CN114590847A

CN114590847A - Ternary positive electrode precursor material, preparation method thereof and ternary positive electrode material

Info

Publication number: CN114590847A
Application number: CN202210148225.6A
Authority: CN
Inventors: 刘会基; 傅有焘
Original assignee: Hunan Lihe Thick Pu Technology Co ltd
Current assignee: Hunan Lihe Thick Pu Technology Co ltd
Priority date: 2022-02-17
Filing date: 2022-02-17
Publication date: 2022-06-07
Also published as: WO2023155366A1

Abstract

The application belongs to the technical field of battery materials, and particularly relates to a ternary cathode precursor material and a preparation method thereof, and a ternary cathode material. Wherein the ternary positive electrode precursor material comprises a chemical general formula of Ni_(1‑y‑z)Co_yMn_zO_xWherein x is more than or equal to 1 and less than or equal to 1.2, y is more than or equal to 0.03 and less than or equal to 0.1, and z is more than or equal to 0.2 and less than or equal to 0.35. The material provided by the application is a ternary anode precursor material, the content of nickel in the ternary anode precursor material is effectively improved by regulating and controlling the proportion of each main metal element in the ternary oxide precursor,the content of cobalt is reduced, so that the ternary cathode precursor material has good structural stability and high capacity, and the cycle stability and gram capacity of the corresponding ternary cathode material are improved.

Description

Ternary positive electrode precursor material, preparation method thereof and ternary positive electrode material

Technical Field

The application belongs to the technical field of battery materials, and particularly relates to a ternary cathode precursor material and a preparation method thereof, and a ternary cathode material.

Background

The new energy automobile adopts unconventional automobile fuel as a power source (or adopts conventional automobile fuel and a novel vehicle-mounted power device), integrates advanced technologies in the aspects of power control and driving of the automobile, and forms an automobile with advanced technical principle, new technology and new structure. With the rapid development of new energy automobiles, the demand of power batteries is increasing, and simultaneously, the demands are also facing more challenges, and particularly, more severe conditions are provided for the performance of the anode material. In the power battery, a ternary anode material precursor product takes nickel salt, cobalt salt and manganese salt as raw materials, wherein the proportion of nickel, cobalt and manganese can be adjusted according to actual needs. At present, most of the disclosed ternary cathode material precursor products are hydroxides, and the mainstream preparation technology is as follows: dissolving nickel salt, manganese salt and cobalt salt to form a mixed solution, mixing the mixed solution with ammonia water and alkali liquor for treatment, forming crystal nuclei through the complexation of the ammonia water and the coprecipitation of the alkali liquor, and continuing to grow crystals through agglomeration to obtain the ternary anode hydroxide precursor.

At present, the preparation process of the ternary positive hydroxide precursor is difficult to control, so that the stability of the product is easily influenced; in addition, the ternary positive electrode precursor hydroxide is a secondary ball, so that the prepared ternary positive electrode material has poor structural stability and low density, and is easy to break in the pole piece rolling process, so that the battery has poor circulation stability and low energy density.

Disclosure of Invention

The application aims to provide a ternary cathode precursor material, a preparation method thereof and the ternary cathode material, and aims to solve the technical problems that the structural stability of a ternary cathode hydroxide precursor in the prior art is poor, the density is low, the cycle stability and the energy density of the ternary cathode material are influenced, and the like.

In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:

in a first aspect, the present application provides a ternary positive electrode precursor material comprising a compound represented by the general chemical formula Ni_(1-y-z)Co_yMn_zO_xWherein x is more than or equal to 1 and less than or equal to 1.2 and 0.03≤y≤0.1，0.2≤z≤0.35。。

In a second aspect, the present application provides a method for preparing a ternary cathode precursor material, comprising the following steps:

mixing a nickel salt solution, a cobalt salt solution and a manganese salt solution, and then concentrating to obtain a mixed solution;

and carrying out atomization roasting treatment on the mixed solution to obtain the ternary anode precursor material.

In a third aspect, the present application provides a ternary cathode material, which is obtained by sintering a lithium source and a ternary cathode precursor material, wherein the ternary cathode precursor material includes the above-mentioned ternary cathode precursor material.

The ternary positive electrode precursor material provided by the first aspect of the application, on the one hand, the precursor exists in an oxide form, and compared with the traditional hydroxide precursor, the content of the main metal of nickel, cobalt and manganese in the oxide precursor is higher, and when the ternary positive electrode material is sintered, the unit loading amount is increased, so that the yield when the ternary positive electrode material is sintered is increased, and the manufacturing cost of the ternary positive electrode material is reduced. On the other hand, Ni_(1-y-z)Co_yMn_zO_xIn the ternary oxide precursor, the proportion of cobalt is only more than or equal to 0.03 and less than or equal to 0.1, the low cobalt content is beneficial to improving the nickel content in the ternary cathode material so as to improve the actual energy density of the ternary cathode material, if the cobalt content is too high, the actual capacity of the material is reduced, and if the cobalt content is too low, the structural stability of the material is reduced. The proportion of the manganese is more than or equal to 0.2 and less than or equal to 0.35, the proportion effectively ensures the stability and the safety of the crystal structure of the ternary oxide precursor, if the content of the manganese is too high, the structural stability of the material is reduced, the specific capacity of the material is reduced, and if the content of the manganese is too low, the structural stability and the safety of the material are also reduced. In addition, the proportion of nickel is not less than 0.55 and not more than 1-y-z and not more than 0.77, so that the ternary cathode precursor material is a high-nickel material, the volume energy density of the ternary cathode material is improved, the gram capacity of the material is reduced if the content of nickel is too low, and lithium and nickel are mixed and discharged if the content of nickel is too high, so that lithium is easily separated out. Therefore, the ternary positive electrode precursor material is prepared by adjustingThe proportion of each main metal element in the ternary oxide precursor is controlled, so that the ternary anode precursor material has good structural stability, and the cycle stability and gram capacity of the corresponding ternary anode material are improved. Compared with a ternary hydroxide precursor material which is required to be prepared by a coprecipitation method and the like and has poor structural stability, low density and poor particle size controllability, the ternary oxide precursor provided by the application can be prepared by one-time crystallization, so that the preparation time is shortened, the preparation efficiency is improved, the structural stability of the precursor material is improved, the density of the precursor material is improved, the particle size controllability is improved, the particle size of the material is refined, the unit pot loading amount of the precursor material is further improved, the preparation efficiency of the ternary cathode material is improved, and the manufacturing cost is reduced.

The preparation method of the ternary anode precursor material provided by the second aspect of the application has the advantages that the process flow is simple, the intermediate flow is few, the reaction process is convenient and flexible to regulate and control, the roasting treatment is carried out while atomizing, the product is ensured to have a smaller particle size, the reaction speed of the product is high, the actual reaction time for obtaining the ternary anode precursor material by atomizing and roasting only needs several seconds, and the production efficiency is high. In addition, anions in the salt solution are converted into gas substances in a high-temperature environment to be removed or recovered, so that the raw material utilization rate is high, the impurity content in the product is low, and the performance is excellent. Meanwhile, compared with the traditional coprecipitation method, the ternary positive electrode precursor material product prepared by the method has more excellent structural stability.

According to the ternary cathode material provided by the third aspect of the application, the ternary cathode material is obtained by sintering the lithium source and the ternary cathode precursor material, and the ternary cathode precursor material is high in nickel content and stable in property, and meanwhile, compared with a hydroxide precursor, the ternary cathode material is a metal oxide, and can be directly generated during sintering with the lithium source, so that the preparation efficiency of the ternary cathode material is improved. Therefore, the ternary cathode material obtained by sintering the ternary cathode material with a lithium source has the characteristics of higher gram capacity, cycling stability, structural stability and the like.

Drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.

FIG. 1 shows Ni provided in examples of the present application_0.67Co_0.05Mn_0.28Scanning electron microscope images of the O ternary oxide precursor;

FIG. 2 shows Ni provided in the examples of the present application_0.67Co_0.05Mn_0.28Scanning electron microscope images of the O ternary oxide precursor;

fig. 3 is a schematic flow chart of a method for preparing a ternary cathode precursor material provided in an embodiment of the present application;

FIG. 4 is a scanning electron microscope image of the ternary cathode material provided in example 1 of the present application;

fig. 5 is an XRD test pattern of the ternary cathode precursor material provided in example 5 of the present application.

Detailed Description

In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.

In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.

In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.

It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.

The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass in the description of the embodiments of the present application may be in units of mass known in the chemical industry, such as μ g, mg, g, and kg.

The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another and are not to be construed as indicating or implying relative importance or to implicitly indicate the number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.

In a first aspect, embodiments of the present application provide a ternary positive electrode precursor material, where the ternary positive electrode precursor material includes Ni as a chemical general formula_(1-y-z)Co_yMn_zO_xWherein x is more than or equal to 1 and less than or equal to 1.2, y is more than or equal to 0.03 and less than or equal to 0.1, and z is more than or equal to 0.2 and less than or equal to 0.35.

The ternary positive electrode precursor material provided by the first aspect of the embodiments of the present application includes a material having a chemical general formula of Ni_(1-y-z)Co_yMn_zO_xThe ternary oxide precursor of (1); on one hand, the precursor exists in an oxide form, compared with the traditional hydroxide precursor, the content of the main metal of nickel, cobalt and manganese in the oxide precursor is higher, and the unit pot loading amount is increased when the precursor is sintered into the ternary cathode material, so that the yield of the sintered ternary cathode material is increased, and the manufacturing cost of the ternary cathode material is reduced. On the other hand, Ni_(1-y-z)Co_yMn_zO_xIn the ternary oxide precursor, the proportion of cobalt is only more than or equal to 0.03 and less than or equal to 0.1, the low cobalt content is beneficial to improving the nickel content in the ternary cathode material so as to improve the actual energy density of the ternary cathode material, if the cobalt content is too high, the actual capacity of the material is reduced, and if the cobalt content is too low, the structural stability of the material is reduced. The proportion of the manganese is more than or equal to 0.2 and less than or equal to 0.35, the proportion effectively ensures the stability and the safety of the crystal structure of the ternary oxide precursor, if the content of the manganese is too high, the structural stability of the material is reduced, the specific capacity of the material is reduced, and if the content of the manganese is too low, the structural stability and the safety of the material are also reduced. In addition, the proportion of nickel is not less than 0.55 and not more than 1-y-z and not more than 0.77, so that the ternary cathode precursor material is a high-nickel material, the volume energy density of the ternary cathode material is improved, the gram capacity of the material is reduced if the content of nickel is too low, and lithium and nickel are mixed and discharged if the content of nickel is too high, so that lithium is easily separated out. Therefore, the ternary cathode precursor material in the embodiment of the application has good structural stability by regulating and controlling the proportion of each main metal element in the ternary oxide precursor, so that the cycle stability and gram capacity of the corresponding ternary cathode material are improved. In addition, compared with the ternary hydroxide precursor material which needs to be prepared by methods such as coprecipitation and the like and has poor structural stability, low density and poor particle size controllability, the ternary oxide precursor provided by the embodiment of the application can be prepared by one-time crystallization, and not only can the ternary oxide precursor be prepared by one-time crystallizationThe preparation time is shortened, the preparation efficiency is improved, the structural stability of the precursor material is improved, the density of the precursor material is improved, the particle size controllability is improved, and the particle size of the material is refined, so that the unit pot loading amount of the precursor material is further improved, the preparation efficiency of the ternary cathode material is improved, and the manufacturing cost is reduced.

In some embodiments, the ternary oxide precursor has the chemical formula Ni_(1-y-z)Co_yMn_zO_xWherein x is more than or equal to 1 and less than or equal to 1.14, y is more than or equal to 0.04 and less than or equal to 0.08, and z is more than or equal to 0.25 and less than or equal to 0.30. By optimizing the proportion of each element in the ternary oxide precursor, the ternary oxide precursor has better structural stability, so that the stability and the capacity of the ternary anode precursor material and the ternary anode material are improved.

In some embodiments, the crystal structure of the ternary oxide precursor is a single crystal structure of one of a hexagonal layered structure, a spinel-type structure, a cubic-type structure, and an octahedral-type structure. The ternary oxide precursor is in a single crystal form, and compared with a secondary hydroxide precursor, the ternary oxide precursor has a more stable material crystal structure, and is favorable for improving the tap density, loose bulk density and other densities of the ternary anode precursor material, so that the cycle stability and specific capacity of the corresponding ternary anode material are improved.

In some embodiments, the ternary cathode precursor material includes, but is not limited to, layered structures such as a hexagonal layered structure, a cubic structure, an octahedral structure, and the like, and multiple crystal forms such as a spinel structure, and by using structural advantages of different crystal forms, the intercalation and deintercalation efficiency of lithium ions can be improved, so that the electrochemical performance of the ternary cathode material is improved.

In some embodiments, the crystalline structure of the ternary oxide precursor may be a hexagonal layered structure; after the ternary cathode material is formed, the hexagonal layered structure is a two-dimensional structure, so that the lithium ions can be conveniently removed and embedded, and the specific capacity of the ternary cathode material can be improved.

In some specific embodiments, the crystal structure of the ternary oxide precursor can also be a cubic structure, which is beneficial to improving the uniformity of the precursor material and reducing the agglomeration phenomenon, and the product has good stability and higher cycle performance and rate capability.

In some embodiments, the crystal structure of the ternary oxide precursor may also be an octahedral structure, the octahedral structure precursor has a high active specific surface area, which is also beneficial to lithium ion deintercalation, and the particle size uniformity of the precursor is high, which is beneficial to improving the film layer compactness, flatness and uniformity of the positive plate, thereby improving the cycle stability of the battery.

In some specific embodiments, the crystal structure of the ternary oxide precursor can be a spinel structure, the spinel structure is a three-dimensional cubic structure, and the stability of the crystal structure is high, which is beneficial to improving the cycle stability and rate capability of the ternary cathode material.

In some embodiments, the ternary positive electrode precursor material includes at least two of a ternary oxide precursor with a hexagonal layered structure, a ternary oxide precursor with a spinel structure, a ternary oxide precursor with a cubic structure, and a ternary oxide precursor with an octahedral structure, and the electrochemical performance of the ternary positive electrode precursor material can be improved more favorably through the synergistic effect of the ternary oxide precursors with two or more different crystal structures.

In some embodiments, the ternary cathode precursor material simultaneously comprises a ternary oxide precursor with a hexagonal layered structure and a ternary oxide precursor with a spinel structure, and the mass ratio of the ternary oxide precursor with the hexagonal layered structure to the ternary oxide precursor with the spinel structure is (50-100): (1-50), wherein the ternary oxide precursor with the two-dimensional layered structure is beneficial to Li ion de-intercalation, and the capacity of the ternary cathode material is improved; the spinel structure is a three-dimensional cubic structure, the stability of the structure is high, and the cycle performance and the rate capability of the ternary cathode material are improved more favorably compared with a two-dimensional layered structure. Therefore, the mass ratio of the organic silicon compound to the organic silicon compound is (50-100): (1-50) the hexagonal layered structure and the spinel-structured ternary oxide precursor cooperate with each other, so that the obtained ternary cathode material has high capacity, high cycle stability and high multiplying power. If the proportion of the ternary oxide precursor with the hexagonal layered structure in the ternary cathode precursor material is too high, the stability of the ternary cathode material can be reduced; if the content of the precursor of the spinel-type ternary oxide is too high, the capacity of the ternary positive electrode material is reduced.

