WO2022264384A1 - リチウムイオン二次電池用負極材、リチウムイオン二次電池用負極及びリチウムイオン二次電池 - Google Patents

リチウムイオン二次電池用負極材、リチウムイオン二次電池用負極及びリチウムイオン二次電池 Download PDF

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Publication number
WO2022264384A1
WO2022264384A1 PCT/JP2021/023112 JP2021023112W WO2022264384A1 WO 2022264384 A1 WO2022264384 A1 WO 2022264384A1 JP 2021023112 W JP2021023112 W JP 2021023112W WO 2022264384 A1 WO2022264384 A1 WO 2022264384A1
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WIPO (PCT)
Prior art keywords
negative electrode
ion secondary
lithium ion
mass
secondary battery
Prior art date
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Ceased
Application number
PCT/JP2021/023112
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English (en)
French (fr)
Japanese (ja)
Inventor
賢匠 星
雄磨 神山
英利 本棒
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Resonac Corp
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Showa Denko Materials Co Ltd
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Filing date
Publication date
Application filed by Showa Denko Materials Co Ltd filed Critical Showa Denko Materials Co Ltd
Priority to EP21943328.1A priority Critical patent/EP4358189A4/en
Priority to PCT/JP2021/023112 priority patent/WO2022264384A1/ja
Priority to JP2022545448A priority patent/JP7768135B2/ja
Priority to US18/009,165 priority patent/US12519108B2/en
Priority to CN202180043572.6A priority patent/CN115997305A/zh
Publication of WO2022264384A1 publication Critical patent/WO2022264384A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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

