WO2024113200A1 - Matériau actif d'électrode positive et son procédé de préparation, feuille d'électrode positive, batterie secondaire et appareil électrique - Google Patents

Matériau actif d'électrode positive et son procédé de préparation, feuille d'électrode positive, batterie secondaire et appareil électrique Download PDF

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Publication number
WO2024113200A1
WO2024113200A1 PCT/CN2022/135243 CN2022135243W WO2024113200A1 WO 2024113200 A1 WO2024113200 A1 WO 2024113200A1 CN 2022135243 W CN2022135243 W CN 2022135243W WO 2024113200 A1 WO2024113200 A1 WO 2024113200A1
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positive electrode
active material
electrode active
optionally
battery
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Chinese (zh)
Inventor
吴凯
陈强
吴奇
沈重亨
桓书星
范敬鹏
柳娜
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology Co Ltd
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Priority to CN202280007813.6A priority Critical patent/CN118696435B/zh
Priority to PCT/CN2022/135243 priority patent/WO2024113200A1/fr
Publication of WO2024113200A1 publication Critical patent/WO2024113200A1/fr
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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
    • H01M4/50—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
    • 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

  • the present application relates to the technical field of lithium batteries, and in particular to a positive electrode active material and a preparation method thereof, and a positive electrode sheet, a secondary battery and an electrical device comprising the positive electrode active material.
  • high-nickel ternary materials have significantly improved in energy density compared with other materials, with the increase of nickel content, there will be more serious capacity decay and layered structure damage during the charging and discharging process, which to a certain extent hinders the further development of high-nickel ternary materials. Therefore, it is necessary to adopt certain strategies to optimize high-nickel ternary materials, so as to improve the energy density of the battery and improve the cycle performance and safety performance of the battery.
  • the present application is made in view of the above-mentioned problems, and its purpose is to provide a positive electrode active material with good dispersibility, high compaction density, and improved structural stability, and to provide a preparation method of the positive electrode active material, as well as a positive electrode sheet, a secondary battery, and an electrical device containing the positive electrode active material of the present application.
  • the first aspect of the present application provides a positive electrode active material, wherein the positive electrode active material comprises a first positive electrode active material A and a second positive electrode active material B,
  • the chemical formula of the second positive electrode active material B is Li a2 [Ni x2 Co y2 Mn z2 M2 b2 M4 C2 ]O 2 , wherein 0 ⁇ x2 ⁇ 1, 0 ⁇ y2 ⁇ 0.5, 0 ⁇ z2 ⁇ 0.5, 0.9 ⁇ a2 ⁇ 1.2, 0 ⁇ b2 ⁇ 0.2, 0 ⁇ c2 ⁇ 0.2
  • the present application at least includes the following beneficial effects:
  • the positive electrode active material of the present application not only has a high filling degree between particles, good dispersibility and high compaction density, which can effectively improve the energy density of the battery, but also has improved structural stability, effectively preventing the electrolyte from having side reactions on the surface of the positive electrode active material, thereby improving the cycle performance and safety performance of the battery;
  • the positive electrode active material of the present application can refine the grains of the first positive electrode active material A by doping with the M1 element (i.e., W, Nb or Mo), so that the grains tend to be distributed radially, and the M1 element is enriched at the grain boundary, so that the compressive strength of the polycrystalline first positive electrode active material A is improved, the cracking is reduced, and the side reaction between the crack and the electrolyte is reduced, and the oxygen release is reduced, thereby improving the cycle performance and safety performance of the battery;
  • M1 element i.e., W, Nb or Mo
  • the positive electrode active material of the present application improves the structural stability of the second positive electrode active material B by doping with the M2 (i.e., Sr, Y or V) element having a melting effect, increases the particle size of the single crystal second positive electrode active material B, thereby reducing the side reaction between its surface and the electrolyte, reducing oxygen release, and thus improving the cycle performance and safety performance of the battery.
  • M2 i.e., Sr, Y or V
  • the weight ratio of the first positive electrode active material A to the second positive electrode active material B is 10:1-1:1, and can be optionally 9:1-3:2.
  • the weight ratio of the first positive electrode active material A to the second positive electrode active material B in the positive electrode active material is within the above range, the positive electrode active material has a high compaction density, which can effectively improve the energy density of the battery.
  • the (Dv90-Dv10)/Dv50 of the positive electrode active material is 1.5-2.5, and can be optionally 1.75-2.0.
  • the positive electrode active material particles are continuously distributed, have good dispersibility, and improve space utilization, which is conducive to improving the processing performance of the positive electrode active material.
  • the positive electrode active material satisfies the following formula:
  • ⁇ Dv1, ⁇ Dv3, ⁇ Dv5 are the differences between Dv1, Dv3 and Dv5 of the positive electrode active material and Dv1', Dv3' and Dv5' of the positive electrode active material after being pressurized with a weight of 1 ton.
  • the positive electrode active material satisfies the above formula, the positive electrode active material has good structural stability, high compressive strength of the material and less particle cracking, effectively preventing side reactions between the cracks and the electrolyte, reducing oxygen release, thereby improving the cycle performance and safety performance of the battery.
  • the electrochemically active specific surface area of the positive electrode active material is 1-8 cm 2 /g, and can be 2-6 cm 2 /g.
  • the positive electrode active material has good structural stability, effectively preventing the electrolyte from having side reactions on the surface of the positive electrode active material, thereby improving the cycle performance and safety performance of the battery.
  • the compaction density of the positive electrode active material under a pressure of 5 tons (T) is 3.4-4.0 g/cm 3 , and can be optionally 3.7-3.9 g/cm 3 .
  • the positive electrode active material has a high compaction density and a high filling degree between particles, which is not only conducive to improving the processing performance of the positive electrode active material, but also can effectively improve the energy density of the battery.
  • the amount of M1 in the first positive electrode active material A is 500-8000ppm, optionally 1000-4000ppm, and the amount of M3 is 1000-20000ppm, optionally 3000-15000ppm.
  • the compressive strength of the polycrystalline first positive electrode active material A can be improved, cracking can be reduced, and the side reaction between the cracking and the electrolyte can be effectively reduced, thereby improving the cycle performance and safety performance of the battery.
  • the amount of M2 in the second positive electrode active material B is 500-8000ppm, optionally 1000-4000ppm, and the amount of M4 is 1000-20000ppm, optionally 3000-15000ppm.
  • the structural stability of the single crystal second positive electrode active material B can be improved, the single crystal particle size can be increased, thereby reducing the side reaction between its surface and the electrolyte, reducing oxygen release, and thus improving the cycle performance and safety performance of the battery.
