Zirconia-lanthanum phase co-doped high-nickel ternary material, preparation method and battery

Abstract

This invention discloses a zirconium-lanthanum bulk co-doped high-nickel ternary material, its preparation method, and a battery. The zirconium-lanthanum bulk co-doped high-nickel ternary material is a ternary cathode material with bulk co-doped zirconium and lanthanum; the chemical formula of the ternary cathode material is LiNi. x Co y Mn (1‑x‑y) O2, wherein 0.8≤x≤0.9, 0≤y≤0.1; the total molar amount of zirconium and lanthanum is 1%~5% of the total molar amount of nickel, cobalt and manganese. The zirconium-lanthanum bulk co-doped high-nickel ternary material provided by the present invention enhances the mechanical strength of the ternary material through the bulk co-doping of zirconium and lanthanum, suppresses cracking and pulverization of the ternary material during charge and discharge, and improves cycle stability; at the same time, the two elements Zr and La synergistically stabilize the lattice, reduce lithium-nickel mixing, suppress irreversible phase transformation and lattice oxygen precipitation, achieve dual stability of bulk phase and interface, and improve the consistency and stability of the zirconium-lanthanum bulk co-doped high-nickel ternary material.

Description

Technical Field

[0001] This invention belongs to the field of battery technology and relates to a modified cathode material, particularly to a zirconium-lanthanum bulk co-doped high-nickel ternary material, its preparation method, and a battery. Background Technology

[0002] With the large-scale application and technological iteration of lithium-ion batteries in consumer electronics, new energy vehicles, and grid energy storage, there are continuous upgrades in requirements for battery energy density, long cycle life, and service safety. High-nickel layered ternary oxide cathode materials (Ni molar ratio ≥80%) have become the preferred cathode material for constructing high-energy-density lithium-ion batteries due to their advantages such as high reversible specific capacity of over 200mAh / g and relatively low raw material cost.

[0003] However, during charge-discharge cycles, the repeated insertion and extraction of lithium ions in these materials can cause significant anisotropic expansion and contraction of the material lattice, resulting in continuous accumulation of lattice strain. This can easily lead to primary grain boundary cracking and secondary overall particle pulverization. At the same time, it can induce irreversible phase transitions from layered structures to spinel and rock salt phases. Accompanied by the continuous aggravation of lattice oxygen evolution and electrolyte-electrode interface side reactions, this ultimately leads to rapid decay of reversible capacity and a sharp deterioration of cycle stability, which seriously restricts the large-scale commercial application of high-nickel ternary materials in long-life and high-safety battery systems.

[0004] To address these challenges, the industry has conducted extensive research on modification techniques, including element doping, surface coating, and microstructure control. While these techniques can alleviate the material structure degradation caused by lattice stress to some extent, they still cannot achieve synergistic optimization of material mechanical strength, ion and electron conduction performance, and lattice structure stability. Therefore, they cannot fundamentally solve the structural damage and performance degradation during the cycling process of high-nickel ternary materials. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide a zirconium-lanthanum bulk co-doped high-nickel ternary material, its preparation method, and a battery. This zirconium-lanthanum bulk co-doped high-nickel ternary material enhances the mechanical strength and improves cycle stability through the bulk co-doping of zirconium and lanthanum. Simultaneously, the synergistic stabilization of Zr and La stabilizes the crystal lattice, reduces lithium-nickel mixing, and suppresses irreversible phase transitions and lattice oxygen precipitation, achieving dual stability of the bulk phase and interface, thereby improving the consistency and stability of the zirconium-lanthanum bulk co-doped high-nickel ternary material.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] In a first aspect, the present invention provides a zirconium-lanthanum bulk phase co-doped high-nickel ternary material, wherein the zirconium-lanthanum bulk phase co-doped high-nickel ternary material is a ternary cathode material with bulk phase co-doped zirconium and lanthanum;

[0008] The chemical formula of the ternary cathode material is LiNi. x Co y Mn (1-x-y) O2, wherein 0.8≤x≤0.9, 0≤y≤0.1; the total molar amount of zirconium and lanthanum is 1%~5% of the total molar amount of nickel, cobalt and manganese.

[0009] This invention achieves bulk co-doping of Zr and La elements in a ternary precursor, resulting in the in-situ generation of a uniformly dispersed lithium lanthanum zirconate phase within the material particles after sintering. This lithium lanthanum zirconate phase possesses excellent structural rigidity, serving as a rigid support site within the particles. This significantly enhances the mechanical strength of the ternary material particles, effectively suppressing particle cracking and pulverization caused by lattice expansion and contraction during charge-discharge cycles, maintaining electrode structural integrity, and greatly improving the long-cycle stability of the material. Simultaneously, the lithium lanthanum zirconate phase exhibits both excellent lithium-ion conductivity and electronic conductivity, enabling the construction of efficient ion and electron transport channels within the bulk phase of the material. This reduces the lithium-ion migration barrier and electrode polarization, improves lithium-ion transport kinetics and electrochemical reaction reversibility, and optimizes the rate performance and overall electrical performance of the material.

[0010] Furthermore, this invention achieves synergistic lattice stabilization through Zr and La co-doping. La stabilizes transition metal lattice sites and suppresses irreversible phase transitions and lattice oxygen precipitation, while Zr optimizes the local lattice environment and reduces lithium-nickel mixing. The synergistic effect of these two elements, combined with the interface protection provided by the in-situ generated lithium lanthanum zirconate phase, simultaneously achieves dual stability of the bulk structure and particle interfaces, further enhancing the material's cycle stability. This invention utilizes a precursor co-precipitation process to achieve uniform bulk doping of Zr and La, ensuring uniform dispersion of the dopant elements within the material and guaranteeing the consistency and stability of its properties.

[0011] In some embodiments, the molar ratio of zirconium to lanthanum is 1:1.2 to 1:1.6, for example, it can be 1:1.2, 1:1.3, 1:1.4, 1:1.5 or 1:1.6, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0012] Secondly, the present invention provides a method for preparing a zirconium-lanthanum bulk co-doped high-nickel ternary material, the method comprising the following steps: mixing a ternary metal salt solution, a doping salt solution, a precipitant solution, and a complexing agent solution in a co-precipitation reaction under stirring to obtain a bulk doped precursor with a median particle size D50 of 7µm~12µm; mixing the bulk doped precursor with a lithium source and sintering to obtain the zirconium-lanthanum bulk co-doped high-nickel ternary material as described in the first aspect;

[0013] The solute in the doped salt solution includes zirconium salt, lanthanum salt and a first complexing agent;

[0014] The solute in the complexing agent solution includes a second complexing agent.

