WO2016084930A1 - Matériau actif d'électrode positive pour batterie rechargeable à électrolyte non aqueux et son procédé de fabrication, et batterie rechargeable à électrolyte non aqueux utilisant ledit matériau actif d'électrode positive - Google Patents

Matériau actif d'électrode positive pour batterie rechargeable à électrolyte non aqueux et son procédé de fabrication, et batterie rechargeable à électrolyte non aqueux utilisant ledit matériau actif d'électrode positive Download PDF

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Publication number
WO2016084930A1
WO2016084930A1 PCT/JP2015/083367 JP2015083367W WO2016084930A1 WO 2016084930 A1 WO2016084930 A1 WO 2016084930A1 JP 2015083367 W JP2015083367 W JP 2015083367W WO 2016084930 A1 WO2016084930 A1 WO 2016084930A1
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WO
WIPO (PCT)
Prior art keywords
positive electrode
active material
lithium
electrode active
electrolyte secondary
Prior art date
Application number
PCT/JP2015/083367
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English (en)
Japanese (ja)
Inventor
佑樹 古市
小向　哲史
Original Assignee
住友金属鉱山株式会社
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from JP2015212398A external-priority patent/JP6090608B2/ja
Application filed by 住友金属鉱山株式会社 filed Critical 住友金属鉱山株式会社
Priority to CN201580075135.7A priority Critical patent/CN107251285B/zh
Priority to US15/531,616 priority patent/US10784507B2/en
Priority to EP15863730.6A priority patent/EP3226331A4/fr
Priority to KR1020177017668A priority patent/KR101852737B1/ko
Publication of WO2016084930A1 publication Critical patent/WO2016084930A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • 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
    • 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
    • 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

  • Patent Document 3 discloses a metal including at least one selected from Ti, Al, Sn, Bi, Cu, Si, Ga, W, Zr, B, and Mo around the positive electrode active material and / or a plurality of these.
  • a positive electrode active material coated with an intermetallic compound and / or oxide obtained by a combination has been proposed. Such a coating can absorb oxygen gas and ensure safety, but no output characteristics are disclosed.
  • the disclosed manufacturing method is a method of coating using a planetary ball mill, and such a coating method causes physical damage to the positive electrode active material, resulting in deterioration of battery characteristics.
  • a fifteenth aspect of the present invention is a non-aqueous electrolyte secondary battery comprising a positive electrode containing the positive electrode active material for a non-aqueous electrolyte secondary battery according to the ninth to fourteenth aspects.
  • lithium tungstate is formed on the surface of the lithium metal composite oxide particles and on the surface of the primary particles inside, but this lithium tungstate has high lithium ion conductivity and the movement of lithium ions. Has the effect of prompting.
  • the primary particle surface in the present invention refers to the primary particle surface exposed on the outer surface of the secondary particle and the void in the vicinity of the inner surface of the secondary particle through which the electrolyte solution can penetrate through the outer surface of the secondary particle.
  • the exposed primary particle surface and the surface of the primary particle which exists independently are included. Furthermore, even a grain boundary between primary particles is included as long as the primary particles are not completely bonded and the electrolyte solution can penetrate.
  • the contact with the electrolytic solution is not limited to the outer surface of the secondary particles formed by agglomeration of the primary particles, but also the gap between the primary particles in the vicinity of the inner surface of the secondary particles and the incomplete grain boundary.
  • LWO since it also occurs, it is necessary to form LWO also on the surface of the primary particles to promote the movement of lithium ions. Therefore, it is possible to further reduce the reaction resistance of the positive electrode active material by forming LWO on many primary particle surfaces that can be contacted with the electrolytic solution.
  • the property of the primary particle surface of such a lithium metal composite oxide can be judged, for example, by observing with a field emission scanning electron microscope (SEM).
  • SEM field emission scanning electron microscope
  • the moisture content of the lithium metal composite oxide powder in the tungsten mixture (hereinafter simply referred to as the mixture) is 2% by mass or more.
  • the amount of moisture may be 2% by mass or more.
  • the amount of moisture is excessively large, the efficiency of the heat treatment in the subsequent process is reduced, or the elution of lithium from the lithium metal composite oxide particles is increased, resulting in a mixture.
  • Li / Me decreases due to lithium elution at the time of washing with water.
  • a lithium metal composite oxide in which / Me is adjusted may be used.
  • the decrease amount of Li / Me due to general water washing conditions is about 0.03 to 0.08.
  • z indicating Li / Me of the lithium metal composite oxide as a base material is preferably 0.95 ⁇ z ⁇ 1.30, and preferably 0.97 ⁇ z ⁇ 1.20.
  • a positive electrode of a non-aqueous electrolyte secondary battery is produced as follows. First, a powdered positive electrode active material, a conductive material, and a binder are mixed, and, if necessary, a target solvent such as activated carbon and viscosity adjustment is added and kneaded to prepare a positive electrode mixture paste. Each mixing ratio in the positive electrode mixture paste is also an important factor for determining the performance of the non-aqueous electrolyte secondary battery.
  • the obtained positive electrode mixture paste is applied to, for example, the surface of a current collector made of aluminum foil, and dried to disperse the solvent. If necessary, pressurization may be performed by a roll press or the like to increase the electrode density. In this way, a sheet-like positive electrode can be produced.
  • the sheet-like positive electrode can be cut into an appropriate size or the like according to the target battery and used for battery production.
  • the method for manufacturing the positive electrode is not limited to the illustrated one, and other methods may be used.
  • a positive electrode active material, a conductive material, and activated carbon are dispersed, and a solvent that dissolves the binder is added to the positive electrode mixture.
  • a solvent that dissolves the binder is added to the positive electrode mixture.
  • an organic solvent such as N-methyl-2-pyrrolidone can be used as the solvent.
  • Activated carbon can be added to the positive electrode mixture in order to increase the electric double layer capacity.
  • the performance (initial stage discharge capacity, positive electrode resistance) was measured.
  • the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
  • a laminated sheet was formed between the produced positive electrode sheet 5 and negative electrode sheet 6 with a separator 7 made of a polypropylene microporous film (thickness 20.7 ⁇ m, porosity density 43.9%) interposed. Then, this laminated sheet is sandwiched between two aluminum laminate sheets 8 (thickness 0.55 mm), and the three sides of the aluminum laminate sheet are heat-sealed and sealed to assemble a laminate cell having a structure as shown in FIG. It was.
  • a positive electrode active material for a non-aqueous electrolyte secondary battery was obtained in the same manner as in Example 1, except that 2.0 g of LiOH and 10.5 g of WO 3 were used.
  • the mixture after solid-liquid separation was dried, and the water content with respect to the lithium metal composite oxide particles determined from the mass before and after drying was 6.7% by mass.
  • the Li concentration of the liquid component was 1.17 mol / L
  • the tungsten content of the mixture was 0.0023 mol
  • the Li molar ratio was 2.6.
  • a positive electrode active material for a non-aqueous electrolyte secondary battery was obtained in the same manner as in Example 1 except that 2.5 g of LiOH and 15.6 g of WO 3 were used.
  • the mixture after solid-liquid separation was dried, and the water content with respect to the lithium metal composite oxide particles determined from the mass before and after drying was 7.6% by mass.
  • the Li concentration of the liquid component was 1.33 mol / L
  • the tungsten content of the mixture was 0.0039 mol
  • the Li molar ratio was 2.0.

