WO2011021480A1 - 二次電池用正極材料の製造方法 - Google Patents

二次電池用正極材料の製造方法 Download PDF

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Publication number
WO2011021480A1
WO2011021480A1 PCT/JP2010/062620 JP2010062620W WO2011021480A1 WO 2011021480 A1 WO2011021480 A1 WO 2011021480A1 JP 2010062620 W JP2010062620 W JP 2010062620W WO 2011021480 A1 WO2011021480 A1 WO 2011021480A1
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WIPO (PCT)
Prior art keywords
powder
positive electrode
electrode material
secondary battery
granulated
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PCT/JP2010/062620
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English (en)
French (fr)
Japanese (ja)
Inventor
晶弘 木下
正行 片倉
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日清エンジニアリング株式会社
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Application filed by 日清エンジニアリング株式会社 filed Critical 日清エンジニアリング株式会社
Priority to KR1020127002844A priority Critical patent/KR101705927B1/ko
Priority to CN2010800318739A priority patent/CN102473909A/zh
Publication of WO2011021480A1 publication Critical patent/WO2011021480A1/ja

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection 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
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Definitions

  • the present invention relates to a method for producing a positive electrode material of a secondary battery used for a power source of a portable device such as a notebook computer, a mobile phone, and a video camera, an electric vehicle, a hybrid electric vehicle, etc.
  • the present invention relates to a method for producing a positive electrode material for a battery.
  • lithium ion secondary batteries have excellent energy density and output density, and are effective for miniaturization and weight reduction. Therefore, they are used as power sources for portable devices such as laptop computers, mobile phones, and video cameras. Has been. Lithium ion secondary batteries are also attracting attention as power sources for electric vehicles and power load leveling, and are also used as power sources for hybrid electric vehicles.
  • the positive electrode material of the lithium ion secondary battery examples include lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), and lithium manganate (LiMn 2 O 4 ).
  • the positive electrode material of a lithium ion secondary battery is a mixture of a lithium compound, which is a raw material, and a compound such as an oxide or hydroxide, such as nickel, manganese, cobalt, etc., and the mixed powder is placed in a container. , And calcined at 700 to 1100 ° C., and then pulverized into powder.
  • various methods for producing a positive electrode material for a lithium ion secondary battery have been proposed (see Patent Document 1).
  • Patent Document 1 based on the chemical formula of lithium manganese oxide, lithium hydroxide or decomposable lithium salt and manganese oxide or decomposable manganese salt are homogeneously mixed by a theoretical amount, and this homogeneous mixing is performed.
  • the compound is fed to the reactor, the mixed compound is continuously stirred in the reactor, and a gas body rich in air or oxygen is flowed into the reactor and is in the range of about 650 ° C. to about 800 ° C.
  • a gas body rich in air or oxygen is flowed into the reactor and is in the range of about 650 ° C. to about 800 ° C.
  • Patent Document 1 also synthesizes a substantially single-phase lithium manganese oxide having a cubic spinel crystal structure having a chemical formula of Li 1 + x Mn 2 ⁇ x O 4 and 0 ⁇ X ⁇ 0.125. It also describes how to do it.
  • An object of the present invention is to provide a method for producing a positive electrode material for a secondary battery that eliminates the problems based on the above-described conventional technology and has excellent production efficiency.
  • the present invention is a method for producing a positive electrode material for a secondary battery, and a mixed powder is obtained by mixing a raw material lithium compound powder and a metal compound powder, The step of granulating the mixed powder to obtain a granulated powder, and the granulated powder is continuously baked and reacted at a predetermined temperature and time, whereby a composite oxide of lithium and metal is recharged. And a process for obtaining a positive electrode material for a secondary battery.
  • the particle size composition of the granulated powder in the present invention is desirably 40% by mass or less, preferably 25% by mass or less, and more preferably 20% by mass or less when the particle size is less than 250 ⁇ m.
  • the lithium compound is, for example, LiOH, Li 2 O, or Li 2 CO 3
  • the metal compound is, for example, MnO, MnO 2 , Mn 2 O 3 , Mn 3 O 4
  • MnCO 3 MnCO 3 , CoO, CoCO 3 , Co 3 CO 4 , NiO, or Ni (OH) 3
  • the composite oxide is preferably LiMn 2 O 4 , LiCoO 2 , or LiNiO 2 , for example.
  • the present invention by using a granulated powder of a lithium compound and a metal compound, the granulated powder does not adhere to the rotary kiln during the firing and does not clog, etc., and continuously with high production efficiency.
