WO2025028315A1 - 非水電解質二次電池用正極活物質の粒子破壊強度の測定方法および測定装置 - Google Patents

非水電解質二次電池用正極活物質の粒子破壊強度の測定方法および測定装置 Download PDF

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Publication number
WO2025028315A1
WO2025028315A1 PCT/JP2024/026080 JP2024026080W WO2025028315A1 WO 2025028315 A1 WO2025028315 A1 WO 2025028315A1 JP 2024026080 W JP2024026080 W JP 2024026080W WO 2025028315 A1 WO2025028315 A1 WO 2025028315A1
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positive electrode
electrode active
active material
particle
measuring
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English (en)
French (fr)
Japanese (ja)
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魁星 増本
勝哉 井之上
毅 小笠原
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to CN202480047059.8A priority patent/CN121532861A/zh
Publication of WO2025028315A1 publication Critical patent/WO2025028315A1/ja
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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
    • H01M4/48—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

  • This disclosure relates to a method and device for measuring the particle fracture strength of positive electrode active materials for non-aqueous electrolyte secondary batteries.
  • non-aqueous electrolyte secondary batteries such as lithium-ion batteries have been widely used in applications that require high capacity, such as in-vehicle applications and power storage applications.
  • the performance of the positive electrode active material contained in the positive electrode has a significant impact on achieving high capacity, so it is important to evaluate the characteristics of the positive electrode active material.
  • the particle breaking strength of the positive electrode active material is an important physical property value related to the rolling properties during positive electrode production and the battery life, and it is desirable to quantify it accurately.
  • the particle breaking strength of the positive electrode active material is measured based on the "Method of measuring the breaking strength and deformation strength of microparticles" defined in JIS Z8844-2019.
  • Patent Documents 1 and 2 describe measuring the particle breaking strength using a micro-compression tester.
  • Patent documents 1 and 2 do not describe the variability in the measured values or methods for reducing it, and there is still room for improvement in order to measure particle breaking strength more accurately.
  • the objective of this disclosure is to provide a measurement method and device that can reduce the variability in the measured particle fracture strength of positive electrode active materials for non-aqueous electrolyte secondary batteries.
  • the method for measuring the particle breaking strength of a positive electrode active material for a non-aqueous electrolyte secondary battery which is one aspect of the present disclosure, is characterized in that the particle breaking strength of the positive electrode active material is measured while maintaining the dew point at or below 0°C.
  • the device for measuring the particle fracture strength of a positive electrode active material for a non-aqueous electrolyte secondary battery which is one aspect of the present disclosure, is characterized by having a mechanism for measuring the particle fracture strength of the positive electrode active material while maintaining the dew point of the sample exposure area at or below 0°C.
  • the method for measuring the particle fracture strength of a positive electrode active material for a non-aqueous electrolyte secondary battery can reduce the variability in the measured values.
  • the above measurement method can be carried out by using a device for measuring the particle fracture strength of a positive electrode active material for a non-aqueous electrolyte secondary battery, which is one aspect of the present disclosure.
  • FIG. 1 is a schematic diagram illustrating a configuration of a measurement device according to an embodiment. 1 is a flowchart illustrating an example of a measurement method according to an embodiment.
  • the particle crushing strength of positive electrode active materials is measured using a commercially available hardness tester.
  • commercially available hardness testers are designed to measure a wide range of objects, detailed consideration of the conditions for measuring the particle crushing strength of positive electrode active materials has been insufficient.
  • the positive electrode active material to be measured includes, for example, a lithium transition metal composite oxide.
  • the lithium transition metal composite oxide contains, for example, Ni.
  • the Ni content in the lithium transition metal composite oxide may be 60 mol% or more, 80 mol% or more, or 90 mol% or more, based on the total number of moles of metal elements other than Li in the lithium transition metal composite oxide.
  • the Ni content is preferably 98 mol% or less.
  • a positive electrode active material such as a lithium transition metal composite oxide absorbs moisture in the atmosphere, and alkaline components such as Li are easily eluted. The eluted alkaline components change the surface condition of the particles, which causes variation in the measurement of particle breaking strength. This tendency is more pronounced as the Ni content in the positive electrode active material increases, so measuring the particle breaking strength in an atmosphere where the dew point is kept below 0°C is effective in reducing the variation in the measured value.
  • the positive electrode active material may contain a lithium transition metal composite oxide other than that represented by the above general formula, or other compounds, within the scope of the present disclosure.
  • the molar fraction of the metal element contained in the entire particle of the lithium transition metal composite oxide can be measured by inductively coupled plasma (ICP) emission spectroscopy.
  • ICP inductively coupled plasma
  • the lithium transition metal composite oxide may have a layered structure.
  • the layered structure of the lithium transition metal composite oxide include a layered structure belonging to the space group R-3m and a layered structure belonging to the space group C2/m. From the viewpoint of high capacity and stability of the crystal structure, it is preferable that the lithium transition metal composite oxide has a layered structure belonging to the space group R-3m.
  • the layered structure of the lithium transition metal composite oxide may include a transition metal layer, a Li layer, and an oxygen layer.
  • the lithium transition metal composite oxide may contain secondary particles formed by agglomeration of primary particles.
  • the particle size of the primary particles is, for example, 0.02 ⁇ m or more and 2 ⁇ m or less.
  • the particle size of the primary particles is measured as the diameter of the circumscribed circle in a particle image observed by a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the average particle size of the secondary particles is, for example, 2 ⁇ m or more and 30 ⁇ m or less.
  • the average particle size means the volume-based median diameter (D50).
  • D50 means the particle size at which the cumulative frequency is 50% from the smallest particle size in the volume-based particle size distribution, and is also called the median diameter.
  • the particle size distribution of the secondary particles can be measured using a laser diffraction type particle size distribution measuring device (for example, MT3000II manufactured by Microtrack Bell Co., Ltd.) using water as a dispersion medium.
  • FIG. 1 is a schematic diagram showing the configuration of a measuring device 10, which is an example of an embodiment.
  • the measuring device 10 includes, for example, a movable sample stage 11, a low-magnification microscope 12, a high-magnification microscope 13, a hardness tester 15 having an indenter 14, and a camera 16.
  • the inside of the measuring device 10 is a sample exposure area 20, and the positive electrode active material, which is a sample, is exposed in the sample exposure area 20.
  • the movable sample stage 11 can be moved left and right in FIG. 1, and the particles of positive electrode active material to be measured can be placed on it and moved under the microscopes 12 and 13 and hardness meter 15.
  • the low-magnification microscope 12 is used to focus on the surface of the particle to be measured.
  • the high-magnification microscope 13 is used to select the particle to be measured. Specifically, by adjusting the sample stage 11 so that the particle to be measured is located at the center of the field of view of the microscope 13, the indenter 14 can be pressed near the center of the particle.
  • a commercially available device may be used as the hardness meter 15.
  • An example of a commercially available device is the Dynamic Ultra-Micro Hardness Tester DUH-211S manufactured by Shimadzu Corporation.
  • the indenter 14 an indenter that comes with a commercially available device may also be used. From the test force-displacement diagram obtained from a test using the hardness meter 15, the pressing force of the indenter at which the particle breaks can be determined.
  • the particle breaking strength can be calculated by the following formula (1).
  • the particle breaking strength may be measured for a plurality of particles of the positive electrode active material, and the average value may be used as the particle breaking strength of the positive electrode active material.
  • the particle breaking strength may be calculated by measuring 10 to 30 particles of the positive electrode active material.
  • Camera 16 is used, for example, to observe the process of particle destruction by hardness meter 15.
  • the type of camera 16 is not particularly limited, and may be, for example, a CCD camera or a CMOS camera.
  • the measuring device 10 has a mechanism for measuring the particle fracture strength of the positive electrode active material in a state where the dew point of the sample exposure region 20 is kept at or below 0° C. In other words, the atmosphere inside the measuring device 10 is kept so that the dew point is at or below 0° C. This reduces the effect of moisture in the atmosphere on the particle fracture strength, and the variation in the measured values can be reduced. 1, a measurement device 10 is provided with an inlet and an outlet for dry air, and dry air is allowed to flow inside, thereby making it possible to measure the particle crushing strength of the positive electrode active material in an atmosphere with a dew point kept at or below 0° C.
  • the temperature of the sample exposure region 20 is not particularly limited, but is, for example, room temperature, more specifically, 23° C. ⁇ 5° C.
  • the particle breaking strength of the positive electrode active material is preferably measured in an atmosphere where the dew point is kept at -10°C or less, more preferably in an atmosphere where the dew point is kept at -20°C or less, and particularly preferably in an atmosphere where the dew point is kept at -30°C or less.
  • the inventors' studies have revealed that the higher the dew point of the atmosphere, the lower the particle breaking strength tends to be. It is believed that when the dew point of the atmosphere is high, the surfaces of the primary particles that make up the positive electrode active material become wet, making it easier for slippage to occur between the primary particles, resulting in lower particle breaking strength. The lower the dew point temperature, the more stable the surface condition of the particles, which reduces the variability in the measured particle breaking strength.
  • the particle breaking strength of the positive electrode active material is preferably measured in an atmosphere where the dew point is kept constant.
  • an atmosphere where the dew point is kept constant means an atmosphere where the dew point is kept within a range of the average value ⁇ 2°C.