According to the embodiment of the application, the proportion of the ternary oxide precursor with the layered structure and the ternary oxide precursor with the spinel structure in the ternary cathode precursor material is adjusted, so that the performances of high capacity, high cycle performance and high rate capability of the ternary cathode material can be further optimized. In some preferred embodiments, in the ternary cathode precursor material, the mass ratio of the ternary oxide precursor with a hexagonal layered structure to the ternary oxide precursor with a spinel structure is (60-90): (10-40), and further, the mass ratio is (65-80): (20-35), and further, the mass ratio is (65-75): (25-35). In some embodiments, the mass ratio of the hexagonal layered structure ternary oxide precursor to the spinel structure ternary oxide precursor in the ternary cathode precursor material includes, but is not limited to, 100: 1. 90: 10. 80: 20. 75: 25. 70: 30. 68: 32. 65: 35. 60: 40. 50: 50, etc. When the mass ratio of the ternary oxide precursor with the layered structure to the precursor with the spinel structure is 90: at 10, the obtained ternary cathode material has high stability and is most favorable for Li deintercalation under the condition of the mass ratio, and the obtained material has the best charge and discharge performance.

In some embodiments, the ternary cathode precursor material simultaneously comprises a spinel-structured ternary oxide precursor and a cubic-structured ternary oxide precursor, and the mass ratio of the spinel-structured ternary oxide precursor to the cubic-structured ternary oxide precursor is (10-50): (50-90), wherein the cubic ternary oxide precursor provides a structure with uniform size and has a certain spatial structure, so that Li ion deintercalation is facilitated, an excellent charge and discharge effect is realized, and the efficiency is improved; however, the cubic structure has a larger space structure and poorer stability, so that the spinel structure with high mixing stability can improve the structural stability of the ternary cathode material, so that the obtained material has high capacity, high cycle performance and high rate performance, and the electrochemical performance of the obtained ternary cathode material is ensured to be excellent.

According to the embodiment of the application, the high-capacity, high-cycle performance and high-rate performance of the ternary cathode material can be further optimized by adjusting the proportion of the spinel-type structure to the cubic-type structure in the ternary cathode precursor material. In some embodiments, the mass ratio of the spinel-type structure ternary oxide precursor to the cubic-type structure ternary oxide precursor in the ternary oxide precursor includes, but is not limited to, 10: 90. 15: 85. 20: 80. 25: 75. 30: 70. 35: 65. 40: 60. 50: 50, etc. When the mass ratio of the spinel-type structure ternary oxide precursor to the cubic-type structure ternary oxide precursor in the ternary cathode precursor material is 35: and 65, the obtained ternary cathode material has high stability, is most beneficial to Li ion deintercalation, and has the best charge and discharge performance.

In some embodiments, the ternary cathode precursor material simultaneously comprises an octahedron-structure ternary oxide precursor and a spinel-structure ternary oxide precursor, and the mass ratio of the octahedron-structure ternary oxide precursor to the spinel-structure ternary oxide precursor is (50-80): (15-50); the octahedral structure is that a polyhedron formed by eight planes is called an octahedron, a pyramid formed by 6 vertexes and 8 regular triangles has eight faces, each face is an equilateral triangle, and the octahedral structure has large space and is beneficial to the material action; but the stability is low, so the spinel structure is combined with the combined action of the spinel structure, the spinel structure is favorable for stabilizing the octahedral structure, the high stability of the obtained ternary cathode material is favorably ensured by controlling the mass ratio of the spinel structure to the octahedral structure, Li is favorably deintercalated, and the charge and discharge performance of the obtained material is optimal. In some embodiments, the mass ratio of the octahedral structured ternary oxide precursor to the spinel structured ternary oxide precursor in the ternary cathode precursor material includes, but is not limited to, 50: 50. 55: 45. 60: 40. 65: 35. 70: 30. 75: 25. 80: 20, etc.

In some embodiments, when the crystal structure of the ternary oxide precursor is a hexagonal layered structure, a cubic structure, or an octahedral structure, the ternary oxide precursor has a chemical formula of Ni_(1-y-z)Co_yMn_zO; at this time, all the oxygen atoms in the ternary oxide precursor have a valence of-2. When the crystal structure of the precursor of the ternary oxide is a spinel structure, the chemical general formula of the precursor of the ternary oxide is Ni_(1-y-z)Co_yMn_zO_xIn this case, the material is of the spinel type AB2O4, in which nickel and manganese contain ions with a partial +3 valence state, and thus x is greater than 1.

In some embodiments, the ternary positive electrode precursor material comprises: ni_0.67Co_0.05Mn_0.28O、Ni_0.72Co_0.03Mn_0.25O、Ni_0.7Co_0.04Mn_0.26O、Ni_0.65Co_0.06Mn_0.29O、Ni_0.62Co_0.08Mn_0.30O、Ni_0.6Co_0.10Mn_0.30At least one layered ternary oxide precursor in O, and/or Ni_0.67Co_0.05Mn_0.28O_1.02、Ni_0.72Co_0.03Mn_0.25O_1.01、Ni_0.60Co_0.1Mn_0.3O_1.19At least one spinel-type ternary oxide precursor. The specific ternary oxide precursors have good structural stability and high capacity, and are beneficial to improving the cycle stability and gram capacity of the corresponding ternary cathode material.

In some embodiments, provided Ni_0.67Co_0.05Mn_0.28The crystal structure of the O-ternary oxide precursor is a layered structure such as a hexagonal layered structure, a cubic structure, or an octahedral structure, and the like, and electron microscope images thereof are shown in fig. 1 and 2. And Ni_0.67Co_0.05Mn_0.28O_1.02The crystal structure of the ternary oxide precursor is spinel type. The embodiment of the application controls the molar ratio of nickel, cobalt and manganese in the ternary oxide precursor toThe content of cobalt in the ternary oxide precursor is lower, only 4.2%, the property is stable, and the gram capacity and the stability of the corresponding ternary anode material are favorably improved; meanwhile, the precursor is a metal oxide, compared with hydroxide, the content of main metal in the oxide is higher, and the unit bowl loading amount is increased when the precursor is sintered into the ternary cathode material, so that the yield of the sintered ternary cathode material is increased, and the manufacturing cost of the ternary cathode material is reduced.

In some embodiments, provided Ni_0.72Co_0.03Mn_0.25O, the crystal structure of the obtained ternary oxide precursor is a layered structure; and Ni_0.72Co_0.03Mn_0.25O_1.01The crystal structure of the ternary oxide precursor is spinel type. The provided ternary oxide precursor has low cobalt content and high nickel content, so that the energy level density of the obtained ternary material precursor is high, the material capacity is high, and the property is stable. In some embodiments, the resulting Ni is controlled_0.72Co_0.03Mn_0.25The crystal structure of the precursor of the O ternary oxide is a layered structure, and the shape of a macroscopic material of the precursor is a spherical structure, wherein the layered structure is a two-dimensional structure, so that after a positive electrode material is formed, the de-intercalation of lithium ions is facilitated, and the capacity of the lithium ion can be improved; the formed material with the macroscopic spherical structure has complete crystal form, is beneficial to material reaction, and enables the obtained ternary anode precursor material to have excellent properties.

