WO2024087872A1 - 三元正极材料、其制备方法及应用 - Google Patents

三元正极材料、其制备方法及应用 Download PDF

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WO2024087872A1
WO2024087872A1 PCT/CN2023/115676 CN2023115676W WO2024087872A1 WO 2024087872 A1 WO2024087872 A1 WO 2024087872A1 CN 2023115676 W CN2023115676 W CN 2023115676W WO 2024087872 A1 WO2024087872 A1 WO 2024087872A1
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Prior art keywords
positive electrode
electrode material
ternary positive
ternary
polyhedral oligomeric
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PCT/CN2023/115676
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English (en)
French (fr)
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陈志宇
李红磊
吉长印
吕菲
徐宁
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天津巴莫科技有限责任公司
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Publication of WO2024087872A1 publication Critical patent/WO2024087872A1/zh

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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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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-ion battery materials, and in particular to a ternary positive electrode material, a preparation method thereof, and an application thereof.
  • lithium-ion battery positive electrode materials Compared with polycrystalline materials, single crystal materials have advantages in compression resistance and structural stability, but they have large specific surface area and strong water absorption, which leads to the dissolution of active lithium and the increase of residual alkali, thereby increasing the failure risk of positive electrode slurry preparation, such as agglomeration and waste.
  • the increase in the moisture content of the material will also affect the coating effect of the pole piece and the cycle performance of the battery, which greatly limits the development and application of medium/high nickel single crystal materials.
  • the present application provides a ternary positive electrode material, a preparation method thereof, a positive electrode plate, a lithium-ion battery and an electrical device.
  • the present application provides a ternary positive electrode material, comprising a ternary positive electrode material substrate and a coating layer, wherein the surface of the ternary positive electrode material substrate is coated with the coating layer;
  • the ternary positive electrode material matrix includes a material with a chemical formula of LiNi x Co y M 1-xy O 2 , wherein M includes one or more of Mn, Al, Mg, Ti, Zr, Y, Nb, W, Ce, Sb, Sr and Ta, 0.50 ⁇ x ⁇ 0.98, 0 ⁇ y ⁇ 0.25, x+y ⁇ 1; the material of the coating layer includes polyhedral oligomeric silsesquioxane (POSS).
  • PES polyhedral oligomeric silsesquioxane
  • the ternary cathode material matrix includes a material with a chemical formula of LiNi x Co y M 1-xy O 2 , wherein M includes one or more of Mn, Al, Ti and Zr, 0.50 ⁇ x ⁇ 0.98, 0 ⁇ y ⁇ 0.25, and x+y ⁇ 1.
  • the ternary cathode material matrix includes a material with a chemical formula of LiNi x Co y Mn 1-xy O 2 , wherein 0.50 ⁇ x ⁇ 0.98, 0 ⁇ y ⁇ 0.25, and x+y ⁇ 1.
  • the ternary cathode material matrix includes a material with a chemical formula of LiNi x Co y Mn 1-xy O 2 , wherein 0.50 ⁇ x ⁇ 0.98, 0 ⁇ y ⁇ 0.25, and x+y ⁇ 1.
  • the polyhedral oligomeric silsesquioxane includes one or more of polyhedral oligomeric silsesquioxane-alkyl, polyhedral oligomeric silsesquioxane-phenyl, polyhedral oligomeric silsesquioxane-alkenyl, polyhedral oligomeric silsesquioxane-amino, polyhedral oligomeric silsesquioxane-hydroxyl, and polyhedral oligomeric silsesquioxane-acrylate.
  • the polyhedral oligomeric silsesquioxane is polyhedral oligomeric silsesquioxane-amino, polyhedral Oligomeric silsesquioxane-acrylates, and combinations thereof.
  • the polyhedral oligomeric silsesquioxane is polyhedral oligomeric silsesquioxane-amino.
  • the mass ratio of the coating layer to the ternary cathode material matrix is (0.0001-0.05): 1. In some embodiments, the mass ratio of the coating layer to the ternary cathode material matrix is (0.001-0.05): 1.
  • the specific surface area of the ternary cathode material matrix is 0.4 m 2 /g to 2.5 m 2 /g. In some embodiments, the specific surface area of the ternary cathode material matrix is 0.85 m 2 /g to 2.0 m 2 /g.
  • the present application provides a method for preparing the above-mentioned ternary positive electrode material, comprising the following steps:
  • the ternary positive electrode material matrix is mixed with the material of the coating layer, and a first calcination process is performed to obtain a ternary positive electrode material.
  • the ternary positive electrode material matrix includes a material with a chemical formula of LiNi x Co y M 1-xy O 2 , wherein M includes one or more of Mn, Al, Mg, Ti, Zr, Y, Nb, W, Ce, Sb, Sr and Ta, 0.50 ⁇ x ⁇ 0.98, 0 ⁇ y ⁇ 0.25, x+y ⁇ 1; and the material of the coating layer includes polyhedral oligomeric silsesquioxane.
  • the process conditions of the first calcination treatment include: a first calcination temperature of 260° C. to 700° C., and a first calcination time of 4 h to 12 h.
  • the preparation of the ternary cathode material matrix comprises the following steps:
  • the intermediate material is mixed with a second lithium source and subjected to a third calcination to obtain the ternary positive electrode material matrix.
  • the preparation of the ternary cathode material matrix comprises the following steps:
  • the intermediate A is pre-treated by calcination to obtain an intermediate B;
  • the ternary positive electrode material matrix precursor in step (1) or step S1 includes a material with a chemical formula of Ni x Co y M 1-xy (OH) 2 , wherein 0.50 ⁇ x ⁇ 0.98, 0 ⁇ y ⁇ 0.25, x+y ⁇ 1, and M includes one or more of Mn, Al, Mg, Ti, Zr, Y, Nb, W, Ce, Sb, Sr and Ta.
  • the metal element in the metal compound in step (1) or step S1 includes one or more of Al, Mg, Ti, Zr, Y, Nb, W, Ce, Sb, Sr and Ta. In some embodiments, the metal element in the metal compound in step (1) or step S1 is one or more of Al, Ti and Zr.
  • step (1) or step S1 the molar ratio of Li + in the first lithium source: the metal element in the optional metal compound: the ternary cathode material matrix precursor is (0.50-1.06): (0-0.02):1.
  • the first lithium source in step (1) or step S1 and the second lithium source in step (2) or step S3 each independently include one or more of lithium hydroxide and lithium carbonate.
  • the process conditions of the second calcination in step (1) include: a calcination temperature of 400° C. to 650° C. and a calcination time of 3 h to 10 h.
  • the process conditions for the calcination pretreatment in step S2 include: a calcination temperature of 400°C to 650°C, a calcination temperature of 100°C to 500°C, a calcination temperature of 2 ...200°C to 650°C, a calcination temperature of 300°C to 500°C, a calcination temperature of 400°C to 650°C, a calcination temperature of 200°C to 500°C, a cal Burning time: 3h ⁇ 10h.
  • the molar ratio of Li + in the second lithium source in step (2) to the intermediate material is (0-0.55):1.
  • the molar ratio of Li + in the second lithium source in step S3 to the intermediate B is (0-0.55):1.
  • the process conditions of the third calcination in step (2) include: a calcination temperature of 600° C. to 1100° C. and a calcination time of 6 h to 20 h.
  • the second calcination temperature is 600° C. to 1100° C.
  • the second calcination time is 6 h to 20 h.
  • the present application provides a positive electrode plate, comprising the above-mentioned ternary positive electrode material or the ternary positive electrode material prepared by the above-mentioned preparation method.
  • the present application provides a lithium-ion battery comprising the above-mentioned positive electrode plate.
  • the present application provides an electrical device comprising the above-mentioned lithium-ion battery.
  • the present application provides a ternary positive electrode material having at least one of the following characteristics:
  • the moisture content at 25°C and 40% relative humidity for 30 days increases by no more than 97 ppm compared to the moisture content at 0 days, for example, between 13 ppm and 97 ppm;
  • the moisture content at 25°C and 40% relative humidity for 60 days increases by no more than 118 ppm compared to the moisture content at 0 days, for example, between 23 ppm and 118 ppm;
  • the moisture content at 25°C and 80% relative humidity for 30 days does not increase by more than 297 ppm compared to the moisture content at 0 days, for example, between 128 ppm and 297 ppm;
  • the moisture content at 25° C. and 80% relative humidity after 60 days of storage may not increase by more than 315 ppm compared to the moisture content at 0 days of storage, for example, between 133 ppm and 315 ppm.
  • the present application provides a ternary positive electrode material, wherein the 100-week capacity retention rate of a battery prepared from the ternary positive electrode material is not less than 92%, wherein the 100-week capacity retention rate is measured by storing the battery at 45°C and 40% relative humidity or 80% relative humidity for 60 days and then subjecting it to 0.3C constant current charge and discharge for 100 weeks at a voltage of 2.5V to 4.25V.