  • an atmosphere where the dew point is kept below 0°C means an atmosphere where the average dew point value is kept below 0°C.
  • the particle breaking strength of the positive electrode active material is preferably measured in an atmosphere where the dew point is kept constant at -10°C or less, more preferably in an atmosphere where the dew point is kept constant at -20°C or less, and particularly preferably in an atmosphere where the dew point is kept constant at -30°C or less.
  • the particle size of the positive electrode active material used to measure particle breaking strength is preferably constant. This allows the variability in the measured particle breaking strength values to be reduced.
  • Constant particle size of the positive electrode active material means that the particle size of the positive electrode active material is within the range of the average particle size (D50) ⁇ 0.5 ⁇ m.
  • particles with a narrow particle size distribution and particles with a wide particle size distribution are used depending on the purpose.
  • particles with a narrow particle size distribution or particles with a wide particle size distribution may be used alone, or multiple types of particles with different particle size distributions may be mixed and used.
  • the average particle diameter can be calculated from the particle size distribution, and measurements can be made using particles with an average particle diameter of ⁇ 0.5 ⁇ m.
  • measurements can be made using particles with a particle diameter of ⁇ 0.5 ⁇ m for each particle diameter corresponding to each peak top position in the particle size distribution.
  • the particle size of the positive electrode active material used to measure particle crushing strength is preferably 3 ⁇ m or more. This reduces the effect of the indenter being displaced from the center of the particle, thereby reducing the variability of the measured value.
  • Figure 2 is a flow chart showing an example of a measurement method according to an embodiment.
  • the laminate containing the positive electrode active material particles is opened, and the positive electrode active material particles are placed on the sample stage 11 (S1).
  • the positive electrode active material particles placed on the sample stage 11 are observed with a low-magnification microscope 12, and the focal position is adjusted so that the focus is on the surface of the particle (S2).
  • a high-magnification microscope 13 is used to select the particle to be measured (S3).
  • the position of the sample stage 11 is adjusted so that the indenter 14 is pressed into the vicinity of the center of the particle.
  • the indenter 14 After moving the sample stage 11 to below the hardness meter, the indenter 14 is pressed into the particle while observing with the camera 16, and the pressing force of the indenter 14 when the particle breaks is measured (S4).
  • the particle breaking strength is calculated using the breaking strength calculation method described above (S5), and this flow ends. If the breaking strength of other particles is to be measured next, steps S2 to S5 are executed again.
  • Example 1-1 Using the measuring device shown in FIG. 1, the measurement was performed so that the temperature of the sample exposure area was kept constant at 25°C and the dew point was kept constant at -5°C.
  • the hardness tester a dynamic ultra-micro hardness tester DUH-211S manufactured by Shimadzu Corporation was used.
  • the laminate in which the lithium transition metal composite oxide particles represented by the general formula LiNi 0.6 Co 0.2 Mn 0.2 O 2 were enclosed was opened, and the particle breaking strength of the lithium transition metal composite oxide was measured. Measurement was performed for 10 particles with a particle size in the range of the average particle size (D50) ⁇ 0.5 ⁇ m, and the average value of the measurement results was calculated and used as the particle breaking strength.
  • the particle size of the lithium transition metal composite oxide particles used in the measurement was 3 ⁇ m or more in all cases.
  • Example 1-3 The standard deviation was calculated in the same manner as in Example 1-1, except that the dew point in the sample exposure area was kept constant at -25°C.
  • Example 1-4 The standard deviation was calculated in the same manner as in Example 1-1, except that the dew point in the sample exposure area was kept constant at -35°C.
  • Example 1-5> The standard deviation was calculated from a total of 28 measurement results obtained in Examples 1-1 to 1-4. That is, the standard deviation is shown when the dew point of the sample exposure area was not constant but was varied in the range of -5°C to -35°C.
  • Configuration 1 A method for measuring particle fracture strength of a positive electrode active material for a non-aqueous electrolyte secondary battery, the method comprising measuring the particle fracture strength of the positive electrode active material in an atmosphere whose dew point is kept at 0° C. or lower.
  • Configuration 2 2. The method for measuring particle fracture strength of the positive electrode active material for a non-aqueous electrolyte secondary battery according to claim 1, wherein the measurement is performed in an atmosphere in which a dew point is kept constant.
  • Configuration 3 3.
  • Configuration 11 11. The method for measuring particle fracture strength of a positive electrode active material for a non-aqueous electrolyte secondary battery according to any one of claims 1 to 10, wherein the particle size of the positive electrode active material is 3 ⁇ m or more.
  • Configuration 12 An apparatus for measuring particle fracture strength of a positive electrode active material for a non-aqueous electrolyte secondary battery, the apparatus having a mechanism for measuring particle fracture strength of the positive electrode active material while maintaining the dew point of a sample exposure area at 0° C. or lower.

