WO2024142695A1 - 非水電解質二次電池用正極活物質の製造方法 - Google Patents

非水電解質二次電池用正極活物質の製造方法 Download PDF

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Publication number
WO2024142695A1
WO2024142695A1 PCT/JP2023/042178 JP2023042178W WO2024142695A1 WO 2024142695 A1 WO2024142695 A1 WO 2024142695A1 JP 2023042178 W JP2023042178 W JP 2023042178W WO 2024142695 A1 WO2024142695 A1 WO 2024142695A1
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Prior art keywords
lithium
transition metal
positive electrode
composite oxide
metal composite
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PCT/JP2023/042178
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English (en)
French (fr)
Japanese (ja)
Inventor
晃輔 井上
かおる 長田
毅 小笠原
勝哉 井之上
晃宏 河北
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Panasonic Energy Co Ltd
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Panasonic Energy Co Ltd
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Priority to JP2024567305A priority Critical patent/JPWO2024142695A1/ja
Priority to CN202380085903.1A priority patent/CN120322870A/zh
Publication of WO2024142695A1 publication Critical patent/WO2024142695A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • H01M4/52—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

  • a low-resistance positive electrode active material for a non-aqueous electrolyte secondary battery can be obtained.
  • Examples of the conductive agent contained in the positive electrode mixture layer 31 include carbon black such as acetylene black and ketjen black, graphite, carbon nanotubes (CNT), carbon nanofibers, graphene, and other carbon materials.
  • Examples of the binder contained in the positive electrode mixture layer 31 include fluorine-containing resins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), polyimide, acrylic resin, polyolefin, and the like. These resins may also be used in combination with carboxymethylcellulose (CMC) or a salt thereof, polyethylene oxide, and the like.
  • the content of the conductive agent and the binder is, for example, 0.1 to 5.0% by mass, respectively, relative to the mass of the positive electrode mixture layer 31.
  • the lithium-containing transition metal composite oxide preferably contains 50 mol% or more, and more preferably 70 mol% or more of Ni relative to the total number of moles of metal elements excluding Li. Furthermore, the effect of adding a sulfonic acid compound is more pronounced when a lithium-containing transition metal composite oxide with a high Ni content is used.
  • the Ni content may be 80 mol% or more, or may be 90 mol% or more, relative to the total number of moles of metal elements excluding Li.
  • the upper limit of the Ni content is, for example, 95 mol%.
  • R is preferably an alkyl group.
  • the number of carbon atoms in the alkyl group is preferably 5 or less, and more preferably 3 or less. From the viewpoint of reducing reaction resistance, a suitable example of R is an alkyl group having 3 or less carbon atoms, and among these, a methyl group is preferable. Note that in R, some of the hydrogens bonded to the carbons may be substituted with fluorine. Also, n in formula (I) is preferably 1.
  • the water washing step is a step of washing the lithium-containing transition metal composite oxide with water and dehydrating it to obtain a cake-like composition.
  • the particulate lithium-containing transition metal composite oxide obtained in the synthesis step can be used.
  • By washing with water it is possible to remove unreacted lithium compounds added in the synthesis step and impurities other than the lithium compounds.
  • 300 g to 5000 g of the lithium-containing transition metal composite oxide is added per 1 L of water.
  • the water washing may be repeated multiple times. Dehydration after washing with water can be performed, for example, by using a filter press.
  • the upper limit of the heat treatment temperature in the heat treatment step is preferably 250°C or less, and more preferably 170°C or less.
  • the sulfonic acid compound attached to the surface of the lithium-containing transition metal composite oxide can be prevented from volatilizing.
  • the lower limit of the heat treatment temperature is not particularly limited as long as it is a temperature at which moisture can be evaporated from the lithium-containing transition metal composite oxide, but from the viewpoint of efficiency, it is preferably 100°C or more, and more preferably 120°C or more. Therefore, an example of a suitable range of the heat treatment temperature in the heat treatment step is 100°C or more and 250°C or less, and more preferably 120°C or more and 170°C or less.