  • FIG. 1 is a SEM image of the ternary positive electrode material prepared in Example 1 of the present application.
  • FIG. 2 is a SEM image of the ternary positive electrode material prepared in Example 4 of the present application.
  • FIG. 3 is an XRD diagram of the ternary positive electrode material prepared in Example 1 of the present application.
  • first”, “second”, and “third” are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, a feature defined as “first”, “second”, and “third” may explicitly or implicitly include at least one of the features.
  • the term “multiple” in this application means at least two, such as two, three, etc., unless otherwise clearly and specifically defined.
  • An embodiment of the present application provides a ternary positive electrode material, including a ternary positive electrode material substrate and a coating layer, wherein the surface of the ternary positive electrode material substrate is coated with the coating layer;
  • the ternary positive electrode material matrix includes a material with a chemical formula of LiNi x Co y M 1-xy O 2 , wherein M includes one or more of Mn, Al, Mg, Ti, Zr, Y, Nb, W, Ce, Sb, Sr and Ta, 0.50 ⁇ x ⁇ 0.98, 0 ⁇ y ⁇ 0.25, x+y ⁇ 1; the material of the coating layer includes polyhedral oligomeric silsesquioxane.
  • M includes one or more of Mn, Al, Ti and Zr. In some embodiments, M is Mn. In some embodiments, 0.50 ⁇ x ⁇ 0.98, 0 ⁇ y ⁇ 0.25, x+y ⁇ 1. In some embodiments, 0.50 ⁇ x ⁇ 0.98, 0 ⁇ y ⁇ 0.25, x+y ⁇ 1.
  • the coating layer on the surface of the above-mentioned ternary positive electrode material matrix is super hydrophobic and has an organic-inorganic composite structure.
  • the inorganic layer of the hydrophobic coating layer is tightly combined with the ternary positive electrode material matrix inside, and the organic layer of the hydrophobic coating layer is in contact with the air outside, which can effectively reduce the hygroscopicity of the ternary positive electrode material. Therefore, the hydrophobic coating layer can improve the adaptability of the ternary positive electrode material to the storage environment and extend the storage time of the ternary positive electrode material; the super hydrophobic coating layer can restrain the expansion and extension of microcracks, absorb energy, and reduce the stress concentration of the ternary positive electrode material matrix.
  • Its organic active sites can increase the crosslinking degree and compatibility of the system, improve the mechanical properties and strength of the material, thereby maintaining the structural stability of the material and improving the cycle retention rate of the lithium-ion battery; the specific cage structure and intramolecular porous channels of the coating layer are conducive to the conduction of lithium ions and improve the kinetic properties of the main material.
  • x can be, for example, 0.51, 0.52, 0.53, 0.54, 0.55, 0.57, 0.59, 0.60, 0.62, 0.65, 0.70, 0.80, 0.90, 0.95 or 0.98
  • y can be, for example, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.10, 0.15, 0.20, 0.22, 0.24 or 0.25.
  • the polyhedral oligomeric silsesquioxane includes one or more of polyhedral oligomeric silsesquioxane-alkyl, polyhedral oligomeric silsesquioxane-phenyl, polyhedral oligomeric silsesquioxane-alkenyl, polyhedral oligomeric silsesquioxane-amino, polyhedral oligomeric silsesquioxane-hydroxyl, and polyhedral oligomeric silsesquioxane-acrylate.
  • the polyhedral oligomeric silsesquioxane is polyhedral oligomeric silsesquioxane-amino, polyhedral oligomeric silsesquioxane-acrylate, and combinations thereof. In some embodiments, the polyhedral oligomeric silsesquioxane is polyhedral oligomeric silsesquioxane-amino.
  • the mass ratio of the coating layer to the ternary cathode material matrix is (0.0001-0.05):1. It is understood that the mass ratio of the coating layer to the ternary cathode material matrix can be any value between (0.0001-0.05):1, for example: 0.0001: 1, 0.0002:1, 0.0003:1, 0.0005:1, 0.0008:1, 0.001:1, 0.005:1, 0.008:1, 0.01:1, 0.02:1, 0.03:1, 0.04:1 or 0.05:1. In some embodiments, the mass ratio of the coating layer to the ternary positive electrode material matrix is (0.001-0.05):1. It should be noted that the mass ratio of the coating layer to the ternary positive electrode material matrix cannot be too high or too low.
  • the coating layer When the mass ratio is too high, the coating layer is thicker, which will affect the transmission speed of lithium ions. When the mass ratio is too low, the coating layer is thinner and may not be able to effectively reduce the hygroscopicity of the ternary positive electrode material.
  • the coating layer is a continuous layer coating, that is, the coating layer can fully coat the ternary cathode material matrix.
  • the specific surface area of the ternary positive electrode material matrix is 0.4m 2 / g to 2.5m 2 /g. In some embodiments, the specific surface area of the ternary positive electrode material matrix is 0.85m 2 /g to 2.0m 2 /g.
  • the specific surface area of the ternary positive electrode material matrix can be, for example, 0.4m 2 / g, 0.5m 2 / g, 0.6m 2 / g, 0.7m 2 /g, 0.8m 2 /g, 0.9m 2 /g, 1m 2 /g, 1.2m 2 /g, 1.5m 2 /g, 1.7m 2 /g, 2m 2 /g, 2.2m 2 /g, 2.5m 2 /g.
  • the specific surface area of the ternary positive electrode material matrix is controlled to be 0.4m 2 /g to 2.5m 2 /g in order to achieve the best hydrophobic effect of the ternary positive electrode material without affecting its kinetic performance.
  • Another embodiment of the present application provides a method for preparing the above-mentioned ternary positive electrode material, comprising the following steps:
  • the ternary positive electrode material matrix is mixed with the material of the coating layer as described above, and a first calcination treatment is performed.
  • the process conditions of the first calcination treatment include: a first calcination temperature of 260°C to 700°C, and a first calcination time of 4h to 12h.
  • the first calcination temperature may be, for example, 260°C, 280°C, 3000°C, 320°C, 350°C, 370°C, 400°C, 410°C, 430°C, 470°C, 490°C, 500°C, 550°C, 600°C, 650°C or 700°C
  • the first calcination temperature may also be other values between 260°C and 700°C
  • the first calcination time may be any value between 4h and 12h, for example: 4h, 4.2h, 4.5h, 4.7h, 5h, 5.5h, 6h, 6.5h, 7h, 8h, 9h, 10h, 11h or 12h, etc.
  • the preparation of the ternary cathode material matrix comprises the following steps:
  • the intermediate material is mixed with a second lithium source and subjected to a third calcination to obtain the ternary positive electrode material matrix.
  • the preparation of the ternary cathode material matrix comprises the following steps:
  • the intermediate A is pretreated by calcination to obtain an intermediate B;
  • the ternary cathode material matrix precursor in the above step (1) or step S1 includes a material with a chemical formula of Ni x Co y M 1-xy (OH) 2 , wherein 0.50 ⁇ x ⁇ 0.98, 0 ⁇ y ⁇ 0.25, and x + y ⁇ 1.
  • x can be, for example, 0.51, 0.52, 0.53, 0.54, 0.55, 0.57, 0.59, 0.60, 0.62, 0.65, 0.70, 0.80, 0.90, 0.95 or 0.98
  • y can be, for example, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.10, 0.15, 0.20, 0.22, 0.24 or 0.25.
  • the metal element in the metal compound in the above step (1) or step S1 includes one or more of Al, Mg, Ti, Zr, Y, Nb, W, Ce, Sb, Sr and Ta. In some embodiments, the metal element in the metal compound in step (1) or step S1 is one or more of Al, Ti and Zr.
  • the metal compound can be an oxide, hydroxide or carbonate of the above metals, for example: Al 2 O 3 , MgO, TiO 2 , ZrO 2 , Y 2 O 3 , Nb 2 O 5 , WO 3 , CeO 2 , Sb 2 O 3 , Sb 2 O 5 , SrO, Ta 2 O 5 , Al(OH) 3 , Mg(OH) 2 , Zr(OH) 4 , Ti(OH) 4 , Sr(OH) 2 , Al 2 (CO 3 ) 3 , MgCO 3 , SrCO 3 or Zr 3 (CO 3 )O 5 , etc.
  • the molar ratio of Li + in the first lithium source: the metal element in the optional metal compound: the ternary cathode material matrix precursor is (0.50-1.06): (0-0.02):1. It can be understood that the molar amount of the metal compound in step S1 can be 0.