In some embodiments, provided Ni_0.60Co_0.1Mn_0.3O_1.19The crystal structure of the obtained ternary oxide precursor is a spinel structure, and the material has high structural stability and high capacity. And Ni_0.6Co_0.10Mn_0.30The crystal structure of the O ternary oxide precursor is a layered structure such as a hexagonal layered structure, a cubic structure or an octahedral structure. Furthermore, the macroscopic morphology of the ternary anode precursor material is a porous structure, the active specific surface area is large, more reaction sites can be provided, and the obtained material has higher capacity and cycle performance.

In some embodiments, the ternary oxide precursor has a particle size of 50 to 800 nm. The granularity of the ternary oxide precursor crystal particles in the embodiment of the application can reach smaller particles smaller than 100nm and larger particles of 500-800 nm, the distribution range of the granularity of the crystal particles is wide, and the application range of the ternary oxide precursor is widened. The ternary oxide precursor with the single crystal particle size of 50-800 nm has a large active specific surface area, is beneficial to forming a ternary cathode material by subsequent reaction with lithium salt, and is beneficial to improving the film forming uniformity, stability, surface flatness and the like of the ternary cathode material, so that the stability of the cathode plate is further improved. In some preferred embodiments, the ternary oxide precursor has a crystal particle size of 100 to 700nm, further 200 to 600nm, further 300 to 500nm, and the like. In some embodiments, when the grain size of the crystal of the ternary oxide precursor is 100-500 nm, the ternary oxide precursor has complete crystal form, full grain shape, uniform dispersion, stable structure and stable performance, and the preparation period of the ternary cathode material can be shortened.

In some embodiments, the macro morphology of the ternary cathode precursor material comprises at least one of a spherical structure, a porous structure and a three-dimensional polygonal structure, and the contact activity specific surface area of the macro morphology and a lithium source is large, so that the ternary cathode precursor material can be in full contact reaction with the lithium source subsequently, and lithium ions can be combined into a crystal structure to form the ternary cathode material.

In some specific embodiments, the macro morphology of the ternary cathode precursor material is a porous structure, and has a larger active specific surface area, so that the ion transport property and the electrochemical activity of the material can be improved, more lithium storage sites can be generated, and a buffer can be provided for the volume change of an electrode to ensure that the obtained material has high power, high energy and high stability. In some specific embodiments, the macroscopic morphology of the ternary cathode precursor material is a three-dimensional polygonal structure, which is beneficial to improving the cycle performance and the rate performance, so that the material performance is more excellent.

In some embodiments, the macro morphology of the ternary positive electrode precursor material comprises at least one of a spherical structure, a porous structure and a three-dimensional polygonal structure, and the particle size D50 of the macro morphology is 1.5-3.5 μm, further 1.5-3 μm, further 1.5-2 μm.

In some embodiments, the ternary positive electrode precursor material has a loose bulk density of 0.5 to 1.0g/cm³Further, the bulk density of the soil is 0.6 to 0.8g/cm³. In some embodiments, the tap density of the ternary positive electrode precursor material is 1.6-2.4 g/cm³Further, the tap density is 1.8 to 2g/cm³. The ternary cathode material in the embodiment of the application has larger loose bulk density and tap density, and the unit pot loading amount is increased when the ternary cathode material is sintered, so that the yield of the ternary cathode material sintered is increased, and the manufacturing cost of the ternary cathode material is reduced.

In some embodiments, the ternary positive electrode precursor material has a bulk density of 0.5g/cm³The tap density of the ternary positive electrode precursor material is 1.6g/cm³The interior of the obtained ternary anode precursor material is relatively dense and compact. In other embodiments, the ternary positive electrode precursor material has a bulk density of 0.7g/cm³The tap density of the ternary positive electrode precursor material is 2.0g/cm³The obtained ternary positive electrode precursor material is compact in structure and high in purity. In other embodiments, the ternary positive electrode precursor material has a bulk density of 1g/cm³The tap density of the ternary positive electrode precursor material is 2.4g/cm³。

The ternary positive electrode precursor material of the embodiment of the application can be prepared by the following embodiment method.

As shown in fig. 3, a second aspect of the embodiments of the present application provides a method for preparing the above ternary cathode precursor material, including the following steps:

s01, mixing a nickel salt solution, a cobalt salt solution and a manganese salt solution, and concentrating to obtain a mixed solution;

and S02, carrying out atomization roasting treatment on the mixed solution to obtain the ternary anode precursor material.

The second aspect of the embodiments of the present application provides a method for preparing a ternary positive electrode precursor material, according to Ni_(1-y-z)Co_yMn_zO_xThe stoichiometric ratio of metal elements in the chemical general formula is that after a nickel salt solution, a cobalt salt solution and a manganese salt solution are mixed, the concentration of the nickel salt, the cobalt salt and the manganese salt in the mixed solution is regulated and controlled through concentration treatment; and (2) atomizing and roasting the mixed solution, wherein the atomized liquid drops are directly roasted while the mixed solution is atomized into fine liquid drops, so that metal cations such as nickel, cobalt, manganese and the like in the liquid drops rapidly react in a high-temperature environment to generate a ternary oxide precursor single crystal, and anions in the salt solution are converted into gas substances in the high-temperature environment to be removed or recovered, thereby obtaining the ternary anode precursor material with high product purity, small particle size and good uniformity. The preparation method has the advantages of simple process flow, less intermediate flow, convenient and flexible regulation and control of the reaction process, atomization and roasting treatment, so that the product has small particle size, the reaction speed of the product is high, the actual reaction time for obtaining the ternary cathode precursor material by atomization and roasting is only several seconds, and the production efficiency is high. In addition, anions in the salt solution are converted into gas substances in a high-temperature environment to be removed or recovered, so that the raw material utilization rate is high, the impurity content in the product is low, and the performance is excellent. According to the method for directly preparing the ternary anode oxide precursor material by carrying out atomization roasting treatment on the mixed solution, the structural stability of the precursor material is improved, the density of the precursor material is improved, and the particle size of the material is refined, so that the unit loading amount of the precursor material is further increased, the preparation efficiency of the ternary anode material is improved, and the manufacturing cost is reduced. Compared with the traditional method for preparing the ternary hydroxide precursor by a coprecipitation method and the like, the method has the advantages that the preparation efficiency of the material is improved, the process is simplified, the discharge of industrial wastes such as wastewater and the like is reduced, the production process is more environment-friendly, and the production cost is reduced; but also is more beneficial to regulating and controlling the properties of the precursor material such as crystal structure, grain diameter, looseness, density and the like. The method solves the problems of poor structural stability, low density, poor particle size controllability and the like of the conventional secondary crystallization coated ternary hydroxide precursor material.

In some embodiments, in step S01, as Ni_(1-y-z)Co_yMn_zO_xChemical general formulaThe stoichiometric ratio of the medium metal elements is that after a nickel salt solution, a cobalt salt solution and a manganese salt solution are mixed, the mixture is concentrated to obtain a mixed solution, wherein x is more than or equal to 1 and less than or equal to 1.2, y is more than or equal to 0.03 and less than or equal to 0.1, and z is more than or equal to 0.2 and less than or equal to 0.35. The metal salt solution in the mixed solution has proper atomization concentration, which is beneficial to regulating and controlling the reaction rate of the metal salt solution and the particle size of the ternary oxide precursor.

In some embodiments, after mixing the nickel salt solution, the cobalt salt solution and the manganese salt solution, performing concentration treatment, and controlling the concentration of the nickel salt, the cobalt salt and the manganese salt in the obtained mixed solution to be respectively and independently 50-300 g/L, wherein the concentration of the metal salt is favorable for atomization, crystallization and granulation. If the concentration of the metal salt in the mixed solution is lower than 80g/L, the content of the metal salt in atomized liquid drops is too low, the metal salt in the liquid drops is not favorable for full reaction in the roasting process, crystallization and granulation, the obtained product is less, and the enrichment of a precursor is not favorable; if the concentration of the mixed solution is higher than 300g/L, the concentration of the mixed solution is too high, so that the content of metal salt in the obtained atomized liquid drops is too high, crystallization and granulation of metal salt components are not facilitated in the roasting process, the particle size is too large, agglomeration is easy to cause, a single crystal material is not facilitated to be prepared, the crystal form of the material is not facilitated to be regulated, and the stability of the ternary anode precursor is reduced. In some embodiments, the concentrations of the nickel, cobalt and manganese salts in the mixed solution are independently 50g/L, 60g/L, 80g/L, 120g/L, 160g/L, 200g/L, 220g/L, 260g/L, 300g/L, etc.