Landscapes

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

Abstract

L'invention concerne un matériau actif d'électrode positive pour batterie rechargeable à électrolyte non aqueux, qui permet d'obtenir une capacité élevée et une sortie plus élevée quand le matériau actif d'électrode positive est utilisé dans un matériau d'électrode positive. Un procédé de fabrication du matériau actif d'électrode positive pour batterie rechargeable à électrolyte non aqueux comprend : une étape de mélange consistant à obtenir un mélange W de particules d'oxyde composite de Li métallique comprenant des particules primaires représentées par la formule générale : LizNi1-x-yCoxMyO2 (dans laquelle 0 < x ≤ 0,35, 0 ≤ y ≤ 0,35, 0,95 ≤ z ≤ 1,30, et M est au moins un élément choisi parmi Mn, V, Mg, Mo, Nb, Ti et Al) et des particules secondaires formées d'une agrégation des particules primaires, au moins 2 % en poids d'eau par rapport aux particules d'oxyde, et un composé W, ou un composé W et un composé Li, le rapport molaire de la quantité totale de Li contenue dans le composé W ou le composé W et le composé Li qui sont des matières solides et dans l'eau par rapport à la quantité de W contenue étant supérieur ou égal à 1,5 et inférieur à 3,0 ; et une étape de traitement thermique consistant à traiter thermiquement le mélange W afin de former du tungstate de lithium sur la surface des particules primaires.
PCT/JP2015/083367 2014-11-28 2015-11-27 Matériau actif d'électrode positive pour batterie rechargeable à électrolyte non aqueux et son procédé de fabrication, et batterie rechargeable à électrolyte non aqueux utilisant ledit matériau actif d'électrode positive WO2016084930A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201580075135.7A CN107251285B (zh) 2014-11-28 2015-11-27 非水系电解质二次电池用正极活性物质和其制造方法，以及非水系电解质二次电池
US15/531,616 US10784507B2 (en) 2014-11-28 2015-11-27 Positive electrode active material for nonaqueous electrolyte secondary battery, method for producing same, and nonaqueous electrolyte secondary battery using said positive electrode active material
EP15863730.6A EP3226331A4 (fr) 2014-11-28 2015-11-27 Matériau actif d'électrode positive pour batterie rechargeable à électrolyte non aqueux et son procédé de fabrication, et batterie rechargeable à électrolyte non aqueux utilisant ledit matériau actif d'électrode positive
KR1020177017668A KR101852737B1 (ko) 2014-11-28 2015-11-27 비수계 전해질 이차 전지용 정극 활물질과 그 제조 방법, 및 상기 정극 활물질을 이용한 비수계 전해질 이차 전지