[0015] In some embodiments, the ternary metal salt solution includes nickel salt, cobalt salt, and manganese salt;

[0016] The nickel salt includes any one or a combination of at least two of nickel nitrate, nickel sulfate, or nickel chloride;

[0017] The cobalt salt includes any one or a combination of at least two of cobalt nitrate, cobalt sulfate, or cobalt chloride.

[0018] The manganese salt includes any one or a combination of at least two of manganese nitrate, manganese sulfate, or manganese chloride.

[0019] In some embodiments, the total concentration of nickel, cobalt and manganese in the ternary metal salt solution is 2 mol / L to 4 mol / L.

[0020] In some embodiments, the zirconium salt includes any one or a combination of at least two of zirconium oxychloride, zirconium sulfate, zirconium nitrate, or zirconium oxynitrate.

[0021] In some embodiments, the lanthanum salt includes lanthanum nitrate and / or lanthanum sulfate.

[0022] In some embodiments, the total concentration of zirconium and lanthanum in the doped salt solution is 0.1 mol / L to 0.15 mol / L.

[0023] In some embodiments, the molar concentration of the first complexing agent in the doped salt solution is 15% to 25% of the total concentration of zirconium and lanthanum.

[0024] In some embodiments, the first complexing agent comprises any one or a combination of at least two of citric acid, acetic acid, or acetylacetone.

[0025] In some embodiments, the pH value of the coprecipitation reaction is 10.5 to 11.5.

[0026] In some embodiments, the temperature of the coprecipitation reaction is 40°C to 80°C.

[0027] In some embodiments, during the coprecipitation reaction, the concentration of the second complexing agent in the system is 0.1 mol / L to 0.5 mol / L.

[0028] In some embodiments, the second complexing agent comprises any one or a combination of at least two of ammonia, citric acid, or sodium citrate.

[0029] In some embodiments, the stirring speed of the stirring conditions is 200 r / min to 400 r / min.

[0030] In some embodiments, the lithium source includes lithium hydroxide and / or lithium carbonate.

[0031] In some embodiments, the sintering includes a pre-firing and a main firing performed sequentially;

[0032] The pre-firing temperature is 280℃~320℃, and the time is 2.5h~3.5h;

[0033] The main firing temperature is 850℃~1000℃, and the time is 10h~16h.

[0034] Thirdly, the present invention provides a battery comprising the zirconium-lanthanum bulk co-doped high-nickel ternary material described in the first aspect, or the zirconium-lanthanum bulk co-doped high-nickel ternary material prepared by the preparation method described in the second aspect.

[0035] The numerical range described in this invention includes not only the point values ​​listed above, but also any point values ​​within the numerical ranges not listed above. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific point values ​​included in the range.

[0036] Compared with the prior art, the present invention has the following beneficial effects:

[0037] This invention achieves bulk co-doping of Zr and La elements in a ternary precursor, resulting in the in-situ generation of a uniformly dispersed lithium lanthanum zirconate phase within the material particles after sintering. This lithium lanthanum zirconate phase possesses excellent structural rigidity, serving as rigid support sites within the particles, significantly enhancing the mechanical strength of the ternary material particles. It effectively suppresses particle cracking and pulverization caused by lattice expansion and contraction during charge-discharge cycles, maintaining electrode structural integrity and greatly improving the long-cycle stability of the material. Furthermore, the co-doping of Zr and La achieves synergistic lattice stabilization. La stabilizes transition metal lattice sites and suppresses irreversible phase transitions and lattice oxygen precipitation, while Zr optimizes the local lattice environment and reduces lithium-nickel mixing. The synergistic effect of these two elements, combined with the interface protection provided by the in-situ generated lithium lanthanum zirconate phase, simultaneously achieves dual stability of the material's bulk structure and particle interface, further enhancing the material's cycle stability. This invention achieves uniform bulk doping of Zr and La elements through a precursor co-precipitation process, ensuring uniform dispersion of the dopant elements within the material and guaranteeing the consistency and stability of the material's performance. Detailed Implementation

[0038] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0039] The "range" disclosed in this invention can be defined in the form of a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of the specific range. This type of range definition can include or exclude endpoints; any endpoint can be independently included or excluded, and they can be arbitrarily combined, meaning any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60~120 and 80~110 are listed for specific parameters, it is understood that ranges of 60~110 and 80~120 are also expected. Furthermore, if minimum range values ​​1 and 2 are listed, and maximum range values ​​3, 4, and 5 are also listed, then the following ranges are all expected: 1~3, 1~4, 1~5, 2~3, 2~4, and 2~5. In this invention, unless otherwise stated, the numerical range "a~b" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0~5" indicates that all real numbers between "0" and "5" have been listed in this article; "0~5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is described as an integer ≥2, it is equivalent to listing integers such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc. For instance, when a parameter is described as an integer selected from "2~10", it is equivalent to listing the integers 2, 3, 4, 5, 6, 7, 8, 9, and 10.

[0040] In this invention, "a combination of at least two" refers to a quantity greater than or equal to two, unless otherwise specified. For example, "any combination of one or at least two" means one or more or more items. It can be understood that when referring to "a combination of at least two," it refers to any suitable combination of multiple items, that is, a combination of "at least two" items carried out in a manner that does not conflict with and enables the implementation of this invention.

[0041] Unless otherwise specified, all embodiments and optional embodiments of the present invention can be combined with each other to form new technical solutions.

[0042] The term "embodiment" as used in this invention means that a specific feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment or implementation of the invention. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a mutually exclusive, independent, or alternative embodiment. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described in this invention can be combined with other embodiments.

[0043] Those skilled in the art will understand that the order in which the steps are written in the methods of the various embodiments does not imply a strict execution order. The detailed execution order of each step should be determined by its function and possible internal logic. Unless otherwise specified, all steps of the present invention may be performed sequentially or randomly, but are preferably performed sequentially. For example, if the method includes steps (a) and (b), it means that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the method may also include step (c), meaning that step (c) can be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0044] In this invention, open-ended technical features or solutions described using terms such as "comprising" do not exclude additional members beyond those listed unless otherwise specified. They can be considered as providing both closed-ended features or solutions comprised of the listed members and open-ended features or solutions that include additional members beyond the listed members. For example, A includes a1, a2, and a3. Unless otherwise specified, it may also include other members or exclude additional members. This can be considered as providing both technical features or solutions where "A is composed of a1, a2, and a3" or "A is selected from a1, a2, and a3," and technical features or solutions where "A includes not only a1, a2, and a3, but also other members."