  • the molar ratio of Li + in the first lithium source in step S1: the metal element in the metal compound: the ternary positive electrode material matrix precursor can be, for example, 0.50:0.001:1, 0.51:0.002:1, 0.57:0.005:1, 0.60:0.007:1, 0.72:0.009:1, 0.80:0.01:1, 0.90:0.015:1, 0.95:0.017:1, 1.00:0.019:1 or 1.06:0.02:1, etc.; the purpose of adding metal compounds in the present application is to enable the metal elements to play a supporting role between the transition metal layers and to increase the kinetic properties of the ternary positive electrode material, thereby ensuring the stability of the layered structure of the ternary positive electrode material and improving the transportability of lithium ions.
  • the first lithium source in step (1) or step S1 and the second lithium source in step (2) or step S3 each independently include one or more of lithium hydroxide and lithium carbonate.
  • the process conditions of the roasting pretreatment in step S2 include: a roasting pretreatment temperature of 400°C to 650°C, and a roasting pretreatment time of 3h to 10h.
  • the roasting pretreatment temperature can be, for example, 400°C, 420°C, 435°C, 450°C, 465°C, 480°C, 500°C, 550°C, 600°C or 650°C, and the roasting pretreatment temperature can also be other values between 400°C and 650°C;
  • the roasting pretreatment time can be 3h, 3.5h, 4h, 4.5h, 5h, 6h, 7h, 8.5h or 10h, and can also be other values between 3h and 10h.
  • the roasting pretreatment in step S2 corresponds to the second roasting in the above step (1). Therefore, the process conditions of the roasting pretreatment in step S2 are applicable to the second roasting in the above step (1).
  • the ratio of Li + in the second lithium source in step S3 to intermediate B is (0-0.55): 1. It should be noted that when the composition of intermediate B is the same as that of the ternary positive electrode material matrix, no lithium supplementation is required, and the mass of the second lithium source in step S3 is 0.
  • the molar ratio of Li + in the second lithium source to intermediate B can be, for example, 0.01: 1, 0.015: 1, 0.018: 1, 0.02: 1, 0.025: 1, 0.027: 1, 0.03: 1, 0.035: 1, 0.04: 1, 0.045: 1, 0.05: 1 or 0.055: 1.
  • the second lithium source in step S3 corresponds to the second lithium source in step (2) above
  • the intermediate B in step S3 corresponds to the intermediate material in step (2) above. Therefore, the molar ratio of Li + in the second lithium source to the intermediate B in step S3 is applicable to the molar ratio of Li + in the second lithium source to the intermediate material in step (2) above.
  • the second roasting temperature in step S3 is 600°C to 1100°C, and the second roasting time is 6h to 20h. It is understood that the second roasting temperature in step S3 can be, for example, 600°C, 620°C, 650°C, 670°C, 700°C, 800°C, 900°C, 1000°C or 1100°C, and the second roasting time can be, for example, 6h, 6.5h, 7h, 7.5h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h or 20h. Wherein, the second roasting in step S3 corresponds to the third roasting in step (2) above. Therefore, the process conditions of the second roasting in step S3 are applicable to the third roasting in step (2) above.
  • a positive electrode sheet comprising the above-mentioned ternary positive electrode material or the ternary positive electrode material prepared by the above-mentioned preparation method.
  • the above-mentioned positive electrode sheet can be prepared as follows: using the above-mentioned ternary positive electrode material or the ternary positive electrode material prepared by the above-mentioned preparation method, a conductive agent and a binder as raw materials, adding a solvent and stirring evenly to form a positive electrode sheet.
  • the positive electrode slurry is coated on an aluminum foil and dried to obtain the positive electrode sheet.
  • the conductive agent, binder and solvent commonly used in the art can be used.
  • a lithium-ion battery including the above-mentioned positive electrode plate.
  • the above-mentioned lithium-ion battery can be obtained by assembling the positive electrode plate, the separator and the negative electrode plate with the shell after lamination or winding. The shell is also injected with an electrolyte.
  • the negative electrode active material attached to the negative electrode plate can be one or more of graphite, hard carbon, silicon material, lithium titanate and metallic lithium.
  • the above-mentioned separator and electrolyte can be commonly used in the art.
  • an electric device comprising the above-mentioned lithium-ion battery.
  • the above-mentioned lithium-ion battery can be used as a power source or energy storage unit in the electric device.
  • the above-mentioned electric device includes but is not limited to electric vehicles, smart home appliances, computers, mobile phones, digital cameras, etc.
  • the provided ternary cathode material has at least one of the following characteristics:
  • the moisture content at 25°C and 40% relative humidity for 30 days increases by no more than 97 ppm compared to the moisture content at 0 days, for example, between 13 ppm and 97 ppm;
  • the moisture content at 25°C and 40% relative humidity for 60 days increases by no more than 118 ppm compared to the moisture content at 0 days, for example, between 23 ppm and 118 ppm;
  • the moisture content at 25°C and 80% relative humidity for 30 days does not increase by more than 297 ppm compared to the moisture content at 0 days, for example, between 128 ppm and 297 ppm;
  • the moisture content at 25° C. and 80% relative humidity after 60 days of storage may not increase by more than 315 ppm compared to the moisture content at 0 days of storage, for example, between 133 ppm and 315 ppm.
  • the 100-week capacity retention rate of a battery prepared from the provided ternary positive electrode material is not less than 92%, wherein the 100-week capacity retention rate is measured by storing the battery at 45°C and 40% relative humidity or 80% relative humidity for 60 days and then subjecting the battery to 0.3C constant current charge and discharge for 100 weeks at a voltage of 2.5V to 4.25V.
  • the above-mentioned ternary positive electrode material, preparation method thereof, positive electrode sheet, lithium-ion battery and power-consuming device have at least the following advantages:
  • the material of the coating layer includes polyhedral oligomeric silsesquioxane (POSS), which is coated on the surface of the ternary positive electrode material matrix to produce a superhydrophobic effect.
  • PES polyhedral oligomeric silsesquioxane
  • the inorganic layer in the coating layer is tightly combined with the ternary positive electrode material matrix on the inside, and the organic layer in the coating layer is in contact with the air on the outside, which can effectively reduce the hygroscopicity of the ternary positive electrode material, improve the adaptability of the ternary positive electrode material to the storage environment, and extend the storage time of the ternary positive electrode material.
  • the superhydrophobic coating can restrain the expansion and extension of microcracks, absorb energy, and reduce the stress concentration of the matrix of the ternary cathode material. Its organic active sites can increase the crosslinking degree and compatibility of the system, improve the mechanical properties and strength of the ternary cathode material, maintain the structural stability of the ternary cathode material, and thus improve the cycle retention rate of lithium-ion batteries.
  • polyhedral oligomeric silsesquioxane-amino is selected from Xi'an Qiyue Biotechnology POSS-aminopropyl isooctyl cage-shaped silsesquioxane
  • polyhedral oligomeric silsesquioxane-acrylate is selected from Xi'an Qiyue Biotechnology POSS-ethyl methacrylate cage-shaped silsesquioxane.
  • the precursor of the ternary positive electrode material matrix is Ni 0.55 Co 0.05 Mn 0.40 (OH) 2
  • the first lithium source and the second lithium source are both Li 2 CO 3 .
  • the preparation method of the ternary positive electrode material matrix comprises the following steps:
  • the ternary cathode material was prepared as follows:
  • LiNi 0.55 Co 0.05 Mn 0.40 O 2 and POSS-NH 2 were mixed in a mass ratio of 1:0.003, and then calcined at 300°C for 8 h to coat the surface of LiNi 0.55 Co 0.05 Mn 0.40 O 2 with POSS-NH 2 to obtain the ternary positive electrode material LiNi 0.55 Co 0.05 Mn 0.40 O 2 @POSS-NH 2 .
  • the precursor of the ternary cathode material matrix is Ni 0.62 Co 0.25 Mn 0.13 (OH) 2
  • the first lithium source is Li 2 CO 3
  • the second lithium source is LiOH.
  • the preparation method of the ternary positive electrode material matrix comprises the following steps:
  • the ternary cathode material was prepared as follows:
  • LiNi 0.62 Co 0.25 Mn 0.13 O 2 and POSS-acrylate were mixed in a mass ratio of 1:0.002, fully mixed and calcined at 300°C for 8 h to coat the surface of LiNi 0.62 Co 0.25 Mn 0.13 O 2 with POSS-acrylate to obtain the ternary positive electrode material LiNi 0.55 Co 0.05 Mn 0.40 O 2 @POSS-acrylate.
  • the precursor of the ternary positive electrode material matrix is Ni 0.78 Co 0.12 Al 0.10 (OH) 2
  • the first lithium source and the second lithium source are both Li 2 CO 3 .
  • the preparation method of the ternary positive electrode material matrix comprises the following steps:
  • the ternary cathode material was prepared as follows:
  • LiNi 0.78 Co 0.12 Al 0.10 O 2 , POSS-NH 2 and POSS-acrylate were mixed in a mass ratio of 1:0.001:0.001.