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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)
PCT/JP2024/026080 2023-07-28 2024-07-22 非水電解質二次電池用正極活物質の粒子破壊強度の測定方法および測定装置 Pending WO2025028315A1 (ja)

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JP2025537852A JPWO2025028315A1 (https=) 2023-07-28 2024-07-22
CN202480047059.8A CN121532861A (zh) 2023-07-28 2024-07-22 非水电解质二次电池用正极活性物质的颗粒破坏强度的测定方法及测定装置

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004335152A (ja) * 2003-04-30 2004-11-25 Sumitomo Metal Mining Co Ltd 非水系電解質二次電池用正極活物質および非水系電解質二次電池
WO2018003929A1 (ja) * 2016-06-30 2018-01-04 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電極シートおよび蓄電デバイス
WO2018043671A1 (ja) 2016-08-31 2018-03-08 住友化学株式会社 リチウム二次電池用正極活物質、リチウム二次電池用正極及びリチウム二次電池
JP2021114408A (ja) 2020-01-17 2021-08-05 住友化学株式会社 全固体リチウムイオン電池用正極活物質、電極及び全固体リチウムイオン電池
JP2022177291A (ja) * 2018-03-26 2022-11-30 住友金属鉱山株式会社 高強度リチウムイオン二次電池用正極活物質、及び、該正極活物質を用いたリチウムイオン二次電池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004335152A (ja) * 2003-04-30 2004-11-25 Sumitomo Metal Mining Co Ltd 非水系電解質二次電池用正極活物質および非水系電解質二次電池
WO2018003929A1 (ja) * 2016-06-30 2018-01-04 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電極シートおよび蓄電デバイス
WO2018043671A1 (ja) 2016-08-31 2018-03-08 住友化学株式会社 リチウム二次電池用正極活物質、リチウム二次電池用正極及びリチウム二次電池
JP2022177291A (ja) * 2018-03-26 2022-11-30 住友金属鉱山株式会社 高強度リチウムイオン二次電池用正極活物質、及び、該正極活物質を用いたリチウムイオン二次電池
JP2021114408A (ja) 2020-01-17 2021-08-05 住友化学株式会社 全固体リチウムイオン電池用正極活物質、電極及び全固体リチウムイオン電池

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