  • the negative electrode active material contained in the negative electrode mixture layer 41 is not particularly limited as long as it can reversibly absorb and release lithium ions, and generally, carbon materials such as graphite are used.
  • the graphite may be any of natural graphite such as scaly graphite, lump graphite, and earthy graphite, lump artificial graphite, and artificial graphite such as graphitized mesophase carbon microbeads.
  • metals that are alloyed with Li such as Si and Sn, metal compounds containing Si and Sn, and lithium titanium composite oxides may be used.
  • those provided with a carbon coating may be used.
  • a porous sheet having ion permeability and insulation is used for the separator 13.
  • the porous sheet include a microporous thin film, a woven fabric, and a nonwoven fabric.
  • the separator is preferably made of a polyolefin such as polyethylene or polypropylene, or cellulose.
  • the separator 13 may have a single-layer structure or a laminated structure.
  • a highly heat-resistant resin layer such as an aramid resin, or a filler layer containing an inorganic compound filler may be provided on the surface of the separator 13.
  • Example 1 [Preparation of Positive Electrode Active Material]
  • the composite hydroxide represented by [Ni 0.90 Co 0.05 Al 0.05 ] (OH) 2 obtained by the coprecipitation method was calcined at 500 ° C. for 8 hours to obtain a metal oxide (Ni 0.90 CO 0.05 Al 0.05 O 2 ).
  • LiOH and the above metal oxide were mixed so that the molar ratio of Li to the total amount of Ni, Co, and Al was 1.03:1 to obtain a mixture.
  • This mixture was calcined from room temperature to 650 ° C. at a heating rate of 2.0 ° C.
  • the particle size distribution of the lithium-containing transition metal composite oxide and the sulfonic acid compound was measured using a laser diffraction particle size distribution measuring device (Microtrack Bell, MT3000II), and the D50b of the sulfonic acid compound was 15 ⁇ m, and the ratio of D50b of the sulfonic acid compound to D50a of the lithium-containing transition metal composite oxide (D50b/D50a) was 1.0.
  • the composition obtained in the addition process was transferred to a stirrer and stirred for 10 minutes. Then, using a vacuum dryer, a heat treatment process was carried out under conditions of 170°C and 2 hours in a vacuum atmosphere, to obtain the positive electrode active material of Example 1. It was confirmed by Fourier transform infrared spectroscopy (FT-IR) that lithium methanesulfonate was present on the surface of the positive electrode active material.
  • FT-IR Fourier transform infrared spectroscopy
  • the positive electrode active material, acetylene black, and polyvinylidene fluoride were mixed in a mass ratio of 85:10:5, kneaded using an agate mortar and pestle, and molded into thin pellets. The pellets were then rolled to a predetermined thickness using a roller, and punched out into a predetermined circular shape to obtain a positive electrode.
  • Ethylene carbonate (EC), methyl ethyl carbonate (MEC), and dimethyl carbonate (DMC) were mixed in a volume ratio of 3: 3: 4.
  • Lithium hexafluorophosphate (LiPF 6 ) was dissolved in the mixed solvent to a concentration of 1.2 mol/L to prepare a non-aqueous electrolyte.
  • the AC impedance of the test cell was measured at an applied voltage of 10 mV and a measurement frequency range of 0.01 Hz to 200 kHz using Solartron 1255B (manufactured by Solartron).
  • a Nyquist diagram was drawn from the measurement data, and the reaction resistance was calculated from the size of the arc between 10 Hz and 0.1 Hz.
  • Example 6 A test cell was produced and evaluated in the same manner as in Example 1, except that in the preparation of the positive electrode active material, the stirring time in the stirring step was changed to 20 minutes.
  • Example 2 A test cell was prepared and evaluated in the same manner as in Example 1, except that the adding step, the stirring step, and the heat treatment step were not performed in the preparation of the positive electrode active material. In other words, no sulfonic acid compound was added to the positive electrode active material of Comparative Example 2.
  • A is a Group 1 or Group 2 element, R is a hydrocarbon group, and n is 1 or 2.
  • Aspect 2 The method for producing a positive electrode active material for a nonaqueous electrolyte secondary battery according to Aspect 1, wherein a ratio (D50b/D50a) of a volume-based median diameter (D50b) of the sulfonic acid compound to a volume-based median diameter (D50a) of the lithium-containing transition metal composite oxide is 0.5 or more and 2.0 or less.
  • Configuration 3 The method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery according to any one of Configurations 1 and 2, wherein in the heat treatment step, the heat treatment temperature is 250° C. or less.