  • the ingredients were prepared, mixed thoroughly and calcined at 270°C for 6 h to coat the surface of LiNi 0.78 Co 0.12 Al 0.10 O 2 with POSS-NH 2 and POSS-acrylate to obtain the ternary positive electrode material LiNi 0.78 Co 0.12 Al 0.10 O 2 @POSS-NH 2 /POSS-acrylate.
  • the precursor of the ternary positive electrode material matrix is Ni 0.82 Co 0.06 Mn 0.12 (OH) 2
  • the first lithium source and the second lithium source are both LiOH
  • the metal compound is TiO 2 .
  • the preparation method of the ternary positive electrode material matrix comprises the following steps:
  • the ternary cathode material was prepared as follows:
  • LiNi 0.815 Co 0.060 Mn 0.120 Ti 0.005 O 2 and POSS-NH 2 were mixed in a mass ratio of 1:0.003, and then calcined at 270°C for 6 h to coat the surface of LiNi 0.815 Co 0.060 Mn 0.120 Ti 0.005 O 2 with POSS-NH 2 to obtain the ternary positive electrode material LiNi 0.815 Co 0.060 Mn 0.120 Ti 0.005 O 2 @POSS-NH 2 .
  • the precursor of the ternary positive electrode material matrix is Ni 0.90 Co 0.06 Mn 0.04 (OH) 2
  • the first lithium source and the second lithium source are both LiOH
  • the metal compound is Al 2 O 3 and ZrO 2 .
  • the preparation method of the ternary positive electrode material matrix comprises the following steps:
  • the ternary cathode material was prepared as follows:
  • LiNi 0.890 Co 0.060 Mn 0.040 Al 0.006 Zr 0.004 O 2 and POSS-NH 2 were mixed in a mass ratio of 1:0.005, and then calcined at 290°C for 6 h to coat the surface of LiNi 0.890 Co 0.060 Mn 0.040 Al 0.006 Zr 0.004 O 2 with POSS-NH 2 to obtain the ternary positive electrode material LiNi 0.890 Co 0.060 Mn 0.040 Al 0.006 Zr 0.004 O 2 @POSS-NH 2 .
  • the method is basically the same as Example 1, except that when preparing the ternary positive electrode material, LiNi 0.55 Co 0.05 Mn 0.40 O 2 and POSS-NH 2 are mixed in a mass ratio of 1:0.001.
  • the method is basically the same as Example 1, except that when preparing the ternary positive electrode material, LiNi 0.55 Co 0.05 Mn 0.40 O 2 and POSS-NH 2 are mixed in a mass ratio of 1:0.05.
  • the method is basically the same as Example 1, except that when preparing the ternary positive electrode material, LiNi 0.55 Co 0.05 Mn 0.40 O 2 is calcined at 300° C. for 8 h to obtain the ternary positive electrode material LiNi 0.55 Co 0.05 Mn 0.40 O 2 .
  • the morphology of the ternary cathode material prepared in Example 1 was characterized by scanning electron microscopy, and the result is shown in Figure 1. As can be seen from Figure 1, the surface of the ternary cathode material prepared in Example 1 is smooth and uniform without aggregates.
  • the XRD test was performed on the ternary cathode material prepared in Example 1. The result is shown in FIG3 . It can be seen that the ternary cathode material has a sharp diffraction peak, indicating that the crystal structure is good and the crystallinity is high.
  • the morphology of the ternary positive electrode material obtained in Example 4 was characterized by scanning electron microscopy. The result is shown in Figure 2. It can be seen that the surface of the ternary positive electrode material is smooth and uniform without aggregates. Since the coating layer material POSS- NH2 in the ternary positive electrode material of Example 4 accounts for a small proportion, and the crystallinity of the coating layer material POSS- NH2 is much lower than that of the ternary positive electrode material matrix, it is not easy to be detected. Therefore, the peak shape of the coating layer material is not shown in Figure 2.
  • the moisture content of the ternary positive electrode materials prepared in Examples 1 to 7 and Comparative Example 1 was tested under two conditions: a temperature of 25°C and a relative humidity of 40%, and a temperature of 25°C and a relative humidity of 80%.
  • the tested storage days were 0 days, 1 day, 10 days, 30 days and 60 days. The results are shown in Table 1.
  • the ternary positive electrode materials prepared in Examples 1 to 7 and Comparative Example 1 were assembled into button cells.