  • the Dv50 of the first positive electrode active material A is 7-15 ⁇ m, (Dv90-Dv10)/Dv50 is 0.5-1.5, and can be 1.0-1.45; the Dv50 of the second positive electrode active material B is 2-4 ⁇ m, (Dv90-Dv10)/Dv50 is 0.5-1.5, and can be 1.0-1.45.
  • the positive electrode active material of the present application can have a high filling degree between particles, good dispersibility and high compaction density, and can effectively improve the energy density of the battery.
  • a third aspect of the present application provides a positive electrode sheet, comprising a positive electrode current collector and a positive electrode film layer disposed on at least one surface of the positive electrode current collector, wherein the positive electrode film layer comprises the positive electrode active material of the first aspect of the present application or the positive electrode active material prepared by the method of the second aspect of the present application, and when the coating amount of the positive electrode sheet is less than 0.025 g/cm 2 , the compaction density of the positive electrode sheet is ⁇ 3.3 g/cm 3 , and can be optionally ⁇ 3.4 g/cm 3 .
  • a fifth aspect of the present application provides an electrical device comprising a secondary battery selected from the fourth aspect of the present application.
  • the electric device of the present application includes the secondary battery provided by the present application, and thus has at least the same advantages as the secondary battery.
  • FIG. 2 is an exploded view of the secondary battery according to the embodiment of the present application shown in FIG. 1 .
  • FIG. 3 is a schematic diagram of a battery module according to an embodiment of the present application.
  • FIG. 4 is a schematic diagram of a battery pack according to an embodiment of the present application.
  • FIG. 5 is an exploded view of the battery pack shown in FIG. 4 according to an embodiment of the present application.
  • range disclosed in the present application is defined in the form of a lower limit and an upper limit, and a given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundaries of a particular range.
  • the range defined in this way can be inclusive or exclusive of end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a range. For example, if a range of 60-120 and 80-110 is listed for a specific parameter, it is understood that the range of 60-110 and 80-120 is also expected.
  • the numerical range "a-b" represents the abbreviation of any real number combination between a and b, wherein a and b are real numbers.
  • the numerical range "0-5" represents that all real numbers between "0-5" have been fully listed herein, and "0-5" is just the abbreviation of these numerical combinations.
  • a parameter is expressed as an integer ⁇ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.
  • the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially.
  • the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.
  • the “include” and “comprising” mentioned in this application represent open-ended or closed-ended expressions.
  • the “include” and “comprising” may represent that other components not listed may also be included or only the listed components may be included or only the listed components may be included.
  • the term "or” is inclusive.
  • the phrase “A or B” means “A, B, or both A and B”. More specifically, any of the following conditions satisfies the condition "A or B”: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).
  • first and second are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the quantity of the indicated technical features.
  • the high-nickel ternary positive electrode material combines the synergistic effects of the three elements Ni-Co-Mn.
  • the Ni element can effectively increase the specific capacity of the material and improve the energy density of the material;
  • the Co element has excellent electrochemical activity, which reduces the mixing of Li + and Ni2 + cations in the material, while improving the electronic conductivity of the material and improving the cycle performance; and
  • the Mn element can reduce material costs, improve battery safety and stability, and stabilize the crystal structure of the material.
  • Ni2 + occupies the Li + position, making it impossible for Li + to be embedded in the lithium layer when the material is discharged, resulting in loss of material capacity and reduced rate performance; 2) Since Ni4 + is reducible and easily generates Ni3 + , in order to maintain charge balance, oxygen will be released from the material, resulting in the destruction of the material structure and reduced thermal stability; 3) Since Li + diffusion is affected by kinetic factors, the amount of Li released increases, causing the transition metal ions to be reduced. In order to maintain its electrical neutrality, the material is prone to form new phases and pores on the surface, resulting in unstable structure of high-nickel cathode materials. The structural instability is accelerated under overcharge conditions, because it is accompanied by partial structural transformation to spinel and NiO rock salt phases, and oxygen is generated, which poses certain hidden dangers to the safety of the battery.
  • the electrochemical properties of materials are usually improved by means of surface coating, ion doping, and size particle grading.
  • large particles are polycrystalline, which are secondary large particles formed by the agglomeration of small particle single crystals, and have high discharge capacity and first cycle efficiency.
  • the present application provides a positive electrode active material, wherein the positive electrode active material comprises a first positive electrode active material A and a second positive electrode active material B.
  • the chemical formula of the second positive electrode active material B is Li a2 [Ni x2 Co y2 Mn z2 M2 b2 M4 C2 ]O 2 , wherein 0 ⁇ x2 ⁇ 1, 0 ⁇ y2 ⁇ 0.5, 0 ⁇ z2 ⁇ 0.5, 0.9 ⁇ a2 ⁇ 1.2, 0 ⁇ b2 ⁇ 0.2, 0 ⁇ c2 ⁇ 0.2
  • the positive electrode active material of the present application not only has a high filling degree between particles, good dispersibility and high compaction density, which can effectively improve the energy density of the battery, but also has improved structural stability, effectively preventing the electrolyte from having side reactions on the surface of the positive electrode active material.
  • the positive electrode active material of the present application can refine the grains of the first positive electrode active material A by doping with M1 (i.e.
  • the positive electrode active material of the present application improves the structural stability of the second positive electrode active material B by doping with M2 (i.e. Sr, Y or V) elements with a melting effect, increases the particle size of the second positive electrode active material B, thereby reducing the side reaction between its surface and the electrolyte, reducing oxygen release, thereby improving the cycle performance and safety performance of the battery.
  • M2 i.e. Sr, Y or V
  • the first positive electrode active material A can be a polycrystalline material, that is, a plurality of primary particles are aggregated together to form spherical or quasi-spherical secondary particles;
  • the second positive electrode active material B can be a single crystal material, that is, a single particle without obvious agglomeration, and a primary particle with a size greater than 1 ⁇ m.
  • the weight ratio of the first positive electrode active material A to the second positive electrode active material B is 10:1-1:1, and can be 9:1-3:2.
  • the weight ratio of the first positive electrode active material A to the second positive electrode active material B in the positive electrode active material is within the above range, the positive electrode active material has a high compaction density, which can effectively improve the energy density of the battery.
  • the (Dv90-Dv10)/Dv50 of the positive electrode active material is 1.5-2.5, and optionally 1.75-2.0.
  • the positive electrode active material particles are continuously distributed, have good dispersibility, and improve space utilization, which is conducive to improving the processing performance of the positive electrode active material.