[0045] In this invention, unless otherwise specified, the features or solutions corresponding to "and / or" include any one of two or more of the related listed items, as well as any and all combinations of the related listed items. These arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. For example, "A and / or B" represents a group consisting of A, B, and "a combination of A and B". "Containing A and / or B" can mean "containing A, containing B, and containing A and B", or "containing A, containing B, or containing A and B", and can be appropriately understood according to the context.

[0046] In this invention, the terms "first aspect," "second aspect," "third aspect," "fourth aspect," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first," "second," "third," "fourth," etc., serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on the quantity.

[0047] In this invention, "optional" means that something is optional, that is, it refers to either "with" or "without". If there are multiple "optional" options in a technical solution, unless otherwise specified, and there are no contradictions or mutual constraints, then each "optional" option is independent.

[0048] An embodiment of the present invention provides a zirconium-lanthanum bulk phase co-doped high-nickel ternary material, wherein the zirconium-lanthanum bulk phase co-doped high-nickel ternary material is a ternary cathode material co-doped with zirconium and lanthanum in bulk phase;

[0049] The chemical formula of the ternary cathode material is LiNi. x Co y Mn (1-x-y) O2, wherein 0.8≤x≤0.9, 0≤y≤0.1; the total molar amount of zirconium and lanthanum is 1% to 5% of the total molar amount of nickel, cobalt and manganese (for example, it can be 1%, 2%, 3%, 4% or 5%, etc.).

[0050] This invention achieves bulk co-doping of Zr and La elements in a ternary precursor, resulting in the in-situ generation of a uniformly dispersed lithium lanthanum zirconate phase within the material particles after sintering. This lithium lanthanum zirconate phase possesses excellent structural rigidity, serving as a rigid support site within the particles. This significantly enhances the mechanical strength of the ternary material particles, effectively suppressing particle cracking and pulverization caused by lattice expansion and contraction during charge-discharge cycles, maintaining electrode structural integrity, and greatly improving the long-cycle stability of the material. Simultaneously, the lithium lanthanum zirconate phase exhibits both excellent lithium-ion conductivity and electronic conductivity, enabling the construction of efficient ion and electron transport channels within the bulk phase of the material. This reduces the lithium-ion migration barrier and electrode polarization, improves lithium-ion transport kinetics and electrochemical reaction reversibility, and optimizes the rate performance and overall electrical performance of the material.

[0051] Furthermore, this invention achieves synergistic lattice stabilization through Zr and La co-doping. La stabilizes transition metal lattice sites and suppresses irreversible phase transitions and lattice oxygen precipitation, while Zr optimizes the local lattice environment and reduces lithium-nickel mixing. The synergistic effect of these two elements, combined with the interface protection provided by the in-situ generated lithium lanthanum zirconate phase, simultaneously achieves dual stability of the bulk structure and particle interfaces, further enhancing the material's cycle stability. This invention utilizes a precursor co-precipitation process to achieve uniform bulk doping of Zr and La, ensuring uniform dispersion of the dopant elements within the material and guaranteeing the consistency and stability of its properties.

[0052] In some embodiments, the molar ratio of zirconium to lanthanum is 1:1.2 to 1:1.6, for example, it can be 1:1.2, 1:1.3, 1:1.4, 1:1.5 or 1:1.6, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable. Preferably, it is 1:1.4 to 1:1.6, and more preferably 1:1.5.

[0053] An embodiment of the present invention provides a method for preparing a zirconium-lanthanum bulk co-doped high-nickel ternary material. The preparation method includes the following steps: mixing a ternary metal salt solution, a dopant salt solution, a precipitant solution, and a complexing agent solution in a bottom solution in parallel flow, and carrying out a co-precipitation reaction under stirring to obtain a bulk doped precursor with a median particle size D50 of 7µm~12µm (e.g., 7µm, 8µm, 9µm, 10µm, 11µm, or 12µm, etc.); mixing the bulk doped precursor with a lithium source and sintering to obtain the zirconium-lanthanum bulk co-doped high-nickel ternary material as described in any embodiment.

[0054] The solute in the doped salt solution includes zirconium salt, lanthanum salt and a first complexing agent;

[0055] The solute in the complexing agent solution includes a second complexing agent.

[0056] In some embodiments, the ternary metal salt solution includes nickel salt, cobalt salt, and manganese salt;

[0057] The nickel salt includes any one or a combination of at least two of nickel nitrate, nickel sulfate, or nickel chloride. Typical but non-limiting combinations include combinations of nickel nitrate and nickel sulfate, nickel sulfate and nickel chloride, nickel nitrate and nickel chloride, or combinations of nickel nitrate, nickel sulfate, and nickel chloride.

[0058] The cobalt salt includes any one or a combination of at least two of cobalt nitrate, cobalt sulfate, or cobalt chloride. Typical but non-limiting combinations include combinations of cobalt nitrate and cobalt sulfate, cobalt nitrate and cobalt chloride, cobalt sulfate and cobalt chloride, or cobalt nitrate, cobalt sulfate, and cobalt chloride.

[0059] The manganese salt includes any one or a combination of at least two of manganese nitrate, manganese sulfate, or manganese chloride. Typical but non-limiting combinations include combinations of manganese nitrate and manganese sulfate, manganese nitrate and manganese chloride, manganese sulfate and manganese chloride, or combinations of manganese nitrate, manganese sulfate, and manganese chloride.

[0060] In some embodiments, the total concentration of nickel, cobalt and manganese in the ternary metal salt solution is 2 mol / L to 4 mol / L, for example, it can be 2 mol / L, 2.5 mol / L, 3 mol / L, 3.5 mol / L or 4 mol / L, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0061] In some embodiments, the zirconium salt comprises any one or a combination of at least two of zirconium oxychloride, zirconium sulfate, zirconium nitrate, or zirconium oxynitrate. Typical but non-limiting combinations include combinations of zirconium oxychloride and zirconium sulfate, zirconium sulfate and zirconium nitrate, zirconium sulfate and zirconium oxynitrate, zirconium oxychloride and zirconium oxynitrate, or combinations of zirconium oxychloride, zirconium sulfate, zirconium nitrate, and zirconium oxynitrate.

[0062] In some embodiments, the lanthanum salt includes lanthanum nitrate and / or lanthanum sulfate.

[0063] In some embodiments, the total concentration of zirconium and lanthanum in the doped salt solution is 0.1 mol / L to 0.15 mol / L, for example, it can be 0.1 mol / L, 0.11 mol / L, 0.12 mol / L, 0.13 mol / L, 0.14 mol / L or 0.15 mol / L, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0064] In some embodiments, the molar concentration of the first complexing agent in the doped salt solution is 15% to 25% of the total concentration of zirconium and lanthanum, for example, it can be 15%, 18%, 20%, 21%, 24% or 25%, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0065] In some embodiments, the first complexing agent comprises any one or a combination of at least two of citric acid, acetic acid, or acetylacetone. Typical but non-limiting combinations include combinations of citric acid and acetic acid, acetic acid and acetylacetone, citric acid and acetylacetone, or citric acid, acetic acid, and acetylacetone.

[0066] In some embodiments, the pH value of the coprecipitation reaction is 10.5 to 11.5, for example, it can be 10.5, 10.8, 11, 11.2 or 11.5, but is not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0067] In some embodiments, the temperature of the coprecipitation reaction is 40°C to 80°C, for example, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C or 80°C, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0068] In some embodiments, during the coprecipitation reaction, the concentration of the second complexing agent in the system is 0.1 mol / L to 0.5 mol / L, for example, it can be 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L or 0.5 mol / L, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0069] In some embodiments, the second complexing agent comprises any one or a combination of at least two of ammonia, citric acid, or sodium citrate.

[0070] In some embodiments, the stirring speed of the stirring conditions is 200 r / min to 400 r / min, for example, it can be 200 r / min, 250 r / min, 300 r / min, 350 r / min or 400 r / min, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0071] In some embodiments, the lithium source includes lithium hydroxide and / or lithium carbonate. To compensate for loss on ignition, the molar ratio of the bulk doped precursor to lithium in the lithium source can be 1:1.05 to 1:1.08, for example, 1:1.05, 1:1.06, 1:1.07 or 1:1.08, but is not limited to the listed values; other unlisted values ​​within the range are also applicable.

[0072] In some embodiments, the sintering includes a pre-firing and a main firing performed sequentially;

[0073] The pre-firing temperature is 280℃~320℃, and the time is 2.5h~3.5h;

[0074] The main firing temperature is 850℃~1000℃, and the time is 10h~16h.

[0075] The preheating temperature is 280℃~320℃, for example, it can be 280℃, 290℃, 300℃, 310℃ or 320℃, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0076] The preheating time is 2.5h to 3.5h, for example, it can be 2.5h, 2.7h, 2.8h, 3h, 3.2h or 3.5h, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0077] The main firing temperature is 850℃~1000℃, for example, it can be 850℃, 880℃, 900℃, 950℃, 980℃ or 1000℃, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0078] The main cooking time is 10h to 16h, for example, it can be 10h, 11h, 12h, 13h, 14h, 15h or 16h, but it is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0079] In some embodiments, the precipitant solution may be a sodium hydroxide solution with a concentration of 1.5 mol / L to 2.5 mol / L.

[0080] In some embodiments, the temperature of the base solution is 40°C to 80°C, the pH value is 11 to 12, and the concentration of the second complexing agent is 0.2 mol / L to 0.5 mol / L.

[0081] As a preferred embodiment of the preparation method provided by the present invention, the preparation method includes:

[0082] S1. Mix water, precipitant solution and complexing agent solution to obtain a base solution; the temperature of the base solution is 40℃~80℃, the pH value is 11~12, and the concentration of the second complexing agent is 0.2mol / L~0.5mol / L;

[0083] The precipitant solution is a sodium hydroxide solution with a concentration of 1.5 mol / L to 2.5 mol / L;

[0084] The solute in the complexing agent solution is a second complexing agent, which includes any one or a combination of at least two of ammonia, citric acid, or sodium citrate.

[0085] S2. A ternary metal salt solution, a doped salt solution, a precipitant solution, and a complexing agent solution are mixed in parallel in the bottom liquid. A co-precipitation reaction is carried out under stirring to obtain a bulk doped precursor with a median particle size D50 of 7µm~12µm.

[0086] The ternary metal salt solution includes nickel salt, cobalt salt and manganese salt, and the total concentration of nickel, cobalt and manganese is 2 mol / L to 4 mol / L;

[0087] The solute in the doped salt solution includes zirconium salt, lanthanum salt, and a first complexing agent, and the total concentration of zirconium and lanthanum is 0.1 mol / L to 0.15 mol / L, and the molar concentration of the first complexing agent is 15% to 25% of the total concentration of zirconium and lanthanum.

[0088] The first complexing agent includes any one or a combination of at least two of citric acid, acetic acid, or acetylacetone;

[0089] The precipitant solution is a sodium hydroxide solution with a concentration of 1.5 mol / L to 2.5 mol / L;

[0090] The solute in the complexing agent solution is a second complexing agent, which includes any one or a combination of at least two of ammonia, citric acid, or sodium citrate.

[0091] The stirring speed under the specified stirring conditions is 200 r / min to 400 r / min;

[0092] The coprecipitation reaction is carried out at a pH of 10.5-11.5 and a temperature of 40℃-80℃, with the concentration of the second complexing agent in the system being 0.1mol / L-0.5mol / L.

[0093] S3. Mix the bulk doped precursor with a lithium source and sinter to obtain a zirconium-lanthanum bulk co-doped high-nickel ternary material.

[0094] The sintering process includes pre-firing and main firing performed sequentially; the pre-firing temperature is 280℃~320℃ and the time is 2.5h~3.5h; the main firing temperature is 850℃~1000℃ and the time is 10h~16h.

[0095] The zirconium-lanthanum bulk co-doped high-nickel ternary material is a ternary cathode material co-doped with zirconium and lanthanum; the chemical formula of the ternary cathode material is LiNi. x Co y Mn (1-x-y) O2, wherein 0.8≤x≤0.9, 0≤y≤0.1; the total molar amount of zirconium and lanthanum is 1%~5% of the total molar amount of nickel, cobalt and manganese; the molar ratio of zirconium to lanthanum is 1:1.2~1:1.6.

[0096] An embodiment of the present invention provides a battery comprising a zirconium-lanthanum bulk co-doped high-nickel ternary material as described in any embodiment, or a zirconium-lanthanum bulk co-doped high-nickel ternary material prepared by any of the preparation methods described in any embodiment.