  • the test conditions included: LR 2032, 0.1C, 2.5 to 4.3V, vs. Li + /Li; the positive electrode sheet of the button cell was prepared in a mass ratio of positive electrode material: conductive agent: polyvinylidene fluoride (PVDF) 95:3:2.
  • PVDF polyvinylidene fluoride
  • Examples 1 to 7 are batteries assembled with a ternary cathode material having a POSS-based hydrophobic coating, and their discharge specific capacity, initial efficiency and 100-week capacity retention rate are improved, thanks to the special cage structure of the coating layer that can maintain structural stability, and the porous channels in the coating layer that are conducive to the conduction of lithium ions; the super-hydrophobic coating in Examples 1 to 7 can enable the ternary cathode material to stably exist without failure in a high humidity environment, and still have stable electrochemical properties after being stored for 60 days.

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Abstract

本申请涉及一种三元正极材料、其制备方法及应用。本申请提供的三元正极材料，包括三元正极材料基体和包覆层，三元正极材料基体的表面包覆有包覆层；三元正极材料基体包括化学式为LiNixCoyM1-x-yO2的材料，其中，M包括Mn、Al、Mg、Ti、Zr、Y、Nb、W、Ce、Sb、Sr和Ta中的一种或多种，0.50＜x≤0.98，0≤y≤0.25，x+y＜1；包覆层的材料包括多面体低聚倍半硅氧烷(POSS)。

Description

三元正极材料、其制备方法及应用
相关申请
本申请要求2022年10月24日提交的，申请号为202211302792.9，名称为“三元正极材料、其制备方法及应用”的中国专利申请的优先权，在此将其全文引入作为参考。
技术领域
本申请涉及锂离子电池材料技术领域，特别是涉及一种三元正极材料、其制备方法及应用。
背景技术
锂离子电池在电动车及电动工具上的成熟应用，使当前动力电池的发展追求高续航与高安全性，目前，高镍低钴化以及中镍高压化成为锂离子电池正极材料的两大应用研究方向。相较于多晶材料，单晶材料在抗压性及结构稳定性方面占据着优势，但存在着比表面积大、吸水性强，导致活性锂的溶出及残余碱的增加，从而增加正极浆料制备时的失效风险如团聚作废，而材料含水率升高还会影响极片的涂覆效果和电池的循环性能，极大限制了中/高镍单晶材料的发展应用。
发明内容
基于此，本申请提供一种三元正极材料、其制备方法、正极极片、锂离子电池及用电装置。
第一方面，本申请提供一种三元正极材料，包括三元正极材料基体和包覆层，所述三元正极材料基体的表面包覆有所述包覆层；
所述三元正极材料基体包括化学式为LiNixCoyM1-x-yO2的材料，其中，M包括Mn、Al、Mg、Ti、Zr、Y、Nb、W、Ce、Sb、Sr和Ta中的一种或多种，0.50＜x≤0.98，0≤y≤0.25，x+y＜1；所述包覆层的材料包括多面体低聚倍半硅氧烷(POSS)。
在一些实施方式中，所述三元正极材料基体包括化学式为LiNixCoyM1-x-yO2的材料，其中，M包括Mn、Al、Ti和Zr中的一种或多种，0.50＜x≤0.98，0＜y≤0.25，x+y＜1。
在一些实施方式中，所述三元正极材料基体包括化学式为LiNixCoyMn1-x-yO2的材料，其中，0.50＜x≤0.98，0＜y≤0.25，x+y＜1。
在一些实施方式中，所述三元正极材料基体包括化学式为LiNixCoyMn1-x-yO2的材料，其中，0.50＜x≤0.98，0＜y＜0.25，x+y＜1。
在一些实施方式中，所述多面体低聚倍半硅氧烷包括多面体低聚倍半硅氧烷-烷基、多面体低聚倍半硅氧烷-苯基、多面体低聚倍半硅氧烷-烯基、多面体低聚倍半硅氧烷-氨基、多面体低聚倍半硅氧烷-羟基和多面体低聚倍半硅氧烷-丙烯酸酯中的一种或多种。
在一些实施方式中，所述多面体低聚倍半硅氧烷为多面体低聚倍半硅氧烷-氨基、多面体 低聚倍半硅氧烷-丙烯酸酯、和其组合。
在一些实施方式中，所述多面体低聚倍半硅氧烷为多面体低聚倍半硅氧烷-氨基。
在一些实施方式中，所述包覆层与所述三元正极材料基体的质量比为(0.0001～0.05)：1。在一些实施方式中，所述包覆层与所述三元正极材料基体的质量比为(0.001～0.05)：1。
在一些实施方式中，所述三元正极材料基体的比表面积为0.4m2/g～2.5m2/g。在一些实施方式中，所述三元正极材料基体的比表面积为0.85m2/g～2.0m2/g。
第二方面，本申请提供一种上述三元正极材料的制备方法，包括以下步骤：
制备三元正极材料基体；
将所述三元正极材料基体与包覆层的材料混合，进行第一焙烧处理，从而得到三元正极材料，
其中所述三元正极材料基体包括化学式为LiNixCoyM1-x-yO2的材料，其中，M包括Mn、Al、Mg、Ti、Zr、Y、Nb、W、Ce、Sb、Sr和Ta中的一种或多种，0.50＜x≤0.98，0≤y≤0.25，x+y＜1；所述包覆层的材料包括多面体低聚倍半硅氧烷。
在一些实施方式中，所述第一焙烧处理的工艺条件包括：第一焙烧温度260℃～700℃，第一焙烧时间4h～12h。
在一些实施方式中，所述三元正极材料基体的制备包括以下步骤：
(1)将三元正极材料基体前驱体、第一锂源和任选的金属化合物混合，并且进行第二焙烧，得到中间材料；
(2)将所述中间材料与第二锂源混合，并且进行第三焙烧，得到所述三元正极材料基体。
在一些实施方式中，所述三元正极材料基体的制备包括以下步骤：
S1.将三元正极材料基体前驱体、任选的金属化合物和第一锂源混合，得到中间体A；
S2.对所述中间体A进行焙烧预处理，得到中间体B；
S3.将所述中间体B与第二锂源混合后进行第二焙烧处理，得到所述三元正极材料基体。
在一些实施方式中，步骤(1)或步骤S1中所述三元正极材料基体前驱体包括化学式为NixCoyM1-x-y(OH)2的材料，其中，0.50＜x≤0.98，0≤y≤0.25，x+y＜1，其中，M包括Mn、Al、Mg、Ti、Zr、Y、Nb、W、Ce、Sb、Sr和Ta中的一种或多种。
在一些实施方式中，步骤(1)或步骤S1中所述金属化合物中的金属元素包括Al、Mg、Ti、Zr、Y、Nb、W、Ce、Sb、Sr和Ta中的一种或多种。在一些实施方式中，步骤(1)或步骤S1中所述金属化合物中的金属元素为Al、Ti和Zr中的一种或多种。
在一些实施方式中，以摩尔比计，步骤(1)或步骤S1中第一锂源中的Li+：任选的金属化合物中的金属元素：三元正极材料基体前驱体为(0.50～1.06)：(0～0.02)：1。
在一些实施方式中，步骤(1)或步骤S1中所述第一锂源和步骤(2)或步骤S3中所述第二锂源各自独立地包括氢氧化锂和碳酸锂中的一种或多种。
在一些实施方式中，步骤(1)的第二焙烧的工艺条件包括：焙烧温度400℃～650℃，焙烧时间3h～10h。
在一些实施方式中，步骤S2中焙烧预处理的工艺条件包括：焙烧温度400℃～650℃，焙 烧时间3h～10h。
在一些实施方式中，以摩尔比计，步骤(2)中第二锂源中的Li+：中间材料为(0～0.55)：1。
在一些实施方式中，以摩尔比计，步骤S3中第二锂源中的Li+：中间体B为(0～0.55)：1。
在一些实施方式中，步骤(2)中第三焙烧的工艺条件包括：焙烧温度600℃～1100℃，焙烧时间6h～20h。
在一些实施方式中，步骤S3中第二焙烧温度为600℃～1100℃，第二焙烧时间为6h～20h。
第三方面，本申请提供一种正极极片，包括上述三元正极材料或者上述制备方法制得的三元正极材料。
第四方面，本申请提供一种锂离子电池，包括上述正极极片。
第五方面，本申请提供一种用电装置，包括上述锂离子电池。
第六方面，本申请提供一种三元正极材料，其具有下组至少一种特征：
在25℃的温度和40％的相对湿度下存放30天含水率相比于存放0天含水率增长不超过97ppm，例如在13ppm至97ppm之间；
在25℃的温度和40％的相对湿度下存放60天含水率相比于存放0天含水率增长不超过118ppm，例如在23ppm至118ppm之间；
在25℃的温度和80％的相对湿度下存放30天含水率相比于存放0天含水率增长不超过297ppm，例如在128ppm至297ppm之间；和
在25℃的温度和80％的相对湿度下存放60天含水率相比于存放0天含水率增长不超过315ppm，例如在133ppm至315ppm之间。
第七方面，本申请提供一种三元正极材料，其中由该三元正极材料制备的电池的100周容量保持率不低于92％，其中该100周容量保持率是将该电池在45℃和40％相对湿度或80％相对湿度下存放60天后以2.5V～4.25V的电压进行0.3C恒流充放电100周测定的。