  • the Dv10, Dv50 and Dv90 are the particle sizes of the positive electrode active material measured by volume particle size distribution, wherein the Dv10 is the particle size corresponding to when the cumulative volume percentage of the sample reaches 10%, the Dv50 is the particle size corresponding to when the cumulative volume percentage of the sample reaches 50%, and the Dv90 is the particle size corresponding to when the cumulative volume percentage of the sample reaches 90%.
  • the positive electrode active material satisfies the following formula:
  • ⁇ Dv1, ⁇ Dv3, ⁇ Dv5 are the differences between Dv1, Dv3 and Dv5 of the positive electrode active material and Dv1', Dv3' and Dv5' of the positive electrode active material after being pressurized with a weight of 1 ton.
  • the positive electrode active material satisfies the above formula, the positive electrode active material has good structural stability, high compressive strength of the material and less particle cracking, effectively preventing side reactions between the cracks and the electrolyte, reducing oxygen release, thereby improving the cycle performance and safety performance of the battery.
  • Dv1 is the particle size corresponding to the cumulative volume distribution percentage of the sample when it reaches 1%
  • Dv3 is the particle size corresponding to the cumulative volume distribution percentage of the sample when it reaches 3%
  • Dv5 is the particle size corresponding to the cumulative volume distribution percentage of the sample when it reaches 5%.
  • Dv1' is the particle size corresponding to the cumulative volume distribution percentage of the sample after pressurizing with 1 ton of weight (i.e., pressurizing with 1 ton of weight for 30 seconds on a fixed area of 1.33 cm2 );
  • Dv3' is the particle size corresponding to the cumulative volume distribution percentage of the sample after pressurizing with 1 ton of weight (i.e., pressurizing with 1 ton of weight for 30 seconds on a fixed area of 1.33 cm2 );
  • Dv5' is the particle size corresponding to the cumulative volume distribution percentage of the sample after pressurizing with 1 ton of weight (i.e., pressurizing with 1 ton of weight for 30 seconds on a fixed area of 1.33 cm2 ) when it reaches 5%.
  • ⁇ Dv1 Dv1-Dv1'
  • ⁇ Dv3 Dv3-Dv3'
  • ⁇ Dv5 Dv5-Dv5'.
  • K ⁇ Dv1/Dv1*0.01+ ⁇ Dv3/Dv3*0.03+ ⁇ Dv5/Dv5*0.05 can be used to indicate the weighted crushing degree of the positive electrode active material.
  • K can be ⁇ 7%, ⁇ 5%, ⁇ 4.5%, ⁇ 4%, ⁇ 3.5%, ⁇ 3%, ⁇ 2.5%, ⁇ 2%, ⁇ 1.5%, ⁇ 1% or ⁇ 0.5%.
  • the electrochemically active specific surface area of the positive electrode active material is 1-8 cm 2 /g, and optionally 2-6 cm 2 /g.
  • the positive electrode active material has good structural stability, effectively preventing the electrolyte from having side reactions on the surface of the positive electrode active material, thereby improving the cycle performance and safety performance of the battery.
  • the electrochemically active specific surface area refers to the electroactive effective specific surface area of the material's electrical properties.
  • cyclic voltammetry is used, using an electrochemical workstation VMP3, using the cathode active material of the present application to assemble and buckle, and scanning four cycles of CV of the electroactive probe at scan rates of 1.0 mV/s, 0.5 mV/s, 0.3 mV/s and 0.1 mV/s, respectively.
  • the electrochemically active specific surface area of the cathode active material is obtained by combining the peak current Ip, diffusion coefficient D, scan rate v, electron transfer number n (1) and concentration c (50 mmol/L) in the test.
  • the electrochemically active specific surface area of the positive electrode active material is, for example, 1-8 cm 2 /g, 2-6 cm 2 /g, 3-5.5 cm 2 /g or 3.5-4.5 cm 2 /g.
  • the compaction density of the positive electrode active material under a pressure of 5 tons (T) is 3.4-4.0 g/cm 3 , and can be optionally 3.7-3.9 g/cm 3.
  • the positive electrode active material has a high compaction density and a high filling degree between particles, which is not only conducive to improving the processing performance of the positive electrode active material, but also can effectively improve the energy density of the battery.
  • the compaction density can be measured according to GB/T24533-2009.
  • the amount of M1 in the first positive active material A is 500-8000ppm, optionally 1000-4000ppm, and the amount of M3 is 1000-20000ppm, optionally 3000-15000ppm.
  • the compressive strength of the polycrystalline first positive active material A can be improved, cracking can be reduced, and the side reaction between the cracking and the electrolyte can be effectively reduced, thereby improving the cycle performance and safety performance of the battery.
  • the amount of M1 element and M3 element in the first positive active material is measured by a detection technique commonly used to measure the content of doping elements known in the art, such as inductively coupled plasma emission spectroscopy (ICP).
  • ICP inductively coupled plasma emission spectroscopy
  • the amount of M2 in the second positive active material B is 500-8000ppm, optionally 1000-4000ppm, and the amount of M4 is 1000-20000ppm, optionally 3000-15000ppm.
  • the structural stability of the single-crystal second positive active material B can be improved, the single crystal particle size can be increased, thereby reducing the side reaction between its surface and the electrolyte, reducing oxygen release, thereby improving the cycle performance and safety performance of the battery.
  • the amount of M2 element and M4 element in the first positive active material is measured by a detection technique commonly used to measure the content of doping elements known in the art, such as inductively coupled plasma emission spectroscopy (ICP).
  • ICP inductively coupled plasma emission spectroscopy
  • the molar ratio of M1 to M3 in the first positive electrode active material A is 1:80-4:1, and can be 1:30-3:4.
  • the first positive electrode active material A has high compressive strength, less particle cracking, effectively preventing the electrolyte from having side reactions on the surface of the positive electrode active material, reducing oxygen release, and thus improving the cycle performance and safety performance of the battery.
  • the molar ratio of M2 to M4 in the second positive electrode active material B is 1:40-8:1, optionally 1:20-3:2, and further optionally 1:2-1:1.
  • the second positive electrode active material B has high structural stability, effectively preventing the electrolyte from having side reactions on the surface of the positive electrode active material, reducing oxygen release, and thus improving the cycle performance and safety performance of the battery.
  • the Dv50 of the first positive electrode active material A is 7-15 ⁇ m, (Dv90-Dv10)/Dv50 is 0.5-1.5, and can be 1.0-1.45; the Dv50 of the second positive electrode active material B is 2-4 ⁇ m, (Dv90-Dv10)/Dv50 is 0.5-1.5, and can be 1.0-1.45.