In some embodiments, the nickel salt solution is selected from: at least one of a nickel chloride solution, a nickel nitrate solution, a nickel oxalate solution and a nickel sulfate solution. In some embodiments, the cobalt salt solution is selected from: at least one of cobalt chloride solution, cobalt nitrate solution, cobalt oxalate solution and cobalt sulfate solution. In some embodiments, the manganese salt solution is selected from: at least one of manganese chloride solution, manganese nitrate solution, manganese oxalate solution and manganese sulfate solution. The salt solution of the main metals of nickel, cobalt and manganese in the embodiment of the application is selected from at least one of chloride salt solution, nitrate solution, oxalate solution and sulfate solution, and the salt solutions not only have good dissolving performance, but also chloride ions and nitrate ionsAnions such as oxalate ion and sulfate ion can be converted into HCl, NO and CO during the roasting process₂、SO₂And the gaseous substances are beneficial to recovery, the residual impurity elements in the ternary oxide precursor material are reduced, and the product purity is improved.

In some specific embodiments, a corresponding chloride solution is prepared by dissolving a nickel-cobalt-manganese metal simple substance with hydrochloric acid, the impurity content in the solution is strictly controlled to be low in the preparation process, HCl gas after atomization and sintering can be directly recycled for preparation of the metal salt solution, experiments are recycled, and the generation efficiency is improved.

In some embodiments, the solution containing nickel, cobalt and manganese ions is transferred to a mixing tank to be mixed, so as to prepare the mixed solution containing nickel, cobalt and manganese ions, wherein the material of the mixing tank is an acid-resistant material with certain strength.

In some embodiments, in the step S02, the step of atomizing the baking process includes: the atomization air quantity is 20-1200 m³And atomizing the mixed solution into fine droplets under the condition of/h, roasting the droplets at the temperature of 300-1000 ℃ and the oxygen mass percentage content of 1.0-13.0%, and directly converting the droplets into ternary oxide precursor crystals to obtain the ternary anode precursor material, wherein the reaction rate is high and the efficiency is high. Wherein, 20 to 1200m³The atomization air quantity is/h, so that the mixed solution is ensured to form liquid drops with small and uniform particle sizes, sufficient time is provided for the reaction between metal salts in the liquid drops, if the atomization air quantity is too low, the particle size of the formed liquid drops is too large, the liquid drops with small particle sizes are not beneficial to obtaining, the liquid drops are easy to settle, and the metal salts in the liquid drops are not beneficial to fully reacting in the roasting process; if the atomization air quantity is too high, the residence time of the liquid drops in the roasting environment is too short, and the full contact reaction of metal salts in the liquid drops is also not facilitated. In some preferred embodiments, the atomization air volume is 100-1100 m³Per hour, the further atomization air quantity is 200-1000 m³The further atomization air quantity is 300-800 m³The further atomization air quantity is 400-600 m³H, etc. In addition, the temperature of roasting treatment is 300-1000 ℃, and the temperature condition is favorable for atomizing metal salt in liquid dropsAnd the ternary oxide precursor single crystal material is generated through rapid reaction. If the roasting treatment temperature is lower than 300 ℃, the treatment temperature is too low, which is not favorable for the metal salt in the atomized liquid drops to react to obtain a formed precursor; if the temperature of the roasting treatment is higher than 1000 ℃, the energy consumption is high, and the control of the crystal form of the ternary oxide precursor is not facilitated. The oxygen content can affect the reaction rate of the metal salt in the liquid drop and the crystal form of the generated ternary oxide precursor. In some embodiments, the oxygen content may be 1.0-2%, 2-5%, 5-8%, 8-10%, 10-13.0%, etc.

According to the embodiment of the application, the physical properties such as particle size, crystal form and the like of the prepared ternary cathode precursor material can be flexibly regulated and controlled by regulating the atomization air volume, the roasting temperature and the oxygen content in the atomization roasting treatment process, so that the optimization of the physical and chemical properties of the ternary cathode material is facilitated. In some embodiments, the atomization air volume is 20-1200 m³And atomizing the mixed solution into liquid drops under the condition of h, and roasting at the temperature of 300-900 ℃ and the oxygen mass percentage content of 1.0-13.0%, so that the ternary oxide precursor material with crystal forms such as a hexagonal layered structure, a cubic structure, an octahedral structure and the like can be prepared. In other embodiments, the atomization air volume is 20-1200 m³And atomizing the mixed solution into liquid drops under the condition of/h, and roasting at the temperature of 700-1000 ℃ and the oxygen mass percentage content of 1.0-13.0% to obtain the spinel-structured ternary oxide precursor material.

In some embodiments, the time of the baking treatment is controlled to be 1 to 50 seconds. In the preparation method, the preparation of the formed precursor can be ensured in a short time, the preparation time is short, the efficiency is high, and the wide application is facilitated.

In some embodiments, after the ternary cathode precursor material is prepared, a post-treatment step such as grinding or crushing treatment is further included, and the particle size of the obtained product can be controlled by controlling conditions such as the distance between grinding discs or the pressure flow rate of the crushing gas, so that the particle size distribution of the ternary cathode precursor material is more uniform.

In a third aspect of the embodiments of the present application, a ternary cathode material is obtained by sintering a mixture including a lithium source and a ternary cathode precursor material, where the ternary cathode precursor material is the ternary cathode precursor material in the above embodiments.

According to the ternary cathode material provided by the third aspect of the application, the ternary cathode material is obtained by sintering a lithium source and the ternary cathode precursor material, and the ternary cathode precursor material contains Ni_(1-y-z)Co_yMn_zO_xThe ternary oxide precursor has the advantages that x is more than or equal to 1 and less than or equal to 1.2, y is more than or equal to 0.03 and less than or equal to 0.1, z is more than or equal to 0.2 and less than or equal to 0.35, the nickel content is higher, the property is more stable, meanwhile, the precursor is a metal oxide, compared with a hydroxide precursor, a positive electrode material can be directly generated during lithium source sintering, and the preparation efficiency of the ternary positive electrode material is improved. Therefore, the ternary cathode material obtained by sintering the lithium source has the characteristics of higher gram capacity, cyclic stability, structural stability and the like.

In some embodiments, the lithium source is selected from one or more of lithium carbonate, lithium hydroxide monohydrate, lithium acetate, lithium nitrate, lithium oxalate, lithium acetate, lithium hydroxide, and lithium oxide, each of which can be sintered at high temperature with the ternary precursor material to form the ternary cathode material.

In some embodiments, the molar ratio of the ternary cathode precursor material to the lithium source is 1: (1-1.1), the proportion is favorable for the sufficient reaction of the ternary precursor material and lithium salt to generate the nickel-cobalt-manganese ternary cathode material. The molar ratio of the ternary cathode precursor material to the lithium source is controlled, so that the obtained ternary cathode material has high capacity and cycle performance.

In some embodiments, after the ternary precursor material is mixed with the lithium salt, the sintering temperature is 450-_(1-y-z)Co_yMn_zO₂Wherein y is more than or equal to 0.03 and less than or equal to 0.1, and z is more than or equal to 0.2 and less than or equal to 0.35. In some specific embodiments, ternary positive electrode materials include, but are not limited to: LiNi_0.72Co_0.03Mn_0.25O₂、LiNi_0.7Co_0.04Mn_0.26O₂、LiNi_0.67Co_0.05Mn_0.28O₂、LiNi_0.65Co_0.06Mn_0.29O₂、LiNi_0.62Co_0.08Mn_0.30O₂、LiNi_0.6Co_0.10Mn_0.30O₂And the like.

In some embodiments, a method for preparing a ternary cathode material is provided, comprising the steps of: carrying out mixed sintering treatment on the ternary positive electrode precursor material and a lithium source to obtain a ternary positive electrode material; wherein the temperature of the mixed sintering treatment is 300-1000 ℃. And controlling the particle uniformity of the obtained ternary cathode material by grinding or crushing treatment.

In a fourth aspect, the present application provides a secondary battery including the above-described ternary positive electrode material in a positive electrode sheet thereof.

According to the secondary battery provided by the fourth aspect of the application, the positive plate comprises the ternary positive electrode material, and the ternary positive electrode material has the characteristics of higher gram capacity, cyclic stability, structural stability and the like, so that the energy density, the cyclic stability and the safety performance of the secondary battery are improved.

In some embodiments, ternary positive electrode materials include, but are not limited to: LiNi_(1-y-z)Co_yMn_zO₂Wherein y is more than or equal to 0.03 and less than or equal to 0.1, and z is more than or equal to 0.2 and less than or equal to 0.35. In some embodiments, ternary positive electrode materials include, but are not limited to: LiNi_0.72Co_0.03Mn_0.25O₂、LiNi_0.7Co_0.04Mn_0.26O₂、LiNi_0.67Co_0.05Mn_0.28O₂、LiNi_0.65Co_0.06Mn_0.29O₂、LiNi_0.62Co_0.08Mn_0.30O₂、LiNi_0.6Co_0.10Mn_0.30O₂And the like. The ternary anode materials have the characteristics of good structural stability, high capacity, good cycling stability and the like.

In some embodiments, the positive electrode sheet in the secondary battery comprises a current collector and an active material layer, wherein the current collector and the active material layer are arranged in a lamination mode, and the active material layer comprises a ternary material, a conductive agent, a binder and the like.

In some embodiments, the process for preparing the positive electrode material into the positive electrode sheet comprises the following steps: mixing the ternary positive electrode material, the conductive agent and the binder to obtain electrode slurry, coating the electrode slurry on a current collector, and drying, rolling, die cutting and the like to obtain the positive electrode plate.

In some embodiments, the positive electrode current collector includes, but is not limited to, any one of a copper foil, an aluminum foil.

In some embodiments, the binder is present in the electrode slurry in an amount of 2 wt% to 4 wt%. In particular embodiments, the binder may be present in an amount of 2 wt%, 3 wt%, 4 wt%, and the like, which are typical and not limiting. In a specific embodiment, the binder comprises one or more of polyvinylidene chloride, soluble polytetrafluoroethylene, styrene butadiene rubber, hydroxypropyl methylcellulose, carboxymethylcellulose, polyvinyl alcohol, acrylonitrile copolymer, sodium alginate, chitosan, and chitosan derivatives. In some embodiments, the conductive agent is present in the electrode slurry in an amount of 3 wt% to 5 wt%. In specific embodiments, the content of the conductive agent may be 3 wt%, 4 wt%, 5 wt%, and the like, which are typical but not limiting contents. In particular embodiments, the conductive agent includes one or more of graphite, carbon black, acetylene black, graphene, carbon fibers, C60, and carbon nanotubes.

The secondary battery in the embodiment of the present application may be a lithium ion battery or a lithium metal battery or the like.

The negative electrode sheet, the electrolyte, the diaphragm and the like in the secondary battery of the embodiment are not particularly limited, and can be applied to any battery system.

In order to make the details and operations of the above-mentioned embodiments of the present invention clearly understood by those skilled in the art, and to make the advanced performances of the ternary cathode precursor material and the preparation method thereof, the ternary cathode material, and the secondary battery in the embodiments of the present invention obviously appear, the above-mentioned technical solutions are exemplified by a plurality of examples below.

Example 1

Ni with hexagonal layered structure_0.67Co_0.05Mn_0.28The preparation method of the O ternary cathode precursor material comprises the following steps:

according to Ni_0.67Co_0.05Mn_0.28Mixing a nickel chloride solution, a cobalt chloride solution and a manganese chloride solution according to the stoichiometric ratio of metal elements in the O chemical formula, and concentrating to obtain a mixed solution; wherein the concentrations of the nickel salt, the cobalt salt and the manganese salt are 163.7g/L, 12.3g/L and 64.0g/L respectively.

② when the atomization air quantity is 50m³Atomizing the mixed solution into liquid drops under the condition of/h, roasting at the temperature of 710 ℃ and the oxygen mass percentage content of 5.0 percent, and crushing to obtain Ni_0.67Co_0.05Mn_0.28The crystal structure of the O ternary anode precursor material is a hexagonal layered structure, and the morphology of the O ternary anode precursor material is shown in electron micrographs in attached figures 1 and 2.

LiNi_0.67Co_0.05Mn_0.28O₂The preparation process of the ternary cathode material comprises the following steps:

③ mixing Ni_0.67Co_0.05Mn_0.28Weighing corresponding amount of O and LiOH according to the molar ratio of 1.05: 1; mixing, sintering at 600 deg.C for 8 hr, and crushing to obtain LiNi_0.67Co_0.05Mn_0.28O₂The topography of the ternary cathode material is shown in figure 4.

A lithium ion battery, comprising the steps of:

preparing a positive plate: in terms of LiNi_0.67Co_0.05Mn_0.28O₂Ternary cathode material: conductive agent (acetylene black): binder (PVDF) formulation 85 wt.%: 10 wt.%: 5 wt.%, weighing, mixing and grinding. Then, N-methylpyrrolidone (NMP) solvent was added to prepare a uniform positive electrode slurry. And uniformly coating the positive electrode slurry on an aluminum foil by adopting a scraper, and drying to obtain the positive electrode plate which can be directly assembled into the battery.

Assembling batteries: and in a glove box with a high-purity argon atmosphere, assembling the prepared positive plate into a button cell with the model CR2025, and assembling the button cell with lithium as a counter electrode for subsequent electrochemical performance test. Wherein the diaphragm is a polyolefin porous membrane, and the electrolyte is ethylene carbonate.

Example 2

Spinel type Ni_0.67Co_0.05Mn_0.28O_1.02The preparation method of the ternary positive electrode precursor material comprises the following steps:

according to Ni_0.67Co_0.05Mn_0.28O_1.02Mixing a nickel chloride solution, a cobalt chloride solution and a manganese chloride solution according to the stoichiometric ratio of metal elements in the chemical formula, and concentrating to obtain a mixed solution; wherein the concentrations of the nickel salt, the cobalt salt and the manganese salt are respectively 68.2g/L, 5.1g/L and 26.7 g/L.

② when the atomization air quantity is 50m³Atomizing the mixed solution into liquid drops under the condition of/h, roasting at the temperature of 740 ℃ and the oxygen mass percentage content of 11.0 percent, and crushing to obtain Ni_0.67Co_0.05Mn_0.28O_1.02The crystal structure of the ternary positive electrode precursor material is spinel type.

LiNi_0.67Co_0.05Mn_0.28O₂A ternary positive electrode material, which differs from example 1 in that: the ternary cathode material is prepared from Ni in spinel type of example 2_0.67Co_0.05Mn_0.28O_1.02And preparing the ternary anode precursor material.