  • a positive electrode material for a secondary battery can be produced.
  • the positive electrode material for secondary batteries can be manufactured continuously more efficiently by manufacturing using a rotary kiln.
  • FIG. 1 It is a schematic diagram which shows the rotary kiln used for the manufacturing method of the positive electrode material for secondary batteries of this invention.
  • A is a schematic diagram which shows the granulator used for the manufacturing method of the positive electrode material for secondary batteries of this invention
  • (B) is used for the manufacturing method of the positive electrode material for secondary batteries of this invention. It is a top view which shows a granulator.
  • a solid-phase reaction in a mixed raw material of a lithium compound and a compound such as an oxide such as nickel, manganese, cobalt, or a hydroxide is used.
  • the reactant remained and could not be produced with high efficiency.
  • a mixed powder obtained by mixing Li 2 CO 3 powder and MnO 2 powder, which are raw materials for a positive electrode material for a secondary battery is continuously fired and reacted using a rotary kiln, the mixed powder is 6 kg / hour.
  • the theoretical recovery amount of LiMn 2 O 4 obtained by firing is 5.25 kg / hour, but when this mixed powder is actually fired, the yield is 17 after 20 minutes from the start of firing.
  • the yield decreases to 11%, and after 60 minutes from the start of firing, the yield is 0%, that is, the fired body adheres to the rotary kiln and grows to block the rotary kiln. As a result, it was found that the fired body could not be recovered.
  • a mixed powder obtained by mixing a powder of Li 2 CO 3 (lithium compound) and a powder of MnO 2 (metal compound) the mixture is continuously fired and reacted using a rotary kiln, and used for a secondary battery.
  • LiMn 2 O 4 composite oxide
  • the present invention has been made on the basis of the above knowledge. Specifically, a lithium compound powder as a raw material and a metal compound powder are mixed to obtain a mixed powder. By using the granulated powder that has been granulated, the rotary kiln can be continuously fired with high production efficiency without clogging. Thereby, the positive electrode material for secondary batteries can be obtained.
  • the particle size composition of the granulated powder in the present invention is desirably 40% by mass or less, preferably 25% by mass or less, more preferably 20% by mass or less when the particle size is less than 250 ⁇ m.
  • the particle size composition of the granulated powder exceeds 40% by mass when the particle size is less than 250 ⁇ m, the amount of fine powder increases.
  • a lithium compound powder and a metal compound powder are mixed.
  • the rotary kiln is blocked and cannot be fired continuously.
  • the maximum particle size of the granulated powder is determined by whether or not the granulated powder is appropriately fired and reacted in the rotary kiln, but the degree of firing and reaction depends on the raw material particle size before mixing.
  • the maximum particle size of the granulated powder cannot be generally defined because it depends on the firing temperature and the like. Therefore, using the fact that approximately 5% of the cross-sectional area of the rotary kiln is the upper limit of the layer thickness of the workpiece, 30 mm is converted into a granulated powder by converting from the cross-sectional area of the industrial rotary kiln. It is appropriate to set the maximum particle size. If the maximum particle size of the granulated powder exceeds 30 mm, the firing / reaction does not proceed properly and a desired fired product cannot be obtained.
  • a lithium compound for example, LiOH, a Li 2 O or Li 2 CO 3,, metal compounds, for example, MnO, MnO 2, Mn 2 O 3, Mn 3 O 4, MnCO 3 , CoO, CoCO 3 , Co 3 CO 4 , NiO, or Ni (OH) 3 .
  • metal compounds for example, MnO, MnO 2, Mn 2 O 3, Mn 3 O 4, MnCO 3 , CoO, CoCO 3 , Co 3 CO 4 , NiO, or Ni (OH) 3 .
  • the composite oxide obtained as the positive electrode material for the secondary battery include LiMn 2 O 4 , LiCoO 2 , and LiNiO 2 .
  • the rotary kiln 10 shown in FIG. 1 can be used, for example, firing under conditions of a firing temperature of 800 ° C. and a firing time of 60 minutes. It is preferable that the temperature raising time up to 800 ° C. is 40 minutes and the holding time at 800 ° C. is 20 minutes.
  • a rotary kiln 10 shown in FIG. 1 includes a ceramic cylindrical portion 12 that is fired in an interior 12a thereof, a heating element 14 that is provided so as to cover the outer surface 12b of the cylindrical portion 12 with a predetermined distance, and a cylinder.
  • a driving unit (not shown) that rotates the unit 12 around the axis thereof as a rotation axis, and a control unit that controls heating of the cylindrical part 12 by the heating element 14 and rotation by the driving part of the cylindrical part 12.