  • Carbon materials are widely used as negative electrode materials for lithium-ion secondary batteries. Carbon materials used for negative electrode materials are roughly classified into graphite and low-crystalline carbon (including amorphous carbon) having a lower crystallinity than graphite. Since graphite has a structure in which hexagonal mesh planes of carbon atoms are regularly stacked, lithium ion insertion and desorption reactions proceed from the ends of the hexagonal mesh planes, and charging and discharging are performed.
  • Low-crystalline carbon has irregular stacking of hexagonal mesh planes or no hexagonal mesh planes. Therefore, lithium ion intercalation and deintercalation reactions proceed on the entire surface of the negative electrode material. Therefore, the energy density tends to be lower than that of graphite, but it is easy to obtain a lithium ion battery with excellent input characteristics. In addition, the reactivity with the electrolyte is lower than that of graphite, and the storage characteristics (lifetime) of the battery are excellent.
  • a negative electrode material using a carbon material generally has a trade-off relationship between input characteristics and storage characteristics. For example, if the particle size of the negative electrode material is reduced, the contact area with the electrolyte solution increases and the input characteristics improve, but the side reaction with the electrolyte solution is promoted, so the storage characteristics deteriorate.
  • the negative electrode material described in International Publication No. 2012/015054 suppresses deterioration of storage characteristics by coating the surface of graphite particles with low-crystalline carbon, but maintains storage characteristics more effectively. The development of negative electrode materials is awaited.
  • Condition A A histogram of R values obtained by mapping Raman measurement has two or more peaks.
  • Condition B The variance of the maximum peak in the histogram of R values obtained by mapping Raman measurement is 2.0 or more.
  • Condition C The low-crystalline carbon layer contains two or more carbon phases with different crystallinities.
  • negative electrode materials that satisfy at least one of condition A, condition B, or condition C have better storage characteristics than negative electrode materials that satisfy none of condition A, condition B, or condition C. found to be maintained. Furthermore, it was found that this negative electrode material maintains good storage characteristics even when the particle size is reduced in order to improve the input characteristics. Although the reason for this is not necessarily clear, it is believed that the low-crystalline carbon layer that satisfies at least one of Condition A, Condition B, or Condition C is excellent in covering the graphite particles.
  • graphite particles those obtained by pulverizing lumpy natural graphite may be used.
  • Graphite particles obtained by pulverizing lumpy natural graphite may contain impurities, so it is preferable to purify the natural graphite by a refining treatment.
  • the method for refining natural graphite is not particularly limited, and can be appropriately selected from commonly used refining methods. Examples include ore flotation, electrochemical treatment, and chemical treatment.
  • graphite particles pulverized artificial graphite obtained by firing resin materials such as epoxy resins and phenol resins, and pitch materials obtained from petroleum, coal, etc. may be used.
  • the method for obtaining artificial graphite is not particularly limited.
  • a method of obtaining artificial graphite, which is a fired product, can be mentioned.
  • the obtained fired product is pulverized by a known method such as a jet mill, a vibration mill, a pin mill, a hammer mill, etc., and the average particle size is adjusted to about 2 ⁇ m to 40 ⁇ m to produce graphite particles derived from artificial graphite. be able to.
  • the raw material may be heat-treated in advance before calcination.
  • the raw material is heat-treated, for example, the raw material is pre-heated using an autoclave or the like, coarsely pulverized by a known method, and then the heat-treated raw material is calcined in an inert atmosphere at 800° C. or higher in the same manner as described above.
  • Graphite particles derived from artificial graphite can be obtained by pulverizing the obtained artificial graphite, which is the fired product, to adjust the average particle size to about 2 ⁇ m to 40 ⁇ m.
  • the thickness of the low-crystalline carbon layer (maximum thickness if the thickness is not constant) is not particularly limited. For example, it may be selected from the range of 0.5 nm to 500 nm.
  • the thickness of the low-crystalline carbon layer can be measured using, for example, a transmission electron microscope (TEM).
  • Examples of methods for coating the surface of graphite particles with a low-crystalline carbon layer include a method of heat-treating a mixture containing graphite particles and a precursor of the low-crystalline carbon layer.
  • a negative electrode material that satisfies at least one of Condition A, Condition B, or Condition C can be obtained, for example, by using two or more precursors for the low-crystalline carbon layer that coats the graphite particles.
  • a micro Raman spectrometer eg, DXR Imaging Micro Raman, manufactured by Thermo Fisher Scientific
  • the conditions are a laser with a wavelength of 532 nm, a 100-fold lens, and an aperture of 25 ⁇ m ⁇ .
  • the output is 2.0 mW
  • the irradiation time and integration are performed so that a sufficient SN ratio can be obtained.
  • the irradiation time is 2 seconds and the integration is 30 times.
  • the measurement of the R value is carried out at 100 points or more by shifting the measurement point on the particle by 1.5 ⁇ m or more, or by changing the particle, and obtaining a histogram.
  • the average circularity of the negative electrode material can be measured using a wet flow particle size/shape analyzer (eg, FPIA-3000, Malvern).
  • a wet flow particle size/shape analyzer eg, FPIA-3000, Malvern.
  • 0.06 g of the negative electrode material and purified water containing 0.2% by mass of a surfactant (trade name: Liponol T/15, Lion Corporation) were placed in a test tube (12 mm ⁇ 120 mm, Maruem Co., Ltd.), stirred with a test tube mixer (Pasolina NS-80, AS ONE Co., Ltd.) for 20 seconds, and then ultrasonically stirred for 1 minute.
  • US102 high frequency output 100 W, oscillation frequency 38 kHz manufactured by SND Co., Ltd.
  • a thickener is effective for adjusting the viscosity of the slurry.
  • the thickener is not particularly limited, and specific examples include carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, ethylcellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein and salts thereof.
  • a thickener may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the content of the thickener with respect to the mass of the positive electrode mixture layer is preferably 0.1% by mass to 20% by mass, and 0.5% by mass, from the viewpoint of input/output characteristics and battery capacity. It is more preferably from 1% by mass to 15% by mass, and even more preferably from 1% by mass to 10% by mass.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
PCT/JP2021/023112 2021-06-17 2021-06-17 リチウムイオン二次電池用負極材、リチウムイオン二次電池用負極及びリチウムイオン二次電池 Ceased WO2022264384A1 (ja)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP21943328.1A EP4358189A4 (en) 2021-06-17 2021-06-17 Negative electrode material for lithium ion secondary batteries, negative electrode for lithium ion secondary batteries, and lithium ion secondary battery
PCT/JP2021/023112 WO2022264384A1 (ja) 2021-06-17 2021-06-17 リチウムイオン二次電池用負極材、リチウムイオン二次電池用負極及びリチウムイオン二次電池
JP2022545448A JP7768135B2 (ja) 2021-06-17 2021-06-17 リチウムイオン二次電池用負極材、リチウムイオン二次電池用負極及びリチウムイオン二次電池
US18/009,165 US12519108B2 (en) 2021-06-17 2021-06-17 Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery
CN202180043572.6A CN115997305A (zh) 2021-06-17 2021-06-17 锂离子二次电池用负极材料、锂离子二次电池用负极及锂离子二次电池