A lithium ion battery which differs from example 1 in that: the ternary cathode material prepared in example 2 was used for the cathode plate in the lithium ion battery.

Example 3

Ni with octahedral structure_0.67Co_0.05Mn_0.28The preparation method of the O ternary cathode precursor material comprises the following steps:

firstly, according to Ni_0.67Co_0.05Mn_0.28Mixing a nickel chloride solution, a cobalt chloride solution and a manganese chloride solution according to the stoichiometric ratio of metal elements in the O chemical formula, and concentrating to obtain a mixed solution; wherein the concentrations of the nickel salt, the cobalt salt and the manganese salt are respectively 95.5g/L,7.15g/L、37.35g/L。

② when the atomization air quantity is 50m³Atomizing the mixed solution into liquid drops under the condition of/h, roasting at the temperature of 700 ℃ and the oxygen mass percentage content of 7.0 percent, and crushing to obtain Ni_0.67Co_0.05Mn_0.28The crystal structure of the O ternary anode precursor material is an octahedral structure.

LiNi_0.67Co_0.05Mn_0.28O₂A ternary cathode material, which differs from example 1 in that: ternary cathode material comprising example 3 octahedral structural Ni_0.67Co_0.05Mn_0.28And preparing the O ternary anode precursor material.

A lithium ion battery which differs from example 1 in that: the ternary cathode material prepared in example 3 was used as a cathode sheet in a lithium ion battery.

Example 4

Ni with cubic structure_0.67Co_0.05Mn_0.28The preparation method of the O ternary cathode precursor material comprises the following steps:

according to Ni_0.67Co_0.05Mn_0.28Mixing a nickel chloride solution, a cobalt chloride solution and a manganese chloride solution according to the stoichiometric ratio of metal elements in the O chemical formula, and concentrating to obtain a mixed solution; wherein the concentrations of the nickel salt, the cobalt salt and the manganese salt are respectively 95.5g/L, 7.15g/L and 37.35 g/L.

② when the atomization air quantity is 50m³Atomizing the mixed solution into liquid drops under the condition of/h, roasting at the temperature of 680 ℃ and the oxygen mass percentage content of 5.0 percent, and crushing to obtain Ni_0.67Co_0.05Mn_0.28The crystal structure of the O ternary anode precursor material is cubic.

LiNi_0.67Co_0.05Mn_0.28O₂A ternary positive electrode material, which differs from example 1 in that: the ternary cathode material is prepared from Ni with a cubic structure in example 4_0.67Co_0.05Mn_0.28And preparing the O ternary anode precursor material.

A lithium ion battery which differs from example 1 in that: the ternary cathode material prepared in example 4 was used for the cathode plate in the lithium ion battery.

Example 5

Hexagonal layered structure Ni_0.67Co_0.05Mn_0.28O and spinel type Ni_0.67Co_0.05Mn_0.28O_1.02The preparation method of the mixed ternary positive electrode precursor material comprises the following steps:

according to Ni_0.67Co_0.05Mn_0.28Mixing a nickel chloride solution, a cobalt chloride solution and a manganese chloride solution according to the stoichiometric ratio of metal elements in the chemical formula O, and concentrating to obtain a mixed solution; wherein the concentrations of the nickel salt, the cobalt salt and the manganese salt are respectively 150.0g/L, 11.2g/L and 58.8 g/L.

② the atomization air quantity is 75m³Atomizing the mixed solution into liquid drops under the condition of/h, roasting at the temperature of 730 ℃ and the oxygen mass percentage content of 6.0 percent, and crushing to obtain a ternary positive electrode precursor material, wherein the crystal structure of the ternary positive electrode precursor material simultaneously contains hexagonal layered structure Ni_0.67Co_0.05Mn_0.28O and spinel type Ni_0.67Co_0.05Mn_0.28O_1.02Wherein the mass ratio of the hexagonal layered structure to the spinel type is 7: 3. the XRD test pattern is shown in figure 5, and it can be seen from figure 5 that the prepared ternary cathode precursor material simultaneously contains a layered structure peak and a spinel structure peak.

A ternary cathode material which differs from example 1 in that: the ternary cathode material is prepared from example 5, and contains a ternary cathode precursor material with a hexagonal layered structure and a spinel type.

A lithium ion battery which differs from example 1 in that: the ternary cathode material prepared in example 5 was used for the cathode plate in the lithium ion battery.

Example 6

Ni of layered structure_0.72Co_0.03Mn_0.25The preparation method of the O ternary cathode precursor material comprises the following steps:

according to Ni_0.72Co_0.03Mn_0.25Mixing a nickel chloride solution, a cobalt chloride solution and a manganese chloride solution according to the stoichiometric ratio of metal elements in the O chemical formula, and concentrating to obtain a mixed solution; wherein the concentrations of the nickel salt, the cobalt salt and the manganese salt are respectively 68.2g/L, 5.1g/L and 26.7 g/L.

② the atomization air quantity is 50m³Atomizing the mixed solution into liquid drops under the condition of/h, roasting at the temperature of 700 ℃ and the oxygen mass percentage content of 5.0 percent, and crushing to obtain Ni_0.72Co_0.03Mn_0.25The crystal structure of the O ternary anode precursor material is a layered structure.

LiNi_0.72Co_0.03Mn_0.25O₂A ternary cathode material, which differs from example 1 in that: ternary cathode material comprising Ni of layered structure in example 6_0.72Co_0.03Mn_0.25And preparing the O ternary anode precursor material.

A lithium ion battery which differs from example 1 in that: the ternary cathode material prepared in example 6 was used for the cathode plate in the lithium ion battery.

Example 7

Spinel type Ni_0.72Co_0.03Mn_0.25O_1.01The preparation method of the ternary positive electrode precursor material comprises the following steps:

according to Ni_0.72Co_0.03Mn_0.25O_1.01Mixing a nickel chloride solution, a cobalt chloride solution and a manganese chloride solution according to the stoichiometric ratio of metal elements in the chemical formula, and concentrating to obtain a mixed solution; wherein the concentrations of the nickel salt, the cobalt salt and the manganese salt are respectively 68.2g/L, 5.1g/L and 26.7 g/L.

② when the atomization air quantity is 50m³Atomizing the mixed solution into liquid drops under the condition of/h, roasting at the temperature of 730 ℃ and the oxygen mass percentage content of 11.0 percent, and crushing to obtain Ni_0.72Co_0.03Mn_0.25O_1.01The crystal structure of the ternary positive electrode precursor material is spinel type.

LiNi_0.72Co_0.03Mn_0.25O₂A ternary cathode material, which differs from example 1 in that: ternary cathode material made of Ni spinel in example 7_0.72Co_0.03Mn_0.25O_1.01And preparing the ternary anode precursor material.

A lithium ion battery which differs from example 1 in that: the ternary cathode material prepared in example 7 was used for the cathode plate in the lithium ion battery.

Example 8

Ni of layered structure_0.6Co_0.10Mn_0.30The preparation method of the O ternary cathode precursor material comprises the following steps:

according to Ni_0.6Co_0.10Mn_0.30Mixing a nickel chloride solution, a cobalt chloride solution and a manganese chloride solution according to the stoichiometric ratio of metal elements in the chemical formula O, and concentrating to obtain a mixed solution; wherein the concentrations of the nickel salt, the cobalt salt and the manganese salt are respectively 68.2g/L, 5.1g/L and 26.7 g/L.

② when the atomization air quantity is 50m³Atomizing the mixed solution into liquid drops under the condition of/h, roasting at the temperature of 720 ℃ and the oxygen mass percentage content of 5.0 percent, and crushing to obtain Ni_0.6Co_0.10Mn_0.30The crystal structure of the O ternary anode precursor material is a layered structure.

LiNi_0.6Co_0.10Mn_0.30O₂A ternary positive electrode material, which differs from example 1 in that: the ternary cathode material is prepared from Ni with a laminated structure in example 6_0.6Co_0.10Mn_0.30And preparing the O ternary anode precursor material.

Example 9

Spinel type Ni_0.60Co_0.1Mn_0.3O_1.19The preparation method of the ternary positive electrode precursor material comprises the following steps:

according to Ni_0.60Co_0.1Mn_0.3O_1.19Mixing a nickel chloride solution, a cobalt chloride solution and a manganese chloride solution according to the stoichiometric ratio of metal elements in the chemical formula, and concentrating to obtain a mixed solution; wherein the concentrations of the nickel salt, the cobalt salt and the manganese salt are respectively 68.2g/L, 5.1g/L and 26.7 g/L.

② when the atomization air quantity is 50m³Atomizing the mixed solution into liquid drops under the condition of/h, roasting at the temperature of 750 ℃ and the oxygen mass percentage content of 11.0 percent, and crushing to obtain Ni_0.60Co_0.1Mn_0.3O_1.19The crystal structure of the ternary positive electrode precursor material is spinel type.

LiNi_0.60Co_0.1Mn_0.3O₂A ternary positive electrode material, which differs from example 1 in that: the ternary cathode material was made of Ni of spinel type of example 9_0.60Co_0.1Mn_0.3O_1.191And preparing the ternary anode precursor material.

A lithium ion battery which differs from example 1 in that: the ternary cathode material prepared in example 9 was used for the cathode plate in the lithium ion battery.

Comparative example 1

Ni_0.67Co_0.05Mn_0.28(OH)₂The preparation method of the ternary positive electrode precursor material comprises the following steps:

according to Ni_0.67Co_0.05Mn_0.28(OH)₂Mixing a nickel chloride solution, a cobalt chloride solution and a manganese chloride solution according to the stoichiometric ratio of metal elements in the chemical formula; then mixing with ammonia water and NaOH solution according to the ammonia-nickel ratio: 0.5:1, alkali-nickel ratio: 2:1, adding ammonia water and sodium hydroxide, controlling the reaction temperature to be 55 ℃ and the PH value to be 12.0, separating after the reaction to obtain Ni_0.67Co_0.05Mn_0.28(OH)₂And (3) precursor.

LiNi_0.67Co_0.05Mn_0.28O₂A ternary positive electrode material, which differs from example 1 in that: the ternary cathode material is prepared from Ni of spinel type in comparative example 1_0.67Co_0.05Mn_0.28(OH)₂And preparing the ternary anode precursor material.

A lithium ion battery which differs from example 1 in that: the lithium ion battery anode plate adopts the ternary anode material prepared in the comparative example 1.

Further, in order to verify the improvement of the examples of the present application, the loose bulk density, the Tap Density (TD), and the particle size of the ternary positive electrode precursor materials prepared in examples 1 to 9 of the present application and comparative example 1 were measured, respectively. In addition, the lithium ion batteries prepared in examples 1 to 9 and comparative example 1 were respectively discharged at 0.1C, charged to 2.5V at 0.1C, recorded for the first lithium intercalation capacity and the lithium deintercalation capacity, and the first effect was calculated. In addition, the capacity retention rate after 50 weeks of charge and discharge of each battery was measured, as well as the 1c energy density. The test results are shown in table 1 below:

TABLE 1

According to the test results, the ternary cathode oxide precursor material prepared in the embodiments 1-9 has relatively high loose bulk density and tap density; the ternary positive electrode hydroxide material prepared in comparative example 1 is secondary particles, and the loose bulk density and tap density of the ternary positive electrode hydroxide material are lower than those of the ternary oxide precursor prepared in the examples, so that the ternary oxide precursor prepared in the examples has better density and high structural stability. In addition, compared with the lithium ion battery prepared from the hydroxide precursor material in the comparative example 1, the lithium ion battery prepared in the embodiments 1 to 9 has higher energy density, first effect and cycling stability.

The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims

1. The ternary anode precursor material is characterized by comprising Ni_(1-y-z)Co_yMn_zO_xWherein x is more than or equal to 1 and less than or equal to 1.2, y is more than or equal to 0.03 and less than or equal to 0.1, and z is more than or equal to 0.2 and less than or equal to 0.35.

2. The ternary cathode precursor material according to claim 1, wherein the crystal structure of the ternary oxide precursor is a single crystal structure selected from a hexagonal layered structure, a spinel-type structure, a cubic structure, and an octahedral structure.

3. The ternary positive electrode precursor material according to claim 2, wherein the ternary positive electrode precursor material comprises at least two of the ternary oxide precursor having the hexagonal layered structure, the ternary oxide precursor having the spinel-type structure, the ternary oxide precursor having the cubic structure, and the ternary oxide precursor having the octahedral structure.

4. The ternary cathode precursor material according to claim 3, comprising the ternary oxide precursor with the hexagonal layered structure and the ternary oxide precursor with the spinel structure, wherein the mass ratio of the ternary oxide precursor with the hexagonal layered structure to the ternary oxide precursor with the spinel structure is (50-100): (1-50).

5. The ternary cathode precursor material according to claim 3, wherein the ternary cathode precursor material comprises the spinel-structured ternary oxide precursor and the cubic-structured ternary oxide precursor, and the mass ratio of the spinel-structured ternary oxide precursor to the cubic-structured ternary oxide precursor is (10-50): (50-90).

6. The ternary cathode precursor material according to claim 3, wherein the ternary cathode precursor material comprises the octahedral ternary oxide precursor and the spinel ternary oxide precursor, and the mass ratio of the octahedral ternary oxide precursor to the spinel ternary oxide precursor is (50-80): (15-50).

7. The ternary positive electrode precursor material according to claim 3, wherein the ternary oxide precursor has a chemical formula of Ni_(1-y-z)Co_yMn_zAnd O, the crystal structure is a hexagonal layered structure, a cubic structure or an octahedral structure.

8. The ternary positive electrode precursor material according to claim 3, wherein the ternary oxide precursor has a chemical formula of Ni_(1-y-z)Co_yMn_zO_xWherein x is greater than 1; the crystal structure is a spinel structure.

9. The ternary positive electrode precursor material according to claim 1, comprising: ni_0.67Co_0.05Mn_0.28O、Ni_0.67Co_0.05Mn_0.28O_1.02、Ni_0.72Co_0.03Mn_0.25O、Ni_0.72Co_0.03Mn_0.25O_1.01、Ni_0.7Co_0.04Mn_0.26O、Ni_0.65Co_0.06Mn_0.29O、Ni_0.62Co_0.08Mn_0.30O、Ni_0.60Co_0.1Mn_0.3O_1.19At least one ternary oxide precursor.

10. The ternary positive electrode precursor material according to any one of claims 1 to 9, wherein the particle size of the ternary oxide precursor is 50 to 800 nm.

11. The ternary positive electrode precursor material according to any one of claims 1 to 9, wherein the ternary positive electrode precursor material has a loose bulk density of 0.5 to 1.0g/cm³。

12. The ternary positive electrode precursor material according to any one of claims 1 to 9, having a tap density of 1.6 to 2.4g/cm³。

13. The ternary positive electrode precursor material according to any one of claims 1 to 9, wherein the particle diameter D50 of the ternary positive electrode precursor material is 1.5 to 3.5 μm.

14. A method for preparing a ternary positive electrode precursor material according to any one of claims 1 to 13, comprising the steps of:

15. A ternary cathode material is obtained by sintering a mixture comprising a lithium source and a ternary cathode precursor material, wherein the ternary cathode precursor material comprises the ternary cathode precursor material according to any one of claims 1 to 13.