  • the cylindrical part 12 is heated by the heating element 14, heated to a predetermined temperature, for example, 800 ° C., and the granulated powder 16 to be fired is supplied to the inside 12 a of the cylindrical part 12. Then, the cylinder unit 12 is rotated by the drive unit, and the granulated powder 16 is moved from the supply port 13a to the discharge port 13b of the cylinder unit 12 over a predetermined time, while MnO 2 powder and Li Firing and reacting with 2 CO 3 powder. Thereby, a sintered body of LiMn 2 O 4 is obtained as a positive electrode material for a secondary battery. The obtained LiMn 2 O 4 fired body is discharged from the discharge port 13b. In addition, the movement time from the supply port 13a of the cylinder part 12 of the granulated powder 16 to the discharge port 13b is baking time.
  • a predetermined temperature for example, 800 ° C.
  • the fired body of LiMn 2 O 4 is pulverized using a pulverizer such as a super jet mill (manufactured by Nisshin Engineering Co., Ltd.), and further, a classifier such as a turbo classifier (manufactured by Nisshin Engineering Co., Ltd.). ) Or aero fine classifier (manufactured by Nissin Engineering Co., Ltd.).
  • a pulverizer such as a super jet mill (manufactured by Nisshin Engineering Co., Ltd.)
  • a classifier such as a turbo classifier (manufactured by Nisshin Engineering Co., Ltd.).
  • aero fine classifier manufactured by Nissin Engineering Co., Ltd.
  • the granulated powder 16 is obtained as follows. First, for example, by using a granulator 20 shown in FIGS. 2A and 2B, a mixed powder 26 obtained by mixing MnO 2 powder and Li 2 CO 3 powder is granulated and granulated. Processed into granules 28.
  • the particle size composition of the granulated product 28 is 40% by mass or less, preferably 25% by mass or less, more preferably 20% by mass or less, that having a particle size of less than 250 ⁇ m, the granulated product 28 is granulated as it is.
  • the powder 16 is supplied to the inside 12 a of the cylindrical portion 12 of the rotary kiln 10.
  • the granulated product 28 is pulverized using a pulverizer (not shown) or a granulator (see FIG.
  • the granulated powder 16 adjusted to have a desired particle size configuration can be obtained by sizing the particles by a not-shown method. This granulated powder 16 is supplied to the inside 12 a of the cylindrical portion 12 of the rotary kiln 10.
  • the granulator 20 shown in FIGS. 2A and 2B includes a roll pair 22 and a rotation drive unit (not shown) that rotates the rolls 22 a and 22 b of the roll pair 22.
  • a gap 24 is provided between the rolls 22a and 22b, and the roll 22a is pressed in the direction of the roll 22b.
  • a plurality of grooves (lateral grooves) extending in the axial direction are formed in parallel on the surface of each roll 22a, 22b.
  • Each roll 22a, 22b is rotated so as to move the mixed powder 26 from above the gap 24 to below. Accordingly, when a mixed powder 26 of MnO 2 powder and Li 2 CO 3 powder is supplied from above the roll pair 22, the mixture is granulated through the gap 24 to form a granulated product 28.
  • the positive electrode material for a secondary battery can be obtained with high production efficiency without being blocked. Can do.
  • it may replace with the granulator 20 shown to FIG. 2 (A), (B), and may use a grinder, a granulator, or a dry-type compression granulator (not shown).
  • the granulated powder 16 can be obtained, it is not limited to using the granulator 20 shown to FIG. 2 (A) and (B).
  • the granulated powder 16 may be obtained using a rolling granulator or a spray dryer.
  • a binder may be added to the MnO 2 powder and the Li 2 CO 3 powder to facilitate granulation.
  • Granulation conditions Granulator: Roller compactor WP type (Turbo Kogyo Co., Ltd.) Roll gap: 0.5mm (during initial idle operation) Roll diameter: 160 mm x 2 roll surface condition: lateral groove + twill groove Roll linear pressure: 0.4 to 2.0 tons / cm Roll rotation speed: 12rpm Powder supply rate: 60-90kg / hour
  • a rotary kiln shown in FIG. 1 was used to produce a sintered body of LiMn 2 O 4 as a positive electrode material for a secondary battery.
  • Table 1 the particle size distribution shown in Table 1 below, four types of sieves having openings of 2 mm, 1 mm, 0.5 mm, and 0.25 mm were laminated in the order of openings of 2 mm, 1 mm, 0.5 mm, and 0.25 mm. It is obtained by measuring the mass of the powder on each sieve when the granulated product is sieved in order from above.
  • Experimental Example 1 and Experimental Example 2 in which the content of less than 0.25 mm (250 ⁇ m) is less than 21% by mass are continuously used for secondary batteries without the rotary kiln being blocked. A positive electrode material could be obtained.
  • Experimental Example 3 in which the content of less than 0.25 mm (250 ⁇ m) exceeds 40% by mass, the rotary kiln is blocked during firing, and a positive electrode material for a secondary battery cannot be obtained continuously. It was.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
PCT/JP2010/062620 2009-08-21 2010-07-27 二次電池用正極材料の製造方法 WO2011021480A1 (ja)