  • the positive electrode active material of the present application can have a high filling degree between particles, good dispersibility, and can optimize the compaction density of the positive electrode active material, which can effectively improve the energy density of the battery.
  • the second aspect of the present application provides a method for preparing a positive electrode active material, comprising the following steps:
  • the positive electrode active material prepared by the above method not only has a high filling degree between particles, good dispersibility and high compaction density, which can effectively improve the energy density of the battery, but also has improved structural stability, effectively preventing the electrolyte from having side reactions on the surface of the positive electrode active material, thereby improving the cycle performance and safety performance of the battery.
  • the precursor of the first positive electrode active material A and the precursor of the second positive electrode active material B can be prepared by methods known in the prior art, such as a hydroxide co-precipitation method, for example, by the method described in CN 111384372A. More specifically, the precursor of the first positive electrode active material A can include but is not limited to Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 , Ni 0.9 Co 0.05 Mn 0.05 (OH) 2 , Ni 0.7 Co 0.1 Mn 0.2 (OH) 2 , Ni 0.96 Co 0.03 Mn 0.01 (OH) 2 , and Ni 0.75 Co 0.1 Mn 0.15 (OH) 2 .
  • the precursor of the second positive active material B may include but is not limited to Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 , Ni 0.9 Co 0.05 Mn 0.05 (OH) 2 , Ni 0.7 Co 0.1 Mn 0.2 (OH) 2 , Ni 0.96 Co 0.03 Mn 0.01 (OH) 2 , and Ni 0.75 Co 0.1 Mn 0.15 (OH) 2 .
  • the first positive electrode active material A and the second positive electrode active material B are mixed at a weight ratio of 10:1-1:1, optionally 9:1-3:2.
  • a positive electrode active material with a high compaction density can be obtained, which can effectively improve the energy density of the battery.
  • the compound containing the M1 element is one or more of an oxide, carbonate or hydroxide containing the M1 element, and the M1 element is one of W, Nb or Mo;
  • the compound containing the M3 element is one or more of an oxide, carbonate or hydroxide containing the M3 element, and the M3 element is one of Zr, Ti, Mg, Al, Sb, B or Co;
  • the compound containing the M2 element is one or more of an oxide, carbonate or hydroxide containing the M2 element, and the M2 element is one of Sr, Y or V;
  • the compound containing the M4 element is one or more of an oxide, carbonate or hydroxide containing the M4 element, and the M4 element is one of Zr, Ti, Mg, Al, Sb, B or Co.
  • the Dv50 of the precursor of the first positive electrode active material A is 7-15 ⁇ m; the Dv50 of the precursor of the second positive electrode active material B is 2-4 ⁇ m.
  • the sintering temperature is 700-850°C, optionally 700-800°C, the sintering time is 10-20h, and the sintering atmosphere is oxygen or air.
  • the M1 and M3 elements can be enriched at the grain boundaries, the compressive strength of the first positive electrode active material A can be improved, cracking can be reduced, and the electrolyte can be effectively prevented from having side reactions on the surface of the positive electrode active material, reducing oxygen release, thereby improving the cycle performance and safety performance of the battery.
  • the sintering temperature is 750-1000°C, optionally 750-850°C, the sintering time is 10-20h, and the sintering atmosphere is oxygen or air.
  • a third aspect of the present application provides a positive electrode plate, comprising a positive electrode current collector and a positive electrode film layer disposed on at least one surface of the positive electrode current collector, wherein the positive electrode film layer comprises the positive electrode active material of the first aspect of the present application or the positive electrode active material prepared by the method of the second aspect of the present application, and when the coating amount of the positive electrode plate is less than 0.025 g/cm 2 , the compaction density of the positive electrode plate is ⁇ 3.3 g/cm 3 , optionally ⁇ 3.4 g/cm 3 , optionally ⁇ 3.5 g/cm 3 , optionally ⁇ 3.6 g/cm 3 , optionally ⁇ 3.7 g/cm 3 or optionally ⁇ 3.8 g/cm 3 .
  • the coating amount of the positive electrode sheet is less than 0.025 g/cm 2 , for example, 0.015-0.02 g/cm 2 .
  • the fourth aspect of the present application provides a secondary battery, which includes the positive electrode active material of the first aspect of the present application or the positive electrode active material prepared by the method of the second aspect of the present application or the positive electrode plate of the third aspect of the present application.
  • a fifth aspect of the present application provides an electrical device comprising a secondary battery selected from the fourth aspect of the present application.
  • the secondary battery may be in the form of a battery cell, a battery module, or a battery pack.
  • the battery module and the battery pack may include a battery cell, and the battery pack may also include a battery module.
  • the battery cells may be assembled into a battery module. In some embodiments, the battery cells may be assembled into a battery pack. In some embodiments, the battery modules may be assembled into a battery pack.
  • the secondary battery in the form of a battery cell
  • a battery module in the form of a battery cell
  • a battery pack in the form of a battery pack
  • an electric device of the present application is described below with appropriate reference to the drawings.
  • a secondary battery is provided.
  • a secondary battery typically includes a positive electrode sheet, a negative electrode sheet, an electrolyte and a separator.
  • active ions are embedded and removed back and forth between the positive electrode sheet and the negative electrode sheet.
  • the electrolyte plays the role of conducting ions between the positive electrode sheet and the negative electrode sheet.
  • the separator is arranged between the positive electrode sheet and the negative electrode sheet, mainly to prevent the positive and negative electrodes from short-circuiting, while allowing ions to pass through.
  • the battery group margin is 90-95%.
  • the positive electrode plate includes a positive electrode current collector and a positive electrode film layer arranged on at least one surface of the positive electrode current collector, wherein the positive electrode film layer includes the positive electrode active material of the first aspect of the present application.
  • the positive electrode current collector has two surfaces opposite to each other in its thickness direction, and the positive electrode film layer is disposed on any one or both of the two opposite surfaces of the positive electrode current collector.
  • the positive electrode current collector may be a metal foil or a composite current collector.
  • aluminum foil may be used as the metal foil.
  • the composite current collector may include a polymer material base and a metal layer formed on at least one surface of the polymer material base.
  • the composite current collector may be formed by forming a metal material (aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • PP polypropylene
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the positive electrode active material may be the positive electrode active material of the first aspect of the present application.
  • the weight ratio of the positive electrode active material in the positive electrode film layer is 80-100 weight %, based on the total weight of the positive electrode film layer.
  • the positive electrode film layer may also optionally include a binder.
  • the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer and fluorine-containing acrylate resin.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PTFE polytetrafluoroethylene
  • the weight ratio of the binder in the positive electrode film layer is 0-20% by weight, based on the total weight of the positive electrode film layer.