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2021/023112 WO2022264384A1 (ja) 2021-06-17 2021-06-17 リチウムイオン二次電池用負極材、リチウムイオン二次電池用負極及びリチウムイオン二次電池

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WO2022264384A1 true WO2022264384A1 (ja) 2022-12-22

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US (1) US12519108B2 (https=)
EP (1) EP4358189A4 (https=)
JP (1) JP7768135B2 (https=)
CN (1) CN115997305A (https=)
WO (1) WO2022264384A1 (https=)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119852316A (zh) * 2024-07-18 2025-04-18 宁德时代新能源科技股份有限公司 二次电池、用电装置、人造石墨及其制备方法
WO2025118620A1 (zh) * 2023-12-07 2025-06-12 宁德时代新能源科技股份有限公司 石墨负极活性材料及其制备方法、负极极片、二次电池和用电装置

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WO2010110443A1 (ja) * 2009-03-27 2010-09-30 三菱化学株式会社 非水電解液二次電池用負極材料及びこれを用いた非水電解液二次電池
WO2012015054A1 (ja) 2010-07-30 2012-02-02 日立化成工業株式会社 リチウムイオン二次電池用負極材、リチウムイオン二次電池用負極及びリチウムイオン二次電池
JP2013197082A (ja) * 2012-03-23 2013-09-30 Mitsubishi Chemicals Corp 非水系二次電池用炭素材、非水系二次電池用負極及びリチウムイオン二次電池
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JP5668308B2 (ja) * 2009-03-27 2015-02-12 三菱化学株式会社 非水電解液二次電池用負極材料及びこれを用いた非水電解液二次電池
JP5742153B2 (ja) * 2010-09-29 2015-07-01 三菱化学株式会社 非水系二次電池用複層構造炭素材、及びそれを用いた負極材並びに非水系二次電池
JP2013254723A (ja) * 2012-05-11 2013-12-19 Hitachi High-Technologies Corp プラズマ処理装置
JP7099325B2 (ja) * 2016-11-22 2022-07-12 三菱ケミカル株式会社 非水系二次電池用負極材、非水系二次電池用負極及び非水系二次電池
CN110168787B (zh) * 2017-01-06 2022-05-03 昭和电工材料株式会社 锂离子二次电池用负极材、锂离子二次电池用负极和锂离子二次电池
KR102474533B1 (ko) * 2017-05-15 2022-12-05 에스케이온 주식회사 리튬 이차 전지용 음극 및 리튬 이차 전지
WO2020213628A1 (ja) 2019-04-18 2020-10-22 昭和電工株式会社 複合炭素粒子、その製造方法及びその用途

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WO2010110443A1 (ja) * 2009-03-27 2010-09-30 三菱化学株式会社 非水電解液二次電池用負極材料及びこれを用いた非水電解液二次電池
WO2012015054A1 (ja) 2010-07-30 2012-02-02 日立化成工業株式会社 リチウムイオン二次電池用負極材、リチウムイオン二次電池用負極及びリチウムイオン二次電池
JP2013197082A (ja) * 2012-03-23 2013-09-30 Mitsubishi Chemicals Corp 非水系二次電池用炭素材、非水系二次電池用負極及びリチウムイオン二次電池
JP2013254728A (ja) * 2012-05-10 2013-12-19 Jfe Chemical Corp リチウムイオン二次電池用負極材の製造方法

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See also references of EP4358189A4

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025118620A1 (zh) * 2023-12-07 2025-06-12 宁德时代新能源科技股份有限公司 石墨负极活性材料及其制备方法、负极极片、二次电池和用电装置
CN119852316A (zh) * 2024-07-18 2025-04-18 宁德时代新能源科技股份有限公司 二次电池、用电装置、人造石墨及其制备方法

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Publication number Publication date
JPWO2022264384A1 (https=) 2022-12-22
US20240234727A1 (en) 2024-07-11
US12519108B2 (en) 2026-01-06
EP4358189A1 (en) 2024-04-24
JP7768135B2 (ja) 2025-11-12
CN115997305A (zh) 2023-04-21
EP4358189A4 (en) 2025-03-19

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