[0097] Example 1

[0098] This embodiment provides a method for preparing a zirconium-lanthanum bulk co-doped high-nickel ternary material, including the following steps:

[0099] S1. Mix water, precipitant solution and complexing agent solution to obtain a base solution; the temperature of the base solution is 60℃, the pH value is 11.5, and the concentration of the second complexing agent is 0.3mol / L;

[0100] The precipitant solution is a 2 mol / L sodium hydroxide solution;

[0101] The solute in the complexing agent solution is a second complexing agent, which is ammonia.

[0102] S2. A ternary metal salt solution, a doped salt solution, a precipitant solution, and a complexing agent solution are mixed in parallel in the bottom liquid. A co-precipitation reaction is carried out under stirring to obtain a bulk doped precursor with a median particle size D50 of 10µm.

[0103] The ternary metal salt solution includes nickel sulfate, cobalt sulfate and manganese sulfate, and the total concentration of nickel, cobalt and manganese is 2 mol / L;

[0104] The solute in the doped salt solution includes zirconium sulfate, lanthanum sulfate, and a first complexing agent, and the total concentration of zirconium and lanthanum is 0.125 mol / L, and the molar concentration of the first complexing agent is 20% of the total concentration of zirconium and lanthanum.

[0105] The first complexing agent is citric acid;

[0106] The precipitant solution is a 2 mol / L sodium hydroxide solution;

[0107] The solute in the complexing agent solution is a second complexing agent, which is ammonia.

[0108] The stirring speed under the specified stirring conditions is 300 r / min;

[0109] The coprecipitation reaction was carried out at a pH of 11 and a temperature of 60°C, with the concentration of the second complexing agent in the system being 0.3 mol / L.

[0110] S3. The bulk doped precursor is mixed with a lithium source (LiOH, the molar ratio of lithium in the bulk doped precursor to lithium source can be 1:1.06), and sintered to obtain a zirconium-lanthanum bulk co-doped high-nickel ternary material.

[0111] The sintering process includes a pre-firing and a main firing performed sequentially; the pre-firing temperature is 300℃ and the time is 3 hours; the main firing temperature is 900℃ and the time is 12 hours.

[0112] The zirconium-lanthanum bulk co-doped high-nickel ternary material is a ternary cathode material co-doped with zirconium and lanthanum; the chemical formula of the ternary cathode material is LiNi. 0.9 Co 0.05 Mn 0.05 O2; the total molar amount of zirconium and lanthanum is 2.5% of the total molar amount of nickel, cobalt and manganese; the molar ratio of zirconium to lanthanum is 1:1.5.

[0113] Example 2

[0114] This embodiment provides a method for preparing a zirconium-lanthanum bulk co-doped high-nickel ternary material, including the following steps:

[0115] S1. Mix water, precipitant solution and complexing agent solution to obtain a base solution; the temperature of the base solution is 40℃, the pH value is 11, and the concentration of the second complexing agent is 0.2mol / L;

[0116] The precipitant solution is a 2 mol / L sodium hydroxide solution;

[0117] The solute in the complexing agent solution is a second complexing agent, which is ammonia.

[0118] S2. A ternary metal salt solution, a doped salt solution, a precipitant solution, and a complexing agent solution are mixed in parallel in the bottom liquid. A co-precipitation reaction is carried out under stirring to obtain a bulk doped precursor with a median particle size D50 of 7µm.

[0119] The ternary metal salt solution includes nickel sulfate, cobalt sulfate and manganese sulfate, and the total concentration of nickel, cobalt and manganese is 3 mol / L;

[0120] The solute in the doped salt solution includes zirconium sulfate, lanthanum sulfate, and a first complexing agent, and the total concentration of zirconium and lanthanum is 0.1 mol / L, and the molar concentration of the first complexing agent is 15% of the total concentration of zirconium and lanthanum.

[0121] The first complexing agent is citric acid;

[0122] The precipitant solution is a 2 mol / L sodium hydroxide solution;

[0123] The solute in the complexing agent solution is a second complexing agent, which is ammonia.

[0124] The stirring speed under the specified stirring conditions is 200 r / min;

[0125] The coprecipitation reaction was carried out at a pH of 10.5 and a temperature of 40°C, with the concentration of the second complexing agent in the system being 0.2 mol / L.

[0126] S3. The bulk doped precursor is mixed with a lithium source (LiOH, the molar ratio of lithium in the bulk doped precursor to lithium source can be 1:1.06), and sintered to obtain a zirconium-lanthanum bulk co-doped high-nickel ternary material.

[0127] The sintering process includes a pre-firing and a main firing performed sequentially; the pre-firing temperature is 280°C and the time is 3.5 hours; the main firing temperature is 850°C and the time is 16 hours.

[0128] The zirconium-lanthanum bulk co-doped high-nickel ternary material is a ternary cathode material co-doped with zirconium and lanthanum; the chemical formula of the ternary cathode material is LiNi. 0.9 Co 0.05 Mn 0.05O2; the total molar amount of zirconium and lanthanum is 1% of the total molar amount of nickel, cobalt and manganese; the molar ratio of zirconium to lanthanum is 1:1.5.

[0129] Example 3

[0130] This embodiment provides a method for preparing a zirconium-lanthanum bulk co-doped high-nickel ternary material, including the following steps:

[0131] S1. Mix water, precipitant solution and complexing agent solution to obtain a base solution; the temperature of the base solution is 80℃, the pH value is 12, and the concentration of the second complexing agent is 0.5mol / L;

[0132] The precipitant solution is a 2 mol / L sodium hydroxide solution;

[0133] The solute in the complexing agent solution is a second complexing agent, which is ammonia.

[0134] S2. A ternary metal salt solution, a doped salt solution, a precipitant solution, and a complexing agent solution are mixed in parallel in the bottom liquid. A co-precipitation reaction is carried out under stirring to obtain a bulk doped precursor with a median particle size D50 of 12µm.

[0135] The ternary metal salt solution includes nickel sulfate, cobalt sulfate and manganese sulfate, and the total concentration of nickel, cobalt and manganese is 4 mol / L;

[0136] The solute in the doped salt solution includes zirconium sulfate, lanthanum sulfate, and a first complexing agent, and the total concentration of zirconium and lanthanum is 0.15 mol / L, and the molar concentration of the first complexing agent is 25% of the total concentration of zirconium and lanthanum.

[0137] The first complexing agent is citric acid;

[0138] The precipitant solution is a 2 mol / L sodium hydroxide solution;

[0139] The solute in the complexing agent solution is a second complexing agent, which is ammonia.

[0140] The stirring speed under the specified stirring conditions is 400 r / min;

[0141] The coprecipitation reaction was carried out at a pH of 11.5 and a temperature of 80°C, with the concentration of the second complexing agent in the system being 0.5 mol / L.

[0142] S3. The bulk doped precursor is mixed with a lithium source (LiOH, the molar ratio of lithium in the bulk doped precursor to lithium source can be 1:1.06), and sintered to obtain a zirconium-lanthanum bulk co-doped high-nickel ternary material.

[0143] The sintering process includes a pre-firing and a main firing performed sequentially; the pre-firing temperature is 320℃ and the time is 2.5h; the main firing temperature is 1000℃ and the time is 10h.

[0144] The zirconium-lanthanum bulk co-doped high-nickel ternary material is a ternary cathode material co-doped with zirconium and lanthanum; the chemical formula of the ternary cathode material is LiNi. 0.9 Co 0.05 Mn 0.05 O2; the total molar amount of zirconium and lanthanum is 5% of the total molar amount of nickel, cobalt and manganese; the molar ratio of zirconium to lanthanum is 1:1.5.

[0145] Example 4

[0146] This embodiment provides a method for preparing a zirconium-lanthanum bulk co-doped high-nickel ternary material. Except for adjusting the flow rate of the doping salt solution to make the doping amount of zirconium and lanthanum too small, the rest is the same as in Example 1.

[0147] In this embodiment, the zirconium-lanthanum bulk co-doped high-nickel ternary material is a ternary cathode material co-doped with zirconium and lanthanum; the chemical formula of the ternary cathode material is LiNi. 0.9 Co 0.05 Mn 0.05 O2; the total molar amount of zirconium and lanthanum is 0.5% of the total molar amount of nickel, cobalt and manganese; the molar ratio of zirconium to lanthanum is 1:1.5.

[0148] Example 5

[0149] This embodiment provides a method for preparing a zirconium-lanthanum bulk co-doped high-nickel ternary material. Except for adjusting the flow rate of the doping salt solution to make the doping amount of zirconium and lanthanum too high, the rest is the same as in Example 1.

[0150] In this embodiment, the zirconium-lanthanum bulk co-doped high-nickel ternary material is a ternary cathode material co-doped with zirconium and lanthanum; the chemical formula of the ternary cathode material is LiNi. 0.9 Co 0.05 Mn 0.05 O2; the total molar amount of zirconium and lanthanum is 8% of the total molar amount of nickel, cobalt and manganese; the molar ratio of zirconium to lanthanum is 1:1.5.

[0151] Comparative Example 1

[0152] This comparative example provides a method for preparing a high-nickel ternary material. Except for replacing zirconium sulfate with lanthanum sulfate in equal molar amounts, the method is identical to that in Example 1, including the following steps:

[0153] S1. Mix water, precipitant solution and complexing agent solution to obtain a base solution; the temperature of the base solution is 60℃, the pH value is 11.5, and the concentration of the second complexing agent is 0.3mol / L;

[0154] The precipitant solution is a 2 mol / L sodium hydroxide solution;

[0155] The solute in the complexing agent solution is a second complexing agent, which is ammonia.

[0156] S2. A ternary metal salt solution, a doped salt solution, a precipitant solution, and a complexing agent solution are mixed in parallel in the bottom liquid. A co-precipitation reaction is carried out under stirring to obtain a bulk doped precursor with a median particle size D50 of 10µm.

[0157] The ternary metal salt solution includes nickel sulfate, cobalt sulfate and manganese sulfate, and the total concentration of nickel, cobalt and manganese is 2 mol / L;

[0158] The solute in the doped salt solution includes lanthanum sulfate and a first complexing agent, wherein the concentration of lanthanum is 0.125 mol / L and the molar concentration of the first complexing agent is 20% of the concentration of lanthanum.

[0159] The first complexing agent is citric acid;

[0160] The precipitant solution is a 2 mol / L sodium hydroxide solution;

[0161] The solute in the complexing agent solution is a second complexing agent, which is ammonia.

[0162] The stirring speed under the specified stirring conditions is 300 r / min;

[0163] The coprecipitation reaction was carried out at a pH of 11 and a temperature of 60°C, with the concentration of the second complexing agent in the system being 0.3 mol / L.

[0164] S3. The bulk doped precursor is mixed with a lithium source (LiOH, the molar ratio of lithium in the bulk doped precursor to lithium source can be 1:1.06), and sintered to obtain a high-nickel ternary material.

[0165] The sintering process includes a pre-firing and a main firing performed sequentially; the pre-firing temperature is 300℃ and the time is 3 hours; the main firing temperature is 900℃ and the time is 12 hours.

[0166] The high-nickel ternary material is a bulk lanthanum-co-doped ternary cathode material; the chemical formula of the ternary cathode material is LiNi. 0.9 Co 0.05 Mn 0.05 O2; the molar amount of lanthanum is 2.5% of the total molar amount of nickel, cobalt and manganese.

[0167] Comparative Example 2

[0168] This comparative example provides a method for preparing a high-nickel ternary material. Except for replacing an equimolar amount of lanthanum sulfate with zirconium sulfate, the method is identical to that in Example 1, including the following steps:

[0169] S1. Mix water, precipitant solution and complexing agent solution to obtain a base solution; the temperature of the base solution is 60℃, the pH value is 11.5, and the concentration of the second complexing agent is 0.3mol / L;

[0170] The precipitant solution is a 2 mol / L sodium hydroxide solution;

[0171] The solute in the complexing agent solution is a second complexing agent, which is ammonia.

[0172] S2. A ternary metal salt solution, a doped salt solution, a precipitant solution, and a complexing agent solution are mixed in parallel in the bottom liquid. A co-precipitation reaction is carried out under stirring to obtain a bulk doped precursor with a median particle size D50 of 10µm.

[0173] The ternary metal salt solution includes nickel sulfate, cobalt sulfate and manganese sulfate, and the total concentration of nickel, cobalt and manganese is 2 mol / L;

[0174] The solute in the doped salt solution includes zirconium sulfate and a first complexing agent, and the concentration of zirconium is 0.125 mol / L, and the molar concentration of the first complexing agent is 20% of the zirconium concentration;

[0175] The first complexing agent is citric acid;

[0176] The precipitant solution is a 2 mol / L sodium hydroxide solution;

[0177] The solute in the complexing agent solution is a second complexing agent, which is ammonia.

[0178] The stirring speed under the specified stirring conditions is 300 r / min;

[0179] The coprecipitation reaction was carried out at a pH of 11 and a temperature of 60°C, with the concentration of the second complexing agent in the system being 0.3 mol / L.

[0180] S3. The bulk doped precursor is mixed with a lithium source (LiOH, the molar ratio of lithium in the bulk doped precursor to lithium source can be 1:1.06), and sintered to obtain a high-nickel ternary material.

[0181] The sintering process includes a pre-firing and a main firing performed sequentially; the pre-firing temperature is 300℃ and the time is 3 hours; the main firing temperature is 900℃ and the time is 12 hours.

[0182] The high-nickel ternary material is a bulk-phase co-doped zirconium ternary cathode material; the chemical formula of the ternary cathode material is LiNi. 0.9 Co 0.05 Mn 0.05 O2; the molar amount of zirconium is 2.5% of the total molar amount of nickel, cobalt and manganese.

[0183] Comparative Example 3

[0184] This comparative example provides a method for preparing a high-nickel ternary material. Except for replacing lanthanum sulfate in equimolar amounts with cerium sulfate, the method is the same as in Example 1, including the following steps:

[0185] S1. Mix water, precipitant solution and complexing agent solution to obtain a base solution; the temperature of the base solution is 60℃, the pH value is 11.5, and the concentration of the second complexing agent is 0.3mol / L;

[0186] The precipitant solution is a 2 mol / L sodium hydroxide solution;

[0187] The solute in the complexing agent solution is a second complexing agent, which is ammonia.

[0188] S2. A ternary metal salt solution, a doped salt solution, a precipitant solution, and a complexing agent solution are mixed in parallel in the bottom liquid. A co-precipitation reaction is carried out under stirring to obtain a bulk doped precursor with a median particle size D50 of 10µm.

[0189] The ternary metal salt solution includes nickel sulfate, cobalt sulfate and manganese sulfate, and the total concentration of nickel, cobalt and manganese is 2 mol / L;

[0190] The solute in the doped salt solution includes zirconium sulfate, cerium sulfate, and a first complexing agent, and the total concentration of zirconium and cerium is 0.125 mol / L, and the molar concentration of the first complexing agent is 20% of the total concentration of zirconium and cerium.

[0191] The first complexing agent is citric acid;

[0192] The precipitant solution is a 2 mol / L sodium hydroxide solution;

[0193] The solute in the complexing agent solution is a second complexing agent, which is ammonia.

[0194] The stirring speed under the specified stirring conditions is 300 r / min;

[0195] The coprecipitation reaction was carried out at a pH of 11 and a temperature of 60°C, with the concentration of the second complexing agent in the system being 0.3 mol / L.

[0196] S3. The bulk doped precursor is mixed with a lithium source (LiOH, the molar ratio of lithium in the bulk doped precursor to lithium source can be 1:1.06) and sintered to obtain a zirconium-cerium bulk co-doped high-nickel ternary material.

[0197] The sintering process includes a pre-firing and a main firing performed sequentially; the pre-firing temperature is 300℃ and the time is 3 hours; the main firing temperature is 900℃ and the time is 12 hours.

[0198] The zirconium-cerium bulk co-doped high-nickel ternary material is a ternary cathode material with bulk co-doped zirconium and cerium; the chemical formula of the ternary cathode material is LiNi. 0.9 Co 0.05 Mn 0.05 O2; the total molar amount of zirconium and cerium is 2.5% of the total molar amount of nickel, cobalt and manganese; the molar ratio of zirconium to cerium is 1:1.5.

[0199] Performance Characterization

[0200] The positive electrode material, polyvinylidene fluoride, and acetylene black were mixed in a mass ratio of 80:10:10, and NMP (N-methylpyrrolidone) was added. The mixture was stirred to form a slurry, which was then coated onto aluminum foil and dried to form the positive electrode. A lithium sheet was used as the negative electrode to assemble a CR2025 coin cell. The electrochemical performance of the battery was tested at 2.8V~4.3V, and the results are shown in Table 1. The first-cycle discharge specific capacity was tested at a charge-discharge rate of 0.1C, and the cycle capacity retention was tested at a charge-discharge rate of 1C for 50 cycles.

[0201] Table 1

[0202]

[0203] As can be seen from Examples 1 to 3 in the table, when the co-doping amount of Zr and La is within the preferred range defined by the present invention, the prepared ternary cathode material exhibits excellent electrochemical performance, with a first-cycle discharge specific capacity exceeding 211 mAh / g and a cycle capacity retention rate exceeding 97.5%.

[0204] A comparison of Examples 4 and 5 with Example 1 shows that when the co-doping amounts of zirconium and lanthanum are relatively low (Example 4), a sufficient amount of rigid lithium lanthanum zirconate support phase cannot be generated inside the particles, making it difficult to adequately buffer the lattice expansion and contraction stress during charge and discharge. Simultaneously, the low dose of doping elements cannot fully leverage the synergistic lattice stabilizing effect of the two elements, making it difficult to effectively suppress lithium-nickel mixing and local irreversible phase transitions. Therefore, the cycle capacity retention rate of the material only decreases slightly, while the first-cycle discharge specific capacity shows a more significant decrease.

[0205] When the co-doping amount of zirconium and lanthanum is too high (Example 5), the excessive doping elements will introduce too much non-electrochemically active lithium lanthanum zirconate phase, which will directly reduce the proportion of active ternary materials in the material, resulting in a significant decrease in the discharge specific capacity of the material in the first cycle; at the same time, excessive doping is prone to cause local agglomeration of elements, which will have a slight impact on the complete layered lattice structure of the ternary material.

[0206] A comparison of Comparative Example 1 and Example 1 shows that the electrochemical performance of the material is significantly reduced when only lanthanum is doped. This is because although lanthanum doping can stabilize the transition metal lattice sites to some extent through its large ionic radius and suppress lattice oxygen evolution and phase transition, it lacks the synergistic effect of Zr and cannot effectively reduce lithium-nickel mixing or optimize the lithium-ion transport environment within the lattice. At the same time, it cannot generate a lanthanum zirconate phase with high structural rigidity in sintering, and the particles lack effective rigid support, which cannot suppress particle cracking and pulverization caused by lattice expansion and contraction during charge-discharge cycles. Therefore, the discharge specific capacity and cycle capacity retention of the material both decrease.

[0207] A comparison of Comparative Example 2 and Example 1 shows that the electrochemical performance of the material also deteriorates when only zirconium is doped. This is because although Zr doping can reduce lithium-nickel mixing and stabilize the local lattice structure to some extent through its strong bonding ability, it lacks the stabilizing effect of La on the overall lattice and oxygen framework, and cannot suppress irreversible phase transitions and lattice oxygen loss during cycling. At the same time, it is also impossible to generate a rigid support phase of lithium lanthanum zirconate in situ, which cannot alleviate the structural damage caused by lattice expansion and contraction. Therefore, the discharge specific capacity and cycle capacity retention of the material both show a significant decrease.

[0208] As can be seen from the comparison between Comparative Example 3 and Example 1, replacing lanthanum with cerium fails to achieve the optimal technical effect of this invention, and the electrochemical performance is significantly reduced. This is because Ce cannot form a lithium lanthanum zirconate phase with Zr and Li in situ during sintering, which has excellent structural rigidity. This makes it impossible to provide effective rigid support for the particles and fundamentally suppress particle cracking and pulverization during cycling. At the same time, Ce and Zr cannot achieve the synergistic lattice stabilization effect of La and Zr in this invention. They cannot fully stabilize the transition metal lattice sites, suppress lattice oxygen evolution during cycling, or simultaneously suppress lithium-nickel mixing. Thus, they cannot achieve dual stability of the bulk structure and particle interface of the material.

[0209] In summary, this invention, through bulk co-doping of Zr and La elements in a ternary precursor, generates a uniformly dispersed lithium lanthanum zirconate phase in situ within the material particles after sintering. This lithium lanthanum zirconate phase possesses excellent structural rigidity, serving as rigid support sites within the particles, significantly enhancing the mechanical strength of the ternary material particles, effectively suppressing particle cracking and pulverization caused by lattice expansion and contraction during charge-discharge cycles, maintaining electrode structural integrity, and greatly improving the long-cycle stability of the material. Furthermore, the co-doping of Zr and La achieves synergistic lattice stabilization. La stabilizes transition metal lattice sites and suppresses irreversible phase transitions and lattice oxygen precipitation, while Zr optimizes the local lattice environment and reduces lithium-nickel mixing. The synergistic effect of the in-situ generated lithium lanthanum zirconate phase and its interfacial protection simultaneously achieves dual stability of the material's bulk structure and particle interface, further enhancing the material's cycle stability. This invention achieves uniform bulk doping of Zr and La elements through a precursor co-precipitation process, ensuring uniform dispersion of the dopant elements within the material and guaranteeing the consistency and stability of the material's performance.

[0210] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A zirconium-lanthanum bulk co-doped high-nickel ternary material, characterized in that, The zirconium-lanthanum bulk co-doped high-nickel ternary material is a ternary cathode material co-doped with zirconium and lanthanum. The chemical formula of the ternary cathode material is LiNi. x Co y Mn (1-x-y) O2, where 0.8≤x≤0.9, 0≤y≤0.1; The total molar amount of zirconium and lanthanum is 1% to 5% of the total molar amount of nickel, cobalt and manganese.

2. The zirconium-lanthanum bulk co-doped high-nickel ternary material according to claim 1, characterized in that, The molar ratio of zirconium to lanthanum is 1:1.2 to 1:1.

6.

3. A method for preparing a zirconium-lanthanum bulk co-doped high-nickel ternary material, characterized in that, The preparation method includes the following steps: a ternary metal salt solution, a doped salt solution, a precipitant solution, and a complexing agent solution are mixed in parallel in a base liquid, and a co-precipitation reaction is carried out under stirring to obtain a bulk doped precursor with a median particle size D50 of 7µm~12µm; the bulk doped precursor is mixed with a lithium source and sintered to obtain the zirconium-lanthanum bulk co-doped high-nickel ternary material as described in claim 1 or 2. The solute in the doped salt solution includes zirconium salt, lanthanum salt and a first complexing agent; The solute in the complexing agent solution includes a second complexing agent.

4. The preparation method according to claim 3, characterized in that, The ternary metal salt solution includes nickel salt, cobalt salt and manganese salt; The nickel salt includes any one or a combination of at least two of nickel nitrate, nickel sulfate, or nickel chloride; The cobalt salt includes any one or a combination of at least two of cobalt nitrate, cobalt sulfate, or cobalt chloride. The manganese salt includes any one or a combination of at least two of manganese nitrate, manganese sulfate, or manganese chloride.

5. The preparation method according to claim 4, characterized in that, The total concentration of nickel, cobalt and manganese in the ternary metal salt solution is 2 mol / L to 4 mol / L.

6. The preparation method according to any one of claims 3 to 5, characterized in that, The zirconium salt includes any one or a combination of at least two of zirconium oxychloride, zirconium sulfate, zirconium nitrate, or zirconium oxynitrate. And / or, the lanthanum salt includes lanthanum nitrate and / or lanthanum sulfate; And / or, in the doped salt solution, the total concentration of zirconium and lanthanum is 0.1 mol / L to 0.15 mol / L.

7. The preparation method according to claim 6, characterized in that, In the doped salt solution, the molar concentration of the first complexing agent is 15% to 25% of the total concentration of zirconium and lanthanum; And / or, the first complexing agent comprises any one or a combination of at least two of citric acid, acetic acid, or acetylacetone.

8. The preparation method according to claim 3, characterized in that, The pH value of the coprecipitation reaction is 10.5~11.5; And / or, the temperature of the coprecipitation reaction is 40℃~80℃; And / or, during the coprecipitation reaction, the concentration of the second complexing agent in the system is 0.1 mol / L to 0.5 mol / L; And / or, the second complexing agent comprises any one or a combination of at least two of ammonia, citric acid, or sodium citrate; And / or, the stirring speed of the stirring conditions is 200 r / min to 400 r / min.

9. The preparation method according to claim 3, characterized in that, The lithium source includes lithium hydroxide and / or lithium carbonate; And / or, the sintering includes a pre-firing and a main firing performed sequentially; The pre-firing temperature is 280℃~320℃, and the time is 2.5h~3.5h; The main firing temperature is 850℃~1000℃, and the time is 10h~16h.

10. A battery, characterized in that, The battery comprises the zirconium-lanthanum bulk co-doped high-nickel ternary material as described in claim 1 or 2, or the zirconium-lanthanum bulk co-doped high-nickel ternary material prepared by the preparation method described in any one of claims 3 to 9.

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