  • the positive electrode film layer may further include a conductive agent.
  • the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
  • the weight ratio of the conductive agent in the positive electrode film layer is 0-20% by weight, based on the total weight of the positive electrode film layer.
  • the positive electrode sheet can be prepared by the following method: the components for preparing the positive electrode sheet, such as the positive electrode active material, the conductive agent, the binder and any other components are dispersed in a solvent (such as N-methylpyrrolidone) to form a positive electrode slurry; wherein the positive electrode slurry has a solid content of 40-80wt%, and the viscosity at room temperature is adjusted to 5000-25000mPa ⁇ s, and the positive electrode slurry is coated on the positive electrode collector, and after drying, cold pressing and other processes, the positive electrode sheet can be obtained, and the positive electrode powder coating unit area density is 150-350mg/ m2 , and the positive electrode sheet compaction density is ⁇ 3.3g/ cm3 , and can be ⁇ 3.4g/ cm3 .
  • the calculation formula of the compaction density is:
  • Compacted density coating surface density/(thickness of the electrode after extrusion - thickness of the current collector).
  • the negative electrode sheet includes a negative electrode current collector and a negative electrode film layer disposed on at least one surface of the negative electrode current collector, wherein the negative electrode film layer includes a negative electrode active material.
  • the negative electrode current collector has two surfaces opposite to each other in its thickness direction, and the negative electrode film layer is disposed on any one or both of the two opposite surfaces of the negative electrode current collector.
  • the negative electrode current collector may be a metal foil or a composite current collector.
  • the metal foil copper foil may be used.
  • the composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material substrate.
  • the composite current collector may be formed by forming a metal material (copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • PP polypropylene
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the negative electrode active material may adopt the negative electrode active material for the battery known in the art.
  • the negative electrode active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based material, tin-based material and lithium titanate.
  • the silicon-based material may be selected from at least one of elemental silicon, silicon oxide compounds, silicon carbon composites, silicon nitrogen composites and silicon alloys.
  • the tin-based material may be selected from at least one of elemental tin, tin oxide compounds and tin alloys.
  • the present application is not limited to these materials, and other traditional materials that can be used as negative electrode active materials for batteries may also be used.
  • the negative electrode active material may have an average particle size (D 10 ) of 1 ⁇ m-15 ⁇ m, preferably 4 ⁇ m-9 ⁇ m, an average particle size (D 50 ) of 12 ⁇ m-22 ⁇ m, preferably 14 ⁇ m-17 ⁇ m, and an average particle size (D 90 ) of 26 ⁇ m to 40 ⁇ m, preferably 30 ⁇ m-37 ⁇ m.
  • Dv10 is the particle size corresponding to the cumulative volume distribution percentage of the sample reaching 10%
  • Dv50 is the particle size corresponding to the cumulative volume distribution percentage of the sample reaching 50%
  • Dv90 is the particle size corresponding to the cumulative volume distribution percentage of the sample reaching 90%.
  • the weight ratio of the negative electrode active material in the negative electrode film layer is 70-100 weight%, based on the total weight of the negative electrode film layer.
  • the negative electrode film layer may further include a binder.
  • the binder may be selected from at least one of styrene-butadiene rubber (SBR), polyacrylic acid (PAA), sodium polyacrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), polymethacrylic acid (PMAA) and carboxymethyl chitosan (CMCS).
  • SBR styrene-butadiene rubber
  • PAA polyacrylic acid
  • PAAS sodium polyacrylate
  • PAM polyacrylamide
  • PVA polyvinyl alcohol
  • SA sodium alginate
  • PMAA polymethacrylic acid
  • CMCS carboxymethyl chitosan
  • the negative electrode film layer may further include a conductive agent.
  • the conductive agent may be selected from at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
  • the weight ratio of the conductive agent in the negative electrode film layer is 0-20 weight %, based on the total weight of the negative electrode film layer.
  • the negative electrode film layer may further include other additives, such as a thickener (such as sodium carboxymethyl cellulose (CMC-Na)), etc.
  • a thickener such as sodium carboxymethyl cellulose (CMC-Na)
  • the weight ratio of the other additives in the negative electrode film layer is 0-15% by weight, based on the total weight of the negative electrode film layer.
  • the negative electrode sheet can be prepared by the following method: the components for preparing the negative electrode sheet, such as the negative electrode active material, the conductive agent, the binder and any other components are dispersed in a solvent (such as deionized water) to form a negative electrode slurry, wherein the solid content of the negative electrode slurry is 30-70wt%, and the viscosity at room temperature is adjusted to 2000-10000mPa ⁇ s; the negative electrode slurry is coated on the negative electrode collector, and after drying, cold pressing and other processes, the negative electrode sheet can be obtained.
  • the negative electrode powder coating unit area density is 75-220mg/ m2
  • the negative electrode sheet compaction density is 1.2-2.0g/ m3 .
  • the electrolyte plays the role of conducting ions between the positive electrode and the negative electrode.
  • the present application has no specific restrictions on the type of electrolyte, which can be selected according to needs.
  • the electrolyte can be liquid, gel or all-solid.
  • the electrolyte is an electrolyte solution, which includes an electrolyte salt and a solvent.
  • the electrolyte salt may be selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bis(fluorosulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalatoborate, lithium dioxalatoborate, lithium difluorodioxalatophosphate, and lithium tetrafluorooxalatophosphate.
  • the concentration of the electrolyte salt is typically 0.5-5 mol/L.
  • the solvent can be selected from at least one of ethylene carbonate, propylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, 1,4-butyrolactone, cyclopentane sulfone, dimethyl sulfone, methyl ethyl sulfone and diethyl sulfone.
  • the electrolyte may further include additives, such as negative electrode film-forming additives, positive electrode film-forming additives, and additives that can improve certain battery properties, such as additives that improve battery overcharge performance, additives that improve battery high or low temperature performance, etc.
  • additives such as negative electrode film-forming additives, positive electrode film-forming additives, and additives that can improve certain battery properties, such as additives that improve battery overcharge performance, additives that improve battery high or low temperature performance, etc.
  • the secondary battery further includes a separator.
  • the present application has no particular limitation on the type of separator, and any known porous separator with good chemical stability and mechanical stability can be selected.
  • the material of the isolation membrane can be selected from at least one of glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride.
  • the isolation membrane can be a single-layer film or a multi-layer composite film, without particular limitation.
  • the materials of each layer can be the same or different, without particular limitation.
  • the isolation film has a thickness of 6-40 ⁇ m, and optionally 12-20 ⁇ m.