本申请的一个或多个实施方式的细节在下面的附图和描述中提出。本申请的其他特征、目的和优点将从说明书、附图以及权利要求书变得明显。
附图说明
图1为本申请实施例1制备的三元正极材料的SEM图。
图2为本申请实施例4制备的三元正极材料的SEM图。
图3为本申请实施例1制备的三元正极材料的XRD图。
具体实施方式
为使本申请的上述目的、特征和优点能够更加明显易懂，下面对本申请的具体实施方式做详细的说明。在下面的描述中阐述了很多具体细节以便于充分理解本申请。但是本申请能够以很多不同于在此描述的其它方式来实施，本领域技术人员可以在不违背本申请内涵的情 况下做类似改进，因此本申请不受下面公开的具体实施例的限制。
在本申请的说明中，除非另有定义，未明确说明的专业术语、专业用词均与本领域技术人员通常理解的含义相同，且为本领域技术人员的公知常识，未明确说明的方法均为本领域技术人员公知的常规方法。
此外，术语“第一”、“第二”、“第三”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”、“第三”的特征可以明示或者隐含地包括至少一个该特征。本申请中术语“多种”的含义是至少两种，例如两种，三种等，除非另有明确具体的限定。
本申请中，以开放式描述的技术特征中，包括所列举特征组成的封闭式技术方案，也包括包含所列举特征的开放式技术方案。本申请一实施方式提供一种三元正极材料，包括三元正极材料基体和包覆层，三元正极材料基体的表面包覆有包覆层；
三元正极材料基体包括化学式为LiNixCoyM1-x-yO2的材料，其中，M包括Mn、Al、Mg、Ti、Zr、Y、Nb、W、Ce、Sb、Sr和Ta中的一种或多种，0.50＜x≤0.98，0≤y≤0.25，x+y＜1；包覆层的材料包括多面体低聚倍半硅氧烷。
在一些实施方式中，M包括Mn、Al、Ti和Zr中的一种或多种。在一些实施方式中，M为Mn。在一些实施方式中，0.50＜x≤0.98，0＜y≤0.25，x+y＜1。在一些实施方式中，0.50＜x≤0.98，0＜y＜0.25，x+y＜1。由此，可以有效抑制空气中水分在三元正极材料表面的附着，提升其对存储环境的适应性，延长存储时间，进而提升锂离子电池的循环性能。
上述三元正极材料基体表面的包覆层具有超疏水性，并具有有机-无机复合结构，疏水包覆层的无机层在内与三元正极材料基体紧密结合，疏水包覆层的有机层在外与空气接触，可有效降低三元正极材料的吸湿性，因此，该疏水包覆层能够提升三元正极材料对存储环境的适应性，延长三元正极材料的存储时间；该超疏水包覆层可以约束微裂纹的扩大和延伸，吸收能量，减少三元正极材料基体的应力集中，其有机活性位点可以增加体系的交联度和相容性，提高材料的力学性能和强度，进而维持材料的结构稳定性，提升锂离子电池的循环保持率；包覆层特定的笼状结构和分子内多孔孔道有利于锂离子的传导，提升主体材料的动力学性能。
可理解，x例如可以是0.51、0.52、0.53、0.54、0.55、0.57、0.59、0.60、0.62、0.65、0.70、0.80、0.90、0.95或0.98，y例如可以是0.01、0.02、0.03、0.04、0.05、0.06、0.07、0.08、0.10、0.15、0.20、0.22、0.24或0.25。
在一些实施方式中，多面体低聚倍半硅氧烷包括多面体低聚倍半硅氧烷-烷基、多面体低聚倍半硅氧烷-苯基、多面体低聚倍半硅氧烷-烯基、多面体低聚倍半硅氧烷-氨基、多面体低聚倍半硅氧烷-羟基和多面体低聚倍半硅氧烷-丙烯酸酯中的一种或多种。在一些实施方式中，多面体低聚倍半硅氧烷为多面体低聚倍半硅氧烷-氨基、多面体低聚倍半硅氧烷-丙烯酸酯、和其组合。在一些实施方式中，多面体低聚倍半硅氧烷为多面体低聚倍半硅氧烷-氨基。
在一些实施方式中，包覆层与三元正极材料基体的质量比为(0.0001～0.05)：1。可理解，包覆层与三元正极材料基体的质量比可以是(0.0001～0.05)：1之间的任意值，例如：0.0001： 1、0.0002：1、0.0003：1、0.0005：1、0.0008：1、0.001：1、0.005：1、0.008：1、0.01：1、0.02：1、0.03：1、0.04：1或0.05：1。在一些实施方式中，包覆层与三元正极材料基体的质量比为(0.001～0.05)：1。需要说明的是，包覆层与三元正极材料基体的质量比不能过高或者过低，当质量比过高时，包覆层较厚，则会影响锂离子的传输速度，当质量比过低时，包覆层较薄，可能无法有效降低三元正极材料的吸湿性。
在一些实施方式中，包覆层为连续层状包覆。也就是说，包覆层能够将三元正极材料基体全面包覆。
在一些实施方式中，三元正极材料基体的比表面积为0.4m2/g～2.5m2/g。在一些实施方式中，所述三元正极材料基体的比表面积为0.85m2/g～2.0m2/g。可理解，三元正极材料基体的比表面积例如可以是0.4m2/g、0.5m2/g、0.6m2/g、0.7m2/g、0.8m2/g、0.9m2/g、1m2/g、1.2m2/g、1.5m2/g、1.7m2/g、2m2/g、2.2m2/g、2.5m2/g。控制三元正极材料基体的比表面积为0.4m2/g～2.5m2/g，是为了三元正极材料达到最佳的疏水效果，且不影响其动力学性能。
本申请另一实施方式提供一种上述三元正极材料的制备方法，包括以下步骤：
制备三元正极材料基体；
将三元正极材料基体与如上所述的包覆层的材料混合，进行第一焙烧处理。
在一些实施方式中，第一焙烧处理的工艺条件包括：第一焙烧温度260℃～700℃，第一焙烧时间4h～12h。可理解，第一焙烧温度例如可以是260℃、280℃、3000℃、320℃、350℃、370℃、400℃、410℃、430℃、470℃、490℃、500℃、550℃、600℃、650℃或700℃等，第一焙烧温度还可以是260℃～700℃之间的其他值；第一焙烧时间可以是4h～12h之间的任意值，例如：4h、4.2h、4.5h、4.7h、5h、5.5h、6h、6.5h、7h、8h、9h、10h、11h或12h等。
在一些实施方式中，三元正极材料基体的制备包括以下步骤：
(1)将三元正极材料基体前驱体、第一锂源和任选的金属化合物混合，并且进行第二焙烧，得到中间材料；和
(2)将所述中间材料与第二锂源混合，并且进行第三焙烧，得到所述三元正极材料基体。
在一些实施方式中，三元正极材料基体的制备包括以下步骤：
S1.将三元正极材料基体前驱体、任选的金属化合物和第一锂源混合，得到中间体A；
S2.对中间体A进行焙烧预处理，得到中间体B；和
S3.将中间体B与第二锂源混合后进行第二焙烧处理，得到三元正极材料基体。
在一些实施方式中，以上的步骤(1)或步骤S1中三元正极材料基体前驱体包括化学式为NixCoyM1-x-y(OH)2的材料，其中，0.50＜x≤0.98，0≤y≤0.25，x+y＜1。可理解，x例如可以是0.51、0.52、0.53、0.54、0.55、0.57、0.59、0.60、0.62、0.65、0.70、0.80、0.90、0.95或0.98，y例如可以是0.01、0.02、0.03、0.04、0.05、0.06、0.07、0.08、0.10、0.15、0.20、0.22、0.24或0.25。
在一些实施方式中，以上的步骤(1)或步骤S1中金属化合物中的金属元素包括Al、Mg、Ti、Zr、Y、Nb、W、Ce、Sb、Sr和Ta中的一种或多种。在一些实施方式中，步骤(1)或步骤S1中所述金属化合物中的金属元素为Al、Ti和Zr中的一种或多种。需要说明的是， 金属化合物可以是上述金属的氧化物、氢氧化物或者碳酸盐，例如：Al2O3、MgO、TiO2、ZrO2、Y2O3、Nb2O5、WO3、CeO2、Sb2O3、Sb2O5、SrO、Ta2O5、Al(OH)3、Mg(OH)2、Zr(OH)4、Ti(OH)4、Sr(OH)2、Al2(CO3)3、MgCO3、SrCO3或Zr3(CO3)O5等。
在一些实施方式中，以摩尔比计，以上的步骤(1)或步骤S1中第一锂源中的Li+：任选的金属化合物中的金属元素：三元正极材料基体前驱体为(0.50～1.06)：(0～0.02)：1。可理解，步骤S1中金属化合物的摩尔量可以为0，当步骤S1中金属化合物的质量不为0时，步骤S1中第一锂源中的Li+：金属化合物中的金属元素：三元正极材料基体前驱体的摩尔比例如可以是0.50：0.001：1、0.51：0.002：1、0.57：0.005：1、0.60：0.007：1、0.72：0.009：1、0.80：0.01：1、0.90：0.015：1、0.95：0.017：1、1.00：0.019：1或1.06：0.02：1等；本申请添加金属化合物的目的是使金属元素在过渡金属层间起到支撑作用以及增加三元正极材料的动力学性能，从而保证三元正极材料层状结构的稳定性，提升锂离子的传输性。
在一些实施方式中，步骤(1)或步骤S1中第一锂源和步骤(2)或步骤S3中第二锂源各自独立地包括氢氧化锂和碳酸锂中的一种或多种。
在一些实施方式中，步骤S2中焙烧预处理的工艺条件包括：焙烧预处理温度400℃～650℃，焙烧预处理时间3h～10h。可理解，焙烧预处理温度例如可以是400℃、420℃、435℃、450℃、465℃、480℃、500℃、550℃、600℃或650℃，焙烧预处理温度还可以是400℃～650℃之间的其他值；焙烧预处理时间可以是3h、3.5h、4h、4.5h、5h、6h、7h、8.5h或10h，还可以是3h～10h之间的其他值。其中，该步骤S2中焙烧预处理对应于以上步骤(1)中的第二焙烧。因此，步骤S2中焙烧预处理的工艺条件适用于以上步骤(1)中的第二焙烧。