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2014241790 2014-11-28
JP2014-241790 2014-11-28
JP2015-212398 2015-10-28
JP2015212398A JP6090608B2 (ja) 2014-11-28 2015-10-28 非水系電解質二次電池用正極活物質とその製造方法、および該正極活物質を用いた非水系電解質二次電池

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3553856A4 (fr) * 2016-12-07 2020-08-05 Sumitomo Chemical Company, Limited Matériau actif d'électrode positive pour batteries secondaires au lithium, électrode positive pour batteries secondaires au lithium, et batterie secondaire au lithium
CN112242509A (zh) * 2019-07-18 2021-01-19 丰田自动车株式会社 非水电解质二次电池
CN112242506A (zh) * 2019-07-18 2021-01-19 丰田自动车株式会社 非水电解质二次电池
CN112417725A (zh) * 2020-11-20 2021-02-26 苏州凌威新能源科技有限公司 负极片孔隙率的设计方法
EP3806204A4 (fr) * 2018-05-31 2021-08-11 Sumitomo Metal Mining Co., Ltd. Matériau actif d'électrode positive pour batterie secondaire à électrolyte non aqueux et batterie secondaire à électrolyte non aqueux
CN112417725B (zh) * 2020-11-20 2024-07-12 湖南领湃达志科技股份有限公司 负极片孔隙率的设计方法

Citations (5)

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WO2002041419A1 (fr) * 2000-11-20 2002-05-23 Chuo Denki Kogyo Co., Ltd. Cellule secondaire electrolytique non aqueuse et materiau actif d'electrode positive
WO2009029111A1 (fr) * 2007-08-31 2009-03-05 Midwest Research Institute Batteries à base de lithium à film fin et dispositifs électrochromiques fabriqués avec des matériaux d'électrode nanocomposites
WO2012105048A1 (fr) * 2011-02-04 2012-08-09 トヨタ自動車株式会社 Matériau actif revêtu, batterie, et procédé pour produire un matériau actif revêtu
WO2013015069A1 (fr) * 2011-07-28 2013-01-31 三洋電機株式会社 Cellule secondaire à électrolyte non aqueux
JP2013125732A (ja) * 2011-12-16 2013-06-24 Sumitomo Metal Mining Co Ltd 非水系電解質二次電池用正極活物質とその製造方法、および該正極活物質を用いた非水系電解質二次電池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002041419A1 (fr) * 2000-11-20 2002-05-23 Chuo Denki Kogyo Co., Ltd. Cellule secondaire electrolytique non aqueuse et materiau actif d'electrode positive
WO2009029111A1 (fr) * 2007-08-31 2009-03-05 Midwest Research Institute Batteries à base de lithium à film fin et dispositifs électrochromiques fabriqués avec des matériaux d'électrode nanocomposites
WO2012105048A1 (fr) * 2011-02-04 2012-08-09 トヨタ自動車株式会社 Matériau actif revêtu, batterie, et procédé pour produire un matériau actif revêtu
WO2013015069A1 (fr) * 2011-07-28 2013-01-31 三洋電機株式会社 Cellule secondaire à électrolyte non aqueux
JP2013125732A (ja) * 2011-12-16 2013-06-24 Sumitomo Metal Mining Co Ltd 非水系電解質二次電池用正極活物質とその製造方法、および該正極活物質を用いた非水系電解質二次電池

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See also references of EP3226331A4 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3553856A4 (fr) * 2016-12-07 2020-08-05 Sumitomo Chemical Company, Limited Matériau actif d'électrode positive pour batteries secondaires au lithium, électrode positive pour batteries secondaires au lithium, et batterie secondaire au lithium
US11011741B2 (en) 2016-12-07 2021-05-18 Sumitomo Chemical Company, Limited Positive electrode active material for lithium secondary batteries, positive electrode for lithium secondary batteries, and lithium secondary battery
EP3806204A4 (fr) * 2018-05-31 2021-08-11 Sumitomo Metal Mining Co., Ltd. Matériau actif d'électrode positive pour batterie secondaire à électrolyte non aqueux et batterie secondaire à électrolyte non aqueux
US11967713B2 (en) 2018-05-31 2024-04-23 Sumitomo Metal Mining Co., Ltd. Positive electrode active material for non-aqueous electrolyte secondary battery comprising tungsten coating film, and non-aqueous electrolyte secondary battery
CN112242509A (zh) * 2019-07-18 2021-01-19 丰田自动车株式会社 非水电解质二次电池
CN112242506A (zh) * 2019-07-18 2021-01-19 丰田自动车株式会社 非水电解质二次电池
CN112242509B (zh) * 2019-07-18 2024-04-09 丰田自动车株式会社 非水电解质二次电池
CN112417725A (zh) * 2020-11-20 2021-02-26 苏州凌威新能源科技有限公司 负极片孔隙率的设计方法
CN112417725B (zh) * 2020-11-20 2024-07-12 湖南领湃达志科技股份有限公司 负极片孔隙率的设计方法

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