  • the positive electrode sheet, the negative electrode sheet, and the separator may be formed into an electrode assembly by a winding process or a lamination process.
  • the secondary battery may include an outer package that can be used to encapsulate the electrode assembly and the electrolyte.
  • the outer packaging of the secondary battery may be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, etc.
  • the outer packaging of the secondary battery may also be a soft package, such as a bag-type soft package.
  • the material of the soft package may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, and polybutylene succinate.
  • FIG1 is a secondary battery 5 of a square structure as an example.
  • the outer package may include a shell 51 and a cover plate 53.
  • the shell 51 may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plate enclose a receiving cavity.
  • the shell 51 has an opening connected to the receiving cavity, and the cover plate 53 can be covered on the opening to close the receiving cavity.
  • the positive electrode sheet, the negative electrode sheet and the isolation film can form an electrode assembly 52 through a winding process or a lamination process.
  • the electrode assembly 52 is encapsulated in the receiving cavity.
  • the electrolyte is infiltrated in the electrode assembly 52.
  • the number of electrode assemblies 52 contained in the secondary battery 5 can be one or more, and those skilled in the art can select according to specific actual needs.
  • secondary batteries may be assembled into a battery module.
  • the number of secondary batteries contained in the battery module may be one or more, and the specific number may be selected by those skilled in the art according to the application and capacity of the battery module.
  • FIG3 is a battery module 4 as an example.
  • a plurality of secondary batteries 5 may be arranged in sequence along the length direction of the battery module 4. Of course, they may also be arranged in any other manner. Further, the plurality of secondary batteries 5 may be fixed by fasteners.
  • the battery module 4 may further include a housing having a receiving space, and the plurality of secondary batteries 5 are received in the receiving space.
  • the battery modules described above may also be assembled into a battery pack.
  • the battery pack may contain one or more battery modules, and the specific number may be selected by those skilled in the art according to the application and capacity of the battery pack.
  • FIG4 and FIG5 are battery packs 1 as an example.
  • the battery pack 1 may include a battery box and a plurality of battery modules 4 disposed in the battery box.
  • the battery box includes an upper box body 2 and a lower box body 3, and the upper box body 2 can be covered on the lower box body 3 to form a closed space for accommodating the battery modules 4.
  • the plurality of battery modules 4 can be arranged in the battery box in any manner.
  • the present application also provides an electrical device, which includes at least one of the secondary battery, battery module, or battery pack provided in the present application.
  • the secondary battery, battery module, or battery pack can be used as a power source for the electrical device, and can also be used as an energy storage unit for the electrical device.
  • the electrical device may include mobile devices (such as mobile phones, laptops, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but are not limited to these.
  • a secondary battery, a battery module or a battery pack may be selected according to its usage requirements.
  • Fig. 6 is an example of an electric device.
  • the electric device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle, etc.
  • a battery pack or a battery module may be used.
  • the device may be a mobile phone, a tablet computer, a notebook computer, etc.
  • the device is usually required to be thin and light, and a secondary battery may be used as a power source.
  • Nickel sulfate, cobalt sulfate and manganese sulfate were prepared into a 2 mol/L metal salt solution in a molar ratio of 8:1:1, and then the metal salt solution, 8 mol/L ammonia water and 5 mol/L NaOH solution were continuously added into a reactor for reaction.
  • the pH value during the reaction was controlled to be 11.30, the ammonia concentration to be 4.0 g/L, the reaction time to be 20 h, and the stirring rate to be 300 r/min.
  • a precursor of the first positive electrode active material A (Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 ) was prepared by a hydroxide coprecipitation method, and the particle size Dv50 was 10 ⁇ m.
  • Nickel sulfate, cobalt sulfate and manganese sulfate were prepared into a 2 mol/L metal salt solution in a molar ratio of 8:1:1. Subsequently, the metal salt solution, 8 mol/L ammonia water and 5 mol/L NaOH solution were continuously added into a reactor for reaction. The pH value during the reaction was controlled to be 11.60, the ammonia concentration to be 3.0 g/L, the reaction time to be 20 h, and the stirring rate to be 400 r/min. A hydroxide co-precipitation method was used to prepare a precursor of the second positive electrode active material B (Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 ) with a particle size Dv50 of 3 ⁇ m.
  • Lithium hydroxide, the precursor of the first positive electrode active material A, tungsten trioxide, and zirconium oxide were placed in a plow mixer at a molar ratio of 1.03:0.993:0.003:0.004 and mixed evenly. The mixed materials were then placed in a kiln for sintering at a temperature of 750°C for 15 h in an oxygen atmosphere. After cooling, the first positive electrode active material A (Li 1.03 [(Ni 0.8 Co 0.1 Mn 0.1 ) 0.993 W 0.003 Zr 0.004 ]O 2 ) was obtained by mechanical crushing, and the particle size Dv50 was 10 ⁇ m. The tungsten doping amount in the first positive electrode active material was measured to be 6000 ppm by inductively coupled plasma emission spectroscopy (ICP);
  • Lithium hydroxide, a precursor of a second positive electrode active material B, strontium carbonate, and zirconium oxide were mixed uniformly in a plowshare mixer at a molar ratio of 1.03:0.994:0.002:0.004, and then the mixed materials were placed in a kiln for sintering at a temperature of 800° C. for 14 h in an oxygen atmosphere.
  • the second positive electrode active material B Li 1.03 [(Ni 0.8 Co 0.1 Mn 0.1 ) 0.994 Sr 0.002 Zr 0.004 ]O 2
  • the particle size Dv50 was 3 ⁇ m.
  • the strontium doping amount in the second positive electrode active material was measured to be 2000 ppm by inductively coupled plasma emission spectroscopy (ICP).
  • the first positive electrode active material A and the second positive electrode active material B were put into a mixer at a mass ratio of 8:2 and mixed for 1 hour to obtain a positive electrode active material.
  • [Positive electrode sheet] The positive electrode active material obtained above, polyvinylidene fluoride (PVDF), and acetylene black were added to NMP at a weight ratio of 90:5:5, and stirred in a drying room to form a slurry. The slurry was coated on aluminum foil, dried, and cold pressed to form a positive electrode sheet. The coating amount was 0.01g/ cm2 , and the compaction density was 3.5g/ cm3 .
  • Ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) were mixed in a volume ratio of 1:1:1, and then LiPF6 was uniformly dissolved in the above solution to obtain an electrolyte, wherein the concentration of LiPF6 was 1 mol/L.
  • the isolation membrane was purchased from Cellgard, model number is cellgard 2400.