在一些实施方式中，以摩尔比计，步骤S3中第二锂源中的Li+：中间体B＝(0～0.55)：1。需要说明的是，当中间体B的成分与三元正极材料基体的成分相同时无需补锂，此时步骤S3中第二锂源的质量为0，当中间体B的成分与三元正极材料基体的成分不同时，需要加入第二锂源进行补锂，此时第二锂源中的Li+与中间体B的摩尔比例如可以是0.01：1、0.015：1、0.018：1、0.02：1、0.025：1、0.027：1、0.03：1、0.035：1、0.04：1、0.045：1、0.05：1或0.055：1。其中，该步骤S3中的第二锂源对应于以上步骤(2)中的第二锂源，该步骤S3中的中间体B对应于以上步骤(2)中的中间材料。因此，步骤S3中的第二锂源中的Li+与中间体B的摩尔比适用于以上步骤(2)中的第二锂源中的Li+与中间材料的摩尔比。
在一些实施方式中，步骤S3中第二焙烧温度为600℃～1100℃，第二焙烧时间为6h～20h。可理解，步骤S3中第二焙烧温度例如可以是600℃、620℃、650℃、670℃、700℃、800℃、900℃、1000℃或1100℃等，第二焙烧时间例如可以是6h、6.5h、7h、7.5h、8h、9h、10h、11h、12h、13h、14h、15h、16h、17h、18h、19h或20h等。其中，该步骤S3中的第二焙烧对应于以上步骤(2)中的第三焙烧。因此，步骤S3中的第二焙烧的工艺条件适用于以上步骤(2)中的第三焙烧。
本申请另一实施方式提供一种正极极片，包括上述三元正极材料或者上述制备方法制得的三元正极材料。需要说明的是，上述正极极片可以如下制备得到：以上述三元正极材料或者上述制备方法制得的三元正极材料、导电剂和粘结剂为原料，加入溶剂搅拌均匀后形成正 极浆料，涂覆在铝箔上，经干燥后得到该正极极片。其中，导电剂、粘结剂和溶剂采用本领域常用的即可。
本申请另一实施方式提供一种锂离子电池，包括上述正极极片。需要说明的是，上述锂离子电池可以由正极极片、隔膜和负极极片经叠片或者卷绕后与壳体组装得到。壳体中还注入有电解液。负极极片上附着的负极活性物质例如可以是石墨、硬炭、硅材料、钛酸锂和金属锂中的一种或多种。上述隔膜和电解液采用本领域常用的即可。
本申请另一实施方式提供一种用电装置，包括上述锂离子电池。需要说明的是，上述锂离子电池可以作为电源或者能量储存单元用于用电装置中。上述用电装置包括但不限于电动车辆、智能家电产品、电脑、手机、数码相机等。
在本申请的实施方式中，提供的三元正极材料具有下组至少一种特征：
在25℃的温度和40％的相对湿度下存放30天含水率相比于存放0天含水率增长不超过97ppm，例如在13ppm至97ppm之间；
在25℃的温度和40％的相对湿度下存放60天含水率相比于存放0天含水率增长不超过118ppm，例如在23ppm至118ppm之间；
在25℃的温度和80％的相对湿度下存放30天含水率相比于存放0天含水率增长不超过297ppm，例如在128ppm至297ppm之间；和
在25℃的温度和80％的相对湿度下存放60天含水率相比于存放0天含水率增长不超过315ppm，例如在133ppm至315ppm之间。
在本申请的实施方式中，由提供的三元正极材料制备的电池的100周容量保持率不低于92％，其中该100周容量保持率是将该电池在45℃和40％相对湿度或80％相对湿度下存放60天后以2.5V～4.25V的电压进行0.3C恒流充放电100周测定的。
与相关技术相比，上述三元正极材料、其制备方法、正极极片、锂离子电池及用电装置至少具有如下优点：
(1)上述包覆层的材料包括多面体低聚倍半硅氧烷(POSS)，该包覆层包覆于三元正极材料基体的表面使其产生超疏水效应，包覆层中的无机层在内与三元正极材料基体紧密结合，包覆层中的有机层在外与空气接触，可有效降低三元正极材料的吸湿性，提升三元正极材料对存储环境的适应性，延长三元正极材料的存储时间。
(2)超疏水包覆层可以约束微裂纹的扩大和延伸，吸收能量，减少三元正极材料基体的应力集中，其有机活性位点可以增加体系的交联度和相容性，提高三元正极材料的力学性能和强度，维持三元正极材料的结构稳定性，进而提升锂离子电池循环保持率。
以下结合具体实施例和对比例对本申请做进一步详细的说明。本申请以下实施例和对比例中所用的实验原料均可从市场上购买或按照本领域技术人员熟知的常规方法制备得到。
以下实施例和对比例中，多面体低聚倍半硅氧烷-氨基(POSS-NH2)选用西安齐岳生物POSS-氨丙基异辛基笼形倍半硅氧烷，多面体低聚倍半硅氧烷-丙烯酸酯(POSS-丙烯酸酯)选用西安齐岳生物POSS-甲基丙烯酸乙酯化笼形倍半硅氧烷。
实施例1
本实施例中，三元正极材料基体前驱体选用Ni0.55Co0.05Mn0.40(OH)2，第一锂源和第二锂源均选用Li2CO3。
三元正极材料基体的制备方法包括如下步骤：
S1.按照Li2CO3：Ni0.55Co0.05Mn0.40(OH)2＝0.95：1的摩尔比进行配料，充分混合后得到中间体A；
S2.将中间体A在650℃下预焙烧6h，得到中间体B；
S3.按照中间体B：Li2CO3＝1：0.08的摩尔比进行配料，充分混合后在890℃下焙烧14h，得到比表面积为(1.25±0.2)m2/g的三元正极材料基体，其化学式为LiNi0.55Co0.05Mn0.40O2。
按照如下方法制备三元正极材料：
将LiNi0.55Co0.05Mn0.40O2与POSS-NH2按照1：0.003的质量比进行配料，充分混合后在300℃下焙烧8h，以在LiNi0.55Co0.05Mn0.40O2的表面包覆POSS-NH2，得到三元正极材料LiNi0.55Co0.05Mn0.40O2@POSS-NH2。
实施例2
本实施例中，三元正极材料基体前驱体选用Ni0.62Co0.25Mn0.13(OH)2，第一锂源选用Li2CO3，第二锂源选用LiOH。
三元正极材料基体的制备方法包括如下步骤：
S1.按照Li2CO3：Ni0.62Co0.25Mn0.13(OH)2＝0.75：1的摩尔比进行配料，充分混合后得到中间体A；
S2.将中间体A在600℃下预焙烧6h，得到中间体B；
S3.按照中间体B：LiOH＝1：0.27的摩尔比进行配料，充分混合后在860℃下焙烧11h，得到比表面积为(0.85±0.2)m2/g的三元正极材料基体，其化学式为LiNi0.62Co0.25Mn0.13O2。
按照如下方法制备三元正极材料：
将LiNi0.62Co0.25Mn0.13O2与POSS-丙烯酸酯按照1：0.002的质量比进行配料，充分混合后在300℃下焙烧8h，以在LiNi0.62Co0.25Mn0.13O2的表面包覆POSS-丙烯酸酯，得到三元正极材料LiNi0.55Co0.05Mn0.40O2@POSS-丙烯酸酯。
实施例3
本实施例中，三元正极材料基体前驱体选用Ni0.78Co0.12Al0.10(OH)2，第一锂源和第二锂源均选用Li2CO3。
三元正极材料基体的制备方法包括如下步骤：
S1.按照Li2CO3：Ni0.78Co0.12Al0.10(OH)2＝0.90：1的摩尔比进行配料，充分混合后得到中间体A；
S2.将中间体A在600℃下预焙烧4h，得到中间体B；
S3.按照中间体B：Li2CO3＝1：0.15的摩尔比进行配料，充分混合后在800℃下焙烧15h，得到比表面积为(2.0±0.2)m2/g的三元正极材料基体，其化学式为LiNi0.78Co0.12Al0.10O2。
按照如下方法制备三元正极材料：
将LiNi0.78Co0.12Al0.10O2、POSS-NH2与POSS-丙烯酸酯按照1：0.001：0.001的质量比进 行配料，充分混合后在270℃下焙烧6h，以在LiNi0.78Co0.12Al0.10O2的表面包覆POSS-NH2和POSS-丙烯酸酯，得到三元正极材料LiNi0.78Co0.12Al0.10O2@POSS-NH2/POSS-丙烯酸酯。
实施例4
本实施例中，三元正极材料基体前驱体选用Ni0.82Co0.06Mn0.12(OH)2，第一锂源和第二锂源均选用LiOH，金属化合物选用TiO2。
三元正极材料基体的制备方法包括如下步骤：
S1.按照LiOH：TiO2：Ni0.82Co0.06Mn0.12(OH)2＝0.95：0.005：1的摩尔比进行配料，充分混合后得到中间体A；
S2.将中间体A在550℃下预焙烧5h，得到中间体B；
S3.按照中间体B：LiOH＝1：0.08的摩尔比进行配料，充分混合后在760℃下焙烧12h，得到比表面积为(0.45±0.1)m2/g的三元正极材料基体，其化学式为LiNi0.815Co0.060Mn0.120Ti0.005O2。
按照如下方法制备三元正极材料：
将LiNi0.815Co0.060Mn0.120Ti0.005O2与POSS-NH2按照1：0.003的质量比进行配料，充分混合后在270℃下焙烧6h，以在LiNi0.815Co0.060Mn0.120Ti0.005O2的表面包覆POSS-NH2，得到三元正极材料LiNi0.815Co0.060Mn0.120Ti0.005O2@POSS-NH2。
实施例5
本实施例中，三元正极材料基体前驱体选用Ni0.90Co0.06Mn0.04(OH)2，第一锂源和第二锂源均选用LiOH，金属化合物选用Al2O3和ZrO2。
三元正极材料基体的制备方法包括如下步骤：
S1.按照LiOH：Al2O3：ZrO2：Ni0.90Co0.06Mn0.04(OH)2＝1.02：0.003：0.004：1的摩尔比进行配料，充分混合后得到中间体A；
S2.将中间体A在550℃下预焙烧5h，得到中间体B；
S3.按照中间体B：LiOH＝1：0.03的摩尔比进行配料，充分混合后在770℃下焙烧10h，得到比表面积为(0.60±0.15)m2/g的三元正极材料基体，其化学式为LiNi0.890Co0.060Mn0.040Al0.006Zr0.004O2。
按照如下方法制备三元正极材料：
将LiNi0.890Co0.060Mn0.040Al0.006Zr0.004O2与POSS-NH2按照1：0.005的质量比进行配料，充分混合后在290℃下焙烧6h，以在LiNi0.890Co0.060Mn0.040Al0.006Zr0.004O2的表面包覆POSS-NH2，得到三元正极材料LiNi0.890Co0.060Mn0.040Al0.006Zr0.004O2@POSS-NH2。
实施例6
基本同实施例1，所不同的是：制备三元正极材料时，将LiNi0.55Co0.05Mn0.40O2与POSS-NH2按照1：0.001的质量比进行配料。
实施例7
基本同实施例1，所不同的是：制备三元正极材料时，将LiNi0.55Co0.05Mn0.40O2与POSS-NH2按照1：0.05的质量比进行配料。
对比例1
基本同实施例1，所不同的是：制备三元正极材料时，将LiNi0.55Co0.05Mn0.40O2在300℃下焙烧8h，得到三元正极材料LiNi0.55Co0.05Mn0.40O2。
SEM测试和XRD测试
采用扫描电子显微镜对实施例1制备的三元正极材料进行形貌表征，结果如图1所示。由图1可以看出，实施例1制备的三元正极材料表面光滑均匀，无聚集物。
针对实施例1制备的三元正极材料进行XRD测试，结果如图3所示，可以看出三元正极材料有尖锐的衍射峰，表明晶体结构良好，结晶度高。
采用扫描电子显微镜对实施例4得到的三元正极材料进行形貌表征，结果如图2所示，可以看出三元正极材料表面光滑均匀，无聚集物。由于实施例4的三元正极材料中的包覆层材料POSS-NH2所占比例较小，并且包覆层材料POSS-NH2的结晶性远低于三元正极材料基体，不易被检测，因此，图2中未显示包覆层材料的峰形。
含水率测试
在温度为25℃，相对湿度为40％，以及在温度为25℃，相对湿度为80％两种条件下，测试实施例1～7和对比例1制备的三元正极材料的含水率，测试的铺展存放天数为0天、1天、10天、30天与60天，结果如表1所示。
表1

由表1数据可知，实施例1～7制备的三元正极材料在25℃、相对湿度40％和80％条件下存放，样品含水率仅有小幅度上升，这是由于三元正极材料表面形成有POSS基疏水包覆层；对比例1由于未形成包覆层，样品吸水严重，导致含水率明显升高。
电化学性能测试
将实施例1～7和对比例1制备的三元正极材料组装成扣式电池，测试条件包括：LR 2032，0.1C，2.5～4.3V，vs.Li+/Li；扣式电池的正极极片按照正极材料：导电剂：聚偏二氟乙烯(PVDF)＝95：3：2的质量比配料，将组装成的扣式电池在45℃恒温环境下，2.5V～4.25V的电压范围内进行0.3C恒流充放电100周，测试结果如表2所示。
表2

由表2可以看出，与对比例1相比，实施例1至7为具有POSS基疏水包覆层的三元正极材料组装的电池，其放电比容量、首次效率及100周容量保持率有所提升，这得益于包覆层特殊的笼状结构可以维持结构稳定性，包覆层内多孔孔道有利于锂离子的传导；实施例1至7中的超疏水包覆层可使三元正极材料在高湿度环境下稳定存在不失效，存放60天仍具备稳定的电化学性能。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本申请的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对申请专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本申请构思的前提下，还可以做出若干变形和改进，这些都属于本申请的保护范围。因此，本申请专利的保护范围应以所附权利要求为准，说明书及附图可以用于解释权利要求的内容。

Claims (14)

  1. 一种三元正极材料，其特征在于，包括三元正极材料基体和包覆层，所述三元正极材料基体的表面包覆有所述包覆层；
    所述三元正极材料基体包括化学式为LiNixCoyM1-x-yO2的材料，其中，M包括Mn、Al、Mg、Ti、Zr、Y、Nb、W、Ce、Sb、Sr和Ta中的一种或多种，0.50＜x≤0.98，0≤y≤0.25，x+y＜1；所述包覆层的材料包括多面体低聚倍半硅氧烷。
  2. 根据权利要求1所述的三元正极材料，其特征在于，所述三元正极材料基体包括化学式为LiNixCoyM1-x-yO2的材料，其中，M包括Mn、Al、Ti和Zr中的一种或多种，0.50＜x≤0.98，0＜y≤0.25，x+y＜1。
  3. 根据权利要求1或2所述的三元正极材料，其特征在于，所述三元正极材料基体包括化学式为LiNixCoyMn1-x-yO2的材料，其中，0.50＜x≤0.98，0＜y≤0.25，x+y＜1。
  4. 根据权利要求1或2所述的三元正极材料，其特征在于，所述多面体低聚倍半硅氧烷包括多面体低聚倍半硅氧烷-烷基、多面体低聚倍半硅氧烷-苯基、多面体低聚倍半硅氧烷-烯基、多面体低聚倍半硅氧烷-氨基、多面体低聚倍半硅氧烷-羟基和多面体低聚倍半硅氧烷-丙烯酸酯中的一种或多种，
    优选为多面体低聚倍半硅氧烷-氨基、多面体低聚倍半硅氧烷-丙烯酸酯和其组合，更优选为多面体低聚倍半硅氧烷-氨基。
  5. 根据权利要求1或2所述的三元正极材料，其特征在于，所述包覆层与所述三元正极材料基体的质量比为(0.0001～0.05)：1，优选为(0.001～0.05)：1；可选地，所述三元正极材料基体的比表面积为0.4m2/g～2.5m2/g，优选地为0.85m2/g～2.0m2/g。
  6. 一种权利要求1至5任一项所述的三元正极材料的制备方法，其特征在于，包括：
    制备三元正极材料基体；和
    将所述三元正极材料基体与包覆层的材料混合，进行第一焙烧处理，从而得到三元正极材料，
    其中所述三元正极材料基体包括化学式为LiNixCoyM1-x-yO2的材料，其中，M包括Mn、Al、Mg、Ti、Zr、Y、Nb、W、Ce、Sb、Sr和Ta中的一种或多种，0.50＜x≤0.98，0≤y≤0.25，x+y＜1；所述包覆层的材料包括多面体低聚倍半硅氧烷。
  7. 根据权利要求6所述的制备方法，其特征在于，所述第一焙烧处理的工艺条件包括：第一焙烧温度260℃～700℃，第一焙烧时间4h～12h。
  8. 根据权利要求6或7所述的制备方法，其特征在于，所述三元正极材料基体的制备步骤包括：
    (1)将三元正极材料基体前驱体、第一锂源和任选的金属化合物混合，并且进行第二焙烧，得到中间材料；和
    (2)将所述中间材料与第二锂源混合，并且进行第三焙烧，得到所述三元正极材料基体。
  9. 根据权利要求8所述的制备方法，其特征在于，所述三元正极材料基体的制备包括以 下特征中至少一个：
    (1)步骤(1)中所述三元正极材料基体前驱体包括化学式为NixCoyM1-x-y(OH)2的材料，其中，0.50＜x≤0.98，0≤y≤0.25，x+y＜1，其中，M包括Mn、Al、Mg、Ti、Zr、Y、Nb、W、Ce、Sb、Sr和Ta中的一种或多种；
    (2)步骤(1)中所述金属化合物中的金属元素包括Al、Mg、Ti、Zr、Y、Nb、W、Ce、Sb、Sr和Ta中的一种或多种；优选Al、Ti和Zr中的一种或多种；
    (3)以摩尔比计，步骤(1)中所述第一锂源中的Li+：任选的金属化合物中的金属元素：所述三元正极材料基体前驱体为(0.50～1.06)：(0～0.02)：1；
    (4)步骤(1)中所述第一锂源和步骤(2)中所述第二锂源各自独立地包括氢氧化锂和碳酸锂中的一种或多种；
    (5)步骤(1)中所述第二焙烧的工艺条件包括：焙烧温度400℃～650℃，焙烧时间3h～10h；
    (6)以摩尔比计，步骤(2)中所述第二锂源中的Li+：所述中间材料为(0～0.55)：1；和
    (7)步骤(2)中第三焙烧的工艺条件包括：焙烧温度600℃～1100℃，焙烧时间6h～20h。
  10. 一种正极极片，其特征在于，包括权利要求1至5任一项所述的三元正极材料、或者权利要求6至9任一项所述的制备方法制得的三元正极材料。
  11. 一种锂离子电池，其特征在于，包括权利要求10所述的正极极片。
  12. 一种用电装置，其特征在于，包括权利要求11所述的锂离子电池。
  13. 一种三元正极材料，其特征在于，具有下组至少一种特征：
    在25℃的温度和40％的相对湿度下存放30天含水率相比于存放0天含水率增长不超过97ppm，优选在13ppm至97ppm之间；
    在25℃的温度和40％的相对湿度下存放60天含水率相比于存放0天含水率增长不超过118ppm，优选在23ppm至118ppm之间；
    在25℃的温度和80％的相对湿度下存放30天含水率相比于存放0天含水率增长不超过297ppm，优选在128ppm至297ppm之间；和
    在25℃的温度和80％的相对湿度下存放60天含水率相比于存放0天含水率增长不超过315ppm，优选在133ppm至315ppm之间。
  14. 一种三元正极材料，其特征在于，由所述三元正极材料制备的电池的100周容量保持率不低于92％，其中所述100周容量保持率是将所述电池在45℃和40％相对湿度或80％相对湿度下存放60天后以2.5V～4.25V的电压进行0.3C恒流充放电100周测定的。
PCT/CN2023/115676 2022-10-24 2023-08-30 三元正极材料、其制备方法及应用 WO2024087872A1 (zh)

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