CN114520326A - Ternary cathode material and preparation method thereof - Google Patents

Ternary cathode material and preparation method thereof Download PDF

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CN114520326A
CN114520326A CN202210129130.XA CN202210129130A CN114520326A CN 114520326 A CN114520326 A CN 114520326A CN 202210129130 A CN202210129130 A CN 202210129130A CN 114520326 A CN114520326 A CN 114520326A
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ternary
reaction
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reaction kettle
cathode material
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CN114520326B (en
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李加闯
褚凤辉
孟一鸣
成鑫丽
朱用
王梁梁
贺建军
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Nantong Kington Energy Storage Power New Material Co ltd
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Abstract

A ternary positive electrode material with chemical formula LiNixCoyMnzMkZr1‑x‑y‑z‑kO2The M element is one or more of La, Al, W, Y, Eu and B. The preparation method comprises the following steps: firstly, preparing mixed salt solution of Ni, Co, Mn, zirconium salt and M elements, and preparing a precipitator and a complexing agent; keeping the stirring of the reaction kettle open, introducing mixed gas until the oxygen content reaches 10-60 mg/L, and adding the mixed salt solution, a precipitator and a complexing agent into the kettle for coprecipitation; overflowing to a thickener, controlling the solid content in the kettle to be 22-28%, and stopping the reaction when the granularity and the granularity radial distance reach target values; obtaining a ternary precursor after filter pressing, washing and drying; thirdly, the ternary precursor is addedMixing with lithium salt, heating for reaction, crushing and screening to obtain the ternary cathode material. The invention is beneficial to improving the diffusion speed of lithium ions, increasing the contact area with electrolyte and improving the ion transmission efficiency.

Description

Ternary cathode material and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to a ternary anode material and a preparation method thereof.
Background
The rapid development of new energy automobiles drives the increase of the demand of power batteries, and as one of core materials of the power batteries, the market of ternary cathode materials is also wider.
Therefore, in order to make the ternary cathode material better applied to the electric vehicle, researchers have performed a series of modifications on the ternary cathode material. And a small amