the sodium ion battery using the positive electrode material according to Comparative Examples and Examples. At this time, the evaluation was performed at room temperature cycle characteristics at 0.5C to confirm whether the life was improved.
  • FIG. 8 is a graph showing the life characteristics of a sodium ion battery using a cathode material according to Comparative Examples and Examples.
  • the comparative example is 82%, and the example is 88%, which improves the lifespan characteristics with a silicon oxide coating.
  • the present invention by forming a silicon oxide coating layer on the surface of a metal oxide having an O 3 layered structure, the resistance by surface by-products such as sodium residues that may be present on the surface of the anode material is reduced, through which the sodium ion battery It is possible to improve the battery characteristics by securing the stable life characteristics of.

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

Abstract

La présente invention concerne : un matériau de cathode ayant une couche de revêtement d'oxyde de silicium formée sur celui-ci, pouvant améliorer les caractéristiques de batterie d'une batterie au sodium-ion ; une cathode et une batterie au sodium-ion, comprenant chacune celui-ci ; et un procédé de fabrication associé. La présente invention concerne un matériau de cathode pour une batterie au sodium-ion, comprenant : un oxyde métallique ayant une structure en couches O3 représentée par Na1-xMeO2 (dans laquelle Me représente Ni, Fe et Mn, et 0<x<1) ; et une couche de revêtement d'oxyde de silicium formée par revêtement d'oxyde de silicium sur la surface de l'oxyde métallique.
PCT/KR2018/011046 2018-09-19 2018-09-19 Matériau de cathode ayant une couche de revêtement d'oxyde de silicium formée sur celui-ci, cathode le comprenant, batterie au sodium-ion et son procédé de fabrication Ceased WO2020059902A1 (fr)

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PCT/KR2018/011046 WO2020059902A1 (fr) 2018-09-19 2018-09-19 Matériau de cathode ayant une couche de revêtement d'oxyde de silicium formée sur celui-ci, cathode le comprenant, batterie au sodium-ion et son procédé de fabrication

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Application Number Priority Date Filing Date Title
PCT/KR2018/011046 WO2020059902A1 (fr) 2018-09-19 2018-09-19 Matériau de cathode ayant une couche de revêtement d'oxyde de silicium formée sur celui-ci, cathode le comprenant, batterie au sodium-ion et son procédé de fabrication

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115911327A (zh) * 2022-11-28 2023-04-04 广东凯金新能源科技股份有限公司 钠离子正极材料及其制备方法、二次电池
CN117117158A (zh) * 2023-10-23 2023-11-24 浙江帕瓦新能源股份有限公司 一种改性钠离子电池正极材料及其制备方法、钠离子电池

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KR20100120138A (ko) * 2008-02-04 2010-11-12 스미또모 가가꾸 가부시키가이샤 복합 금속 산화물 및 나트륨 이차 전지
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KR20160056319A (ko) * 2012-11-19 2016-05-19 한양대학교 산학협력단 나트륨 이차전지용 양극활물질 및 이의 제조 방법
JP2016103477A (ja) * 2014-11-18 2016-06-02 国立研究開発法人産業技術総合研究所 ナトリウム二次電池用正極材料

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KR20100120138A (ko) * 2008-02-04 2010-11-12 스미또모 가가꾸 가부시키가이샤 복합 금속 산화물 및 나트륨 이차 전지
KR20160056319A (ko) * 2012-11-19 2016-05-19 한양대학교 산학협력단 나트륨 이차전지용 양극활물질 및 이의 제조 방법
KR101493932B1 (ko) * 2012-12-27 2015-02-16 전자부품연구원 실리콘 산화물이 코팅된 리튬 이차전지용 양극 활물질 및 그의 제조 방법
JP2016103477A (ja) * 2014-11-18 2016-06-02 国立研究開発法人産業技術総合研究所 ナトリウム二次電池用正極材料

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Title
XU, LIPENG: "Progress in preparation and modification of LiNi0.6Mn0.2Co0.2O2 cathode material for high energy density Li-ion batteries", INTERNATIONAL JOURNAL OF ELECTROCHEMISTRY, vol. 2018, 6930386, 2 July 2018 (2018-07-02), pages 1 - 12, XP055693896 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115911327A (zh) * 2022-11-28 2023-04-04 广东凯金新能源科技股份有限公司 钠离子正极材料及其制备方法、二次电池
CN117117158A (zh) * 2023-10-23 2023-11-24 浙江帕瓦新能源股份有限公司 一种改性钠离子电池正极材料及其制备方法、钠离子电池
CN117117158B (zh) * 2023-10-23 2024-01-23 浙江帕瓦新能源股份有限公司 一种改性钠离子电池正极材料及其制备方法、钠离子电池

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