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  • 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)
PCT/JP2023/042178 2022-12-28 2023-11-24 非水電解質二次電池用正極活物質の製造方法 Ceased WO2024142695A1 (ja)

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JP2024567305A JPWO2024142695A1 (https=) 2022-12-28 2023-11-24
CN202380085903.1A CN120322870A (zh) 2022-12-28 2023-11-24 非水电解质二次电池用正极活性物质的制造方法

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JP2022-211390 2022-12-28
JP2022211390 2022-12-28

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009187940A (ja) * 2008-01-11 2009-08-20 Sony Corp 正極活物質、並びにこれを用いた正極および非水電解質二次電池
JP2018006164A (ja) * 2016-07-01 2018-01-11 宇部興産株式会社 蓄電デバイスの電極用チタン酸リチウム粉末および活物質材料、並びにそれを用いた蓄電デバイス
WO2020171093A1 (ja) * 2019-02-21 2020-08-27 住友金属鉱山株式会社 リチウムイオン二次電池用正極活物質の製造方法
JP2021005474A (ja) * 2019-06-25 2021-01-14 住友金属鉱山株式会社 リチウムイオン二次電池用正極活物質とその製造方法、及び、リチウムイオン二次電池
WO2023100535A1 (ja) * 2021-11-30 2023-06-08 パナソニックＩｐマネジメント株式会社 非水電解質二次電池用正極活物質、非水電解質二次電池用正極、非水電解質二次電池、及び非水電解質二次電池用正極活物質の製造方法
WO2023100531A1 (ja) * 2021-11-30 2023-06-08 パナソニックＩｐマネジメント株式会社 非水電解質二次電池用正極活物質、非水電解質二次電池用正極、非水電解質二次電池、及び非水電解質二次電池用正極活物質の製造方法
WO2023100532A1 (ja) * 2021-11-30 2023-06-08 パナソニックＩｐマネジメント株式会社 非水電解質二次電池用正極活物質、非水電解質二次電池用正極、非水電解質二次電池、及び非水電解質二次電池用正極活物質の製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009187940A (ja) * 2008-01-11 2009-08-20 Sony Corp 正極活物質、並びにこれを用いた正極および非水電解質二次電池
JP2018006164A (ja) * 2016-07-01 2018-01-11 宇部興産株式会社 蓄電デバイスの電極用チタン酸リチウム粉末および活物質材料、並びにそれを用いた蓄電デバイス
WO2020171093A1 (ja) * 2019-02-21 2020-08-27 住友金属鉱山株式会社 リチウムイオン二次電池用正極活物質の製造方法
JP2021005474A (ja) * 2019-06-25 2021-01-14 住友金属鉱山株式会社 リチウムイオン二次電池用正極活物質とその製造方法、及び、リチウムイオン二次電池
WO2023100535A1 (ja) * 2021-11-30 2023-06-08 パナソニックＩｐマネジメント株式会社 非水電解質二次電池用正極活物質、非水電解質二次電池用正極、非水電解質二次電池、及び非水電解質二次電池用正極活物質の製造方法
WO2023100531A1 (ja) * 2021-11-30 2023-06-08 パナソニックＩｐマネジメント株式会社 非水電解質二次電池用正極活物質、非水電解質二次電池用正極、非水電解質二次電池、及び非水電解質二次電池用正極活物質の製造方法
WO2023100532A1 (ja) * 2021-11-30 2023-06-08 パナソニックＩｐマネジメント株式会社 非水電解質二次電池用正極活物質、非水電解質二次電池用正極、非水電解質二次電池、及び非水電解質二次電池用正極活物質の製造方法

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CN120322870A (zh) 2025-07-15

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