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KR1020127002844A KR101705927B1 (ko) 2009-08-21 2010-07-27 이차전지용 양극 재료의 제조방법
CN2010800318739A CN102473909A (zh) 2009-08-21 2010-07-27 二次电池用正极材料的制造方法

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JP2009192452A JP5401211B2 (ja) 2009-08-21 2009-08-21 二次電池用正極材料の製造方法
JP2009-192452 2009-08-21

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JP2006278031A (ja) * 2005-03-28 2006-10-12 Mitsubishi Chemicals Corp リチウム二次電池用正極材料の製造方法及びリチウム二次電池用正極材料、並びにそれを用いたリチウム二次電池用正極及びリチウム二次電池
JP2009064585A (ja) * 2007-09-04 2009-03-26 Mitsubishi Chemicals Corp リチウム二次電池用遷移金属系化合物の製造方法

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CN114845959A (zh) * 2019-12-20 2022-08-02 株式会社Posco 二次电池正极材料的制备方法
CN113120966A (zh) * 2021-03-24 2021-07-16 安徽博石高科新材料股份有限公司 一种锰酸锂材料的自动化生产方法
WO2023094486A1 (en) * 2021-11-24 2023-06-01 Ev Metals Uk Limited Process for preparing a lithium transition metal oxide, including a roll commpaction step of precursor materials
CN115064683A (zh) * 2022-07-12 2022-09-16 中国人民解放军空军工程大学 一类锰氧化物复合电极材料及其制备方法和在制备锂离子电池负极材料中的应用
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