  • buttons cell CR2032 button cell
  • [Positive electrode sheet] The positive electrode active material obtained above was mixed evenly with acetylene black and polyvinylidene fluoride (PVDF) in a weight ratio of 94:3:3 in an N-methylpyrrolidone solvent system, and then coated on an aluminum foil, dried, and cold pressed to obtain a positive electrode sheet.
  • the coating amount was 0.02g/ cm2
  • the compaction density was 3.5g/ cm3 .
  • Nitative electrode sheet The negative electrode active material artificial graphite, hard carbon, conductive agent acetylene black, binder styrene butadiene rubber (SBR), and thickener sodium carboxymethyl cellulose (CMC-Na) were mixed evenly in deionized water at a weight ratio of 90:5:2:2:1, coated on copper foil, dried, and cold pressed to obtain a negative electrode sheet.
  • the coating amount was 0.015g/ cm2
  • the compaction density was 1.6g/ cm3 .
  • Ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) were mixed in a volume ratio of 1:1:1, and then LiPF6 was uniformly dissolved in the above solution to obtain an electrolyte, wherein the concentration of LiPF6 was 1 mol/L.
  • the positive electrode sheet, separator, and negative electrode sheet are stacked in order, with the separator placed between the positive and negative electrodes to isolate them, and then wound to obtain a bare cell.
  • the bare cell is placed in an outer package, injected with electrolyte and packaged to obtain a full battery (hereinafter referred to as "full battery”).
  • the length ⁇ width ⁇ height of the full battery 90 mm ⁇ 30 mm ⁇ 60 mm, and the battery group margin is 91.0%.
  • Example 2 The same as Example 1, except that: in 3) in the preparation of the first positive electrode active material A, lithium hydroxide, the precursor of the first positive electrode active material A, niobium pentoxide, and zirconium oxide are in a molar ratio of 1.03:0.993:0.0015:0.004, the sintering temperature is 760°C, and the niobium doping amount is measured by inductively coupled plasma emission spectroscopy (ICP) to be 1500ppm.
  • ICP inductively coupled plasma emission spectroscopy
  • Example 3 The same as Example 1, except that: in 3) in the preparation of the first positive electrode active material A, lithium hydroxide, the precursor of the first positive electrode active material A, molybdenum trioxide, and zirconium oxide are in a molar ratio of 1.03:0.993:0.003:0.004, the sintering temperature is 750°C, and the molybdenum doping amount is measured by inductively coupled plasma emission spectroscopy (ICP) to be 3000ppm.
  • ICP inductively coupled plasma emission spectroscopy
  • Example 2 The same as Example 1, except that: in 4) in the preparation of the second positive electrode active material B, lithium hydroxide, the precursor of the second positive electrode active material B, yttrium trioxide, and zirconium oxide are in a molar ratio of 1.03:0.994:0.001:0.004, the sintering temperature is 790°C, and the yttrium doping amount is measured by inductively coupled plasma emission spectroscopy (ICP) to be 2000ppm.
  • ICP inductively coupled plasma emission spectroscopy
  • Example 2 The same as Example 1, except that: in 4) in the preparation of the second positive electrode active material B, lithium hydroxide, the precursor of the second positive electrode active material B, vanadium pentoxide, and zirconium oxide are in a molar ratio of 1.03:0.994:0.001:0.004, the sintering temperature is 790°C, and the vanadium doping amount is measured by inductively coupled plasma emission spectroscopy (ICP) to be 1000ppm.
  • ICP inductively coupled plasma emission spectroscopy
  • Example 2 The same as Example 1, except that the first positive electrode active material A and the second positive electrode active material B are mixed in a mass ratio of 10:1.
  • Example 2 The same as Example 1, except that the first positive electrode active material A and the second positive electrode active material B are mixed in a mass ratio of 9:1.
  • Example 2 The same as Example 1, except that the first positive electrode active material A and the second positive electrode active material B are mixed in a mass ratio of 3:2.
  • Example 2 The same as Example 1, except that the first positive electrode active material A and the second positive electrode active material B are mixed in a mass ratio of 1:1.
  • Example 2 The same as Example 1, except that: the Dv50 of the precursor of the first positive electrode active material A is 7 ⁇ m, and the Dv50 of the precursor of the second positive electrode active material B is 4 ⁇ m.
  • Example 2 The same as Example 1, except that: the Dv50 of the precursor of the first positive electrode active material A is 9 ⁇ m, and the Dv50 of the precursor of the second positive electrode active material B is 4 ⁇ m.
  • Example 2 The same as Example 1, except that: the Dv50 of the precursor of the first positive electrode active material A is 11 ⁇ m, and the Dv50 of the precursor of the second positive electrode active material B is 3 ⁇ m.
  • Example 2 The same as Example 1, except that the Dv50 of the precursor of the first positive electrode active material A is 13 ⁇ m, and the Dv50 of the precursor of the second positive electrode active material B is 2 ⁇ m.
  • the first positive electrode active material A and the second positive electrode active material B are mixed at a mass ratio of 7:3.
  • Example 2 The same as Example 1, except that: in 3) in the preparation of the first positive electrode active material A, lithium hydroxide, the precursor of the first positive electrode active material A, tungsten trioxide, and zirconium oxide are in a molar ratio of 1.03:0.994:0.002:0.004, and the tungsten element doping amount is measured by inductively coupled plasma emission spectroscopy (ICP) to be 4000 ppm.
  • ICP inductively coupled plasma emission spectroscopy
  • Example 2 The same as Example 1, except that: in 3) in the preparation of the first positive electrode active material A, lithium hydroxide, the precursor of the first positive electrode active material A, tungsten trioxide, and zirconium oxide are in a molar ratio of 1.03:0.9955:0.0005:0.004, and the tungsten element doping amount is measured by inductively coupled plasma emission spectroscopy (ICP) to be 1000 ppm.
  • ICP inductively coupled plasma emission spectroscopy
  • Example 2 The same as Example 1, except that: in 4) the preparation of the second positive electrode active material B, lithium hydroxide, the precursor of the second positive electrode active material B, strontium carbonate, and zirconium oxide are in a molar ratio of 1.03:0.99:0.006:0.004, and the strontium doping amount is measured by inductively coupled plasma emission spectroscopy (ICP) to be 6000 ppm.
  • ICP inductively coupled plasma emission spectroscopy
  • Example 2 The same as Example 1, except that: in 4) the preparation of the second positive electrode active material B, the lithium hydroxide, the precursor of the second positive electrode active material B, strontium carbonate, and zirconium oxide are in a molar ratio of 1.03:0.992:0.004:0.004, and the strontium doping amount is 4000ppm as measured by inductively coupled plasma emission spectroscopy (ICP).
