WO2008023622A1 - Procédé de production d'un oxyde composé lithium/manganèse - Google Patents

Procédé de production d'un oxyde composé lithium/manganèse Download PDF

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Publication number
WO2008023622A1
WO2008023622A1 PCT/JP2007/065915 JP2007065915W WO2008023622A1 WO 2008023622 A1 WO2008023622 A1 WO 2008023622A1 JP 2007065915 W JP2007065915 W JP 2007065915W WO 2008023622 A1 WO2008023622 A1 WO 2008023622A1
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WO
WIPO (PCT)
Prior art keywords
lithium
manganese
composite oxide
discharge
compound
Prior art date
Application number
PCT/JP2007/065915
Other languages
English (en)
Japanese (ja)
Inventor
Mitsuharu Tabuchi
Yoko Nabeshima
Kazuaki Ado
Tomonari Takeuchi
Kuniaki Tatsumi
Tetsuhiko Kobayashi
Original Assignee
National Institute Of Advanced Industrial Science And Technology
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
Application filed by National Institute Of Advanced Industrial Science And Technology filed Critical National Institute Of Advanced Industrial Science And Technology
Priority to JP2008530876A priority Critical patent/JP4997609B2/ja
Publication of WO2008023622A1 publication Critical patent/WO2008023622A1/fr

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Classifications

    • 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
    • C01G49/00—Compounds of iron
    • C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
    • 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
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
    • 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
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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 5 Japanese Unexamined Patent Publication No. 2005-154256
  • Example 1 shows how to further clarify the features of the present invention, but the present invention is not limited to these examples. [0073]
  • FIG. 6 is a graph showing initial charge / discharge characteristics of lithium batteries using the positive electrode materials of Example 1 and Comparative Example 1.
  • the upward curve corresponds to the charge curve
  • the downward curve corresponds to the discharge curve.
  • Figure 8 shows the lithium battery using each positive electrode material of Example 1 (solid line in the figure) and Comparative Example 1 (dashed line in the figure) after charging to 30 ° C and 4.8V. It is a graph showing discharge characteristics at different temperatures (30 ° C, 0 ° C, _20 ° C). In addition, Table 3 below shows the charge / discharge derating obtained in this test.
  • FIG. 13 is a graph showing the charge / discharge cycle number dependency of the discharge capacity of each battery. From these results, it was found that the lithium batteries using the Li MnO positive electrode materials of Examples 2 and 3 had a higher capacity over the entire number of cycles compared to the battery using the positive electrode of Comparative Example 3.
  • the Li M ⁇ composite oxide obtained by preparing potassium permanganate as a manganese raw material exhibits excellent charge / discharge characteristics in a charge / discharge test at 30 ° C.
  • FIG. 15 shows the electrons of the iron and titanium-containing Li MnO obtained as the final product in Example 4.
  • the initial discharge energy density is equivalent to the product of the initial discharge capacity and the initial average discharge voltage.
  • Example 4 was prepared using potassium permanganate as the manganese raw material. Compared with the battery using the iron and titanium-containing Li MnO cathode material of Comparative Example 3 prepared using manganese chloride ( ⁇ ) as the raw material for manganese, the battery using the iron and titanium-containing Li MnO cathode material of It is clear that the discharge capacity and energy density are large and the charge and discharge efficiency is excellent.
  • Fig. 20 shows the X-ray diffraction pattern of this final product. From the results of Rietveld analysis (product uses RIETAN-2000), all peaks are unit cells of layered rock-salt-type iron-containing Li MnO
  • FIG. 21 is an electron micrograph of titanium-containing Li MnO obtained as the final product in Example 5.
  • Fig. 20 shows the X-ray diffraction pattern of this final product. From the results of the Rietveld analysis (the product uses RIETAN-2000), all the peaks are single layers of iron-containing Li MnO of layered rock salt type.

Abstract

L'invention concerne un procédé de production d'un oxyde composite du lithium et du manganèse répondant à la formule empirique (1) suivante : Li1+x(Mn1-y-zFeyTiz)1-xO2 (où 0 < x < 1/3, 0 ≤y ≤ 0,75, 0 ≤ z ≤ 0,75 et 0 ≤ y + z <1) et comprenant une phase cristalline de type sel gemme feuilleté. Le procédé de production dudit oxyde composite est caractérisé en ce qu'il comprend les étapes consistant à dissoudre, suivant le même rapport élémentaire que dans la formule (1) ci-dessus, un ou plusieurs composés du manganèse, un composé du fer et un composé du titane dans un solvant comprenant de l'eau ou un mélange eau-alcool afin de préparer une solution de départ ; alcaliniser la solution pour induire une précipitation ; soumettre le précipité à un traitement hydrothermal en présence d'un agent oxydant et d'un composé hydrosoluble du lithium, dans des conditions alcalines ; puis calciner le produit résultant du traitement hydrothermal en présence d'un composé du lithium. Ledit procédé est également caractérisé en ce que les composés du manganèse utilisés en tant que matières premières comprennent un permanganate en une quantité au moins égale à 20 mol%, sur la base de la quantité totale de composés du manganèse. On obtient ainsi un oxyde composite du lithium et du manganèse utilisable en tant que matériau de pour électrode positive à la place d'un matériau pour électrode positive à base de lithium et de cobalt. Ledit oxyde composite offre des performances de charge et de décharge plus élevées.
PCT/JP2007/065915 2006-08-21 2007-08-15 Procédé de production d'un oxyde composé lithium/manganèse WO2008023622A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2008530876A JP4997609B2 (ja) 2006-08-21 2007-08-15 リチウムマンガン系複合酸化物の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006223778 2006-08-21
JP2006-223778 2006-08-21

Publications (1)

Publication Number Publication Date
WO2008023622A1 true WO2008023622A1 (fr) 2008-02-28

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JP (1) JP4997609B2 (fr)
WO (1) WO2008023622A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009179501A (ja) * 2008-01-30 2009-08-13 National Institute Of Advanced Industrial & Technology 規則構造を有する単斜晶系リチウムマンガン系複合酸化物およびその製造方法
JP2009274940A (ja) * 2008-05-19 2009-11-26 National Institute Of Advanced Industrial & Technology 陽イオン規則構造を有する単斜晶系リチウムマンガン系複合酸化物およびその製造方法
JP2012091982A (ja) * 2010-10-28 2012-05-17 National Institute Of Advanced Industrial Science & Technology 立方晶岩塩型構造を有するリチウムマンガン系複合酸化物およびその製造方法
JP2015144131A (ja) * 2010-07-20 2015-08-06 国立研究開発法人産業技術総合研究所 リチウムマンガン系複合酸化物およびその製造方法
WO2018220882A1 (fr) * 2017-05-29 2018-12-06 パナソニックＩｐマネジメント株式会社 Substance active d'électrode positive et batterie
WO2019064816A1 (fr) * 2017-09-27 2019-04-04 パナソニックＩｐマネジメント株式会社 Matériau actif d'électrode positive et batterie
WO2019235573A1 (fr) * 2018-06-06 2019-12-12 国立研究開発法人産業技術総合研究所 Oxyde composite à base de lithium-manganèse et son procédé de production
US11557760B2 (en) 2017-04-24 2023-01-17 Panasonic Intellectual Property Management Co., Ltd. Positive-electrode active material containing lithium composite oxide, and battery including the same

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10134812A (ja) * 1996-10-31 1998-05-22 Matsushita Electric Ind Co Ltd 非水電解質リチウム二次電池およびその正極材料の製造方法
JP2002075358A (ja) * 2000-08-25 2002-03-15 National Institute Of Advanced Industrial & Technology リチウムイオン二次電池正極用材料及びその製造方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3580209B2 (ja) * 2000-02-08 2004-10-20 新神戸電機株式会社 リチウムイオン二次電池

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10134812A (ja) * 1996-10-31 1998-05-22 Matsushita Electric Ind Co Ltd 非水電解質リチウム二次電池およびその正極材料の製造方法
JP2002075358A (ja) * 2000-08-25 2002-03-15 National Institute Of Advanced Industrial & Technology リチウムイオン二次電池正極用材料及びその製造方法

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009179501A (ja) * 2008-01-30 2009-08-13 National Institute Of Advanced Industrial & Technology 規則構造を有する単斜晶系リチウムマンガン系複合酸化物およびその製造方法
JP2009274940A (ja) * 2008-05-19 2009-11-26 National Institute Of Advanced Industrial & Technology 陽イオン規則構造を有する単斜晶系リチウムマンガン系複合酸化物およびその製造方法
JP2015144131A (ja) * 2010-07-20 2015-08-06 国立研究開発法人産業技術総合研究所 リチウムマンガン系複合酸化物およびその製造方法
JP2012091982A (ja) * 2010-10-28 2012-05-17 National Institute Of Advanced Industrial Science & Technology 立方晶岩塩型構造を有するリチウムマンガン系複合酸化物およびその製造方法
US11557760B2 (en) 2017-04-24 2023-01-17 Panasonic Intellectual Property Management Co., Ltd. Positive-electrode active material containing lithium composite oxide, and battery including the same
JP6990855B2 (ja) 2017-05-29 2022-01-12 パナソニックＩｐマネジメント株式会社 正極活物質、および、電池
WO2018220882A1 (fr) * 2017-05-29 2018-12-06 パナソニックＩｐマネジメント株式会社 Substance active d'électrode positive et batterie
US11605814B2 (en) 2017-05-29 2023-03-14 Panasonic Intellectual Property Management Co., Ltd. Positive-electrode active material containing lithium composite oxide, and battery including the same
JPWO2018220882A1 (ja) * 2017-05-29 2020-05-28 パナソニックＩｐマネジメント株式会社 正極活物質、および、電池
JPWO2019064816A1 (ja) * 2017-09-27 2020-09-03 パナソニックＩｐマネジメント株式会社 正極活物質、および、電池
US11233237B2 (en) 2017-09-27 2022-01-25 Panasonic Intellectual Property Management Co., Ltd. Positive electrode active material containing lithium composite oxide and battery including the same
JP7122542B2 (ja) 2017-09-27 2022-08-22 パナソニックＩｐマネジメント株式会社 正極活物質、および、電池
WO2019064816A1 (fr) * 2017-09-27 2019-04-04 パナソニックＩｐマネジメント株式会社 Matériau actif d'électrode positive et batterie
JPWO2019235573A1 (ja) * 2018-06-06 2021-07-08 国立研究開発法人産業技術総合研究所 リチウムマンガン系複合酸化物及びその製造方法
WO2019235573A1 (fr) * 2018-06-06 2019-12-12 国立研究開発法人産業技術総合研究所 Oxyde composite à base de lithium-manganèse et son procédé de production
JP7302826B2 (ja) 2018-06-06 2023-07-04 国立研究開発法人産業技術総合研究所 リチウムマンガン系複合酸化物及びその製造方法

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JP4997609B2 (ja) 2012-08-08

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