  • ICP inductively coupled plasma emission spectroscopy
  • Example 2 The same as Example 1, except that: in 4) the preparation of the second positive electrode active material B, lithium hydroxide, the precursor of the second positive electrode active material B, strontium carbonate, and zirconium oxide are in a molar ratio of 1.03:0.995:0.001:0.004, and the strontium doping amount is measured by inductively coupled plasma emission spectroscopy (ICP) to be 1000 ppm.
  • ICP inductively coupled plasma emission spectroscopy
  • Example 2 The same as Example 1, except that: in 4) the preparation of the second positive electrode active material B, lithium hydroxide, the precursor of the second positive electrode active material B, strontium carbonate, and zirconium oxide are in a molar ratio of 1.03:0.9955:0.0005:0.004, and the strontium doping amount is 500 ppm measured by inductively coupled plasma emission spectroscopy (ICP).
  • ICP inductively coupled plasma emission spectroscopy
  • Example 2 The same as Example 1, except that the first positive electrode active material A and the second positive electrode active material B are mixed in a mass ratio of 1:3.
  • Example 2 The same as Example 1, except that: in 3) the preparation of the first positive electrode active material A, the molar ratio of lithium hydroxide, the precursor of the first positive electrode active material A, and zirconium oxide is 1.03:0.996:0.004. In 4) the preparation of the second positive electrode active material B, the molar ratio of lithium hydroxide, the precursor of the second positive electrode active material B, and zirconium oxide is 1.03:0.996:0.004.
  • the particle size of the positive electrode active material is measured. Take a clean beaker, add an appropriate amount of the above positive electrode active material, add an appropriate amount of pure water, and use ultrasound at 120W/5min to ensure that the material powder is completely dispersed in the water. After the solution is poured into the injection tower of the laser particle size analyzer (Malvern Company, model: Mastersizer3000), it circulates to the test optical path system with the solution.
  • the laser particle size analyzer Malvern Company, model: Mastersizer3000
  • the particles are irradiated by the laser beam, and the particle size distribution characteristics of the particles (shading degree: 8-12%) can be obtained by receiving and measuring the energy distribution of the scattered light, and the corresponding values of Dv1, Dv3, Dv5, Dv10, Dv50, and Dv90 are read.
  • Dv1', Dv3' and Dv5' of the positive electrode active material after being pressed with a 1 ton weight were measured.
  • the test of electrochemical active specific surface area is to test the electrochemical effective specific surface area of the material by cyclic voltammetry, using the electrochemical workstation VMP3, assembling the test material with the button, and scanning the CV of the electroactive probe for four cycles at four scanning rates of 1/0.5/0.3/0.1mV/s.
  • Ip 2.69 ⁇ 10 5 n 3/2 AcD 1/2 v 1/2
  • the electrochemical active specific surface area of the test material can be obtained.
  • the first effect is calculated according to D0/C0*100%.
  • Full batteries with 100% state of charge (SOC) are stored at 70°C.
  • the open circuit voltage (OCV) and AC internal resistance (IMP) of the battery cells are measured before, during and after storage to monitor the SOC, and the volume of the battery cells is measured.
  • the full battery is taken out after every 48 hours of storage, and the OCV and IMP are tested after standing for 1 hour.
  • the volume of the battery cells is measured by the water displacement method after cooling to room temperature.
  • the water displacement method is to first use a balance with automatic unit conversion of dial data to measure the gravity F1 of the battery cell separately, and then place the battery cell completely in deionized water (density is known to be 1g/ cm3 ), and measure the gravity F2 of the battery cell at this time.
  • the battery cell After each volume test, the battery cell is recharged at a constant current of 1C to 4.25V, and then charged at a constant voltage of 4.25V until the current drops to 0.05C. After the recharging is completed, the battery cell is put into the furnace to continue testing.
  • the cell volume was measured, and the increase in cell volume after storage relative to the cell volume before storage, i.e., the gas production, was calculated.
  • the positive electrode active material of the present application has a high filling degree between particles, good dispersibility, and a high compaction density, so that the secondary battery prepared therefrom has a higher energy density;
  • the positive electrode active material of the present application is doped with M1, M2, M3 and M4 elements, so that the structural stability of the positive electrode active material is improved, and the electrolyte is effectively prevented from having side reactions on the surface of the positive electrode active material, especially by doping with M1 (i.e., W, Nb or Mo) elements, the grains of the first positive electrode active material A tend to be radially distributed, and the M1 element is enriched at the grain boundaries, so that the compressive strength of the first positive electrode active material A is improved and the cracking is reduced, and the structural stability of the second positive electrode active material B is improved by doping with M2 (i.e., Sr, Y or V) elements having a melting effect, and

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Abstract

L'invention concerne un matériau actif d'électrode positive et son procédé de préparation. Le matériau actif d'électrode positive comprend un premier matériau actif d'électrode positive A et un second matériau actif d'électrode positive B. La formule chimique du premier matériau actif d'électrode positive A est Lia1[Nix1Coy1Mnz1M1b1M3c1]O2, 0 < x1 < 1, 0 ≤ y1 < 0,5, 0 ≤ z1 < 0,5, 0,9 < a1 < 1,2, 0 < b1 < 0,2, 0 < c1 < 0,2, et x1 + y1 + z1 + b1 + c1 = 1, M1 étant au moins un élément choisi parmi W, Nb et Mo, et M3 étant au moins un élément choisi parmi Zr, Ti, Mg, Al, Sb, B et Co. La formule chimique du second matériau actif d'électrode positive B est Lia2[Nix2Coy2Mnz2M2b2M4c2]O2, 0 < x2 < 1, 0 ≤ y2 < 0,5, 0 ≤ z2 < 0,5, 0,9 < a2 < 1,2, 0 < b2 < 0,2, 0 < c2 < 0,2, et x2 + y2 + z2 + b2 + c2 = 1, M2 étant au moins un élément choisi parmi Sr, Y et V, et M4 étant au moins un élément choisi parmi Zr, Ti, Mg, Al, Sb, B et Co.
PCT/CN2022/135243 2022-11-30 2022-11-30 Matériau actif d'électrode positive et son procédé de préparation, feuille d'électrode positive, batterie secondaire et appareil électrique Ceased WO2024113200A1 (fr)

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PCT/CN2022/135243 WO2024113200A1 (fr) 2022-11-30 2022-11-30 Matériau actif d'électrode positive et son procédé de préparation, feuille d'électrode positive, batterie secondaire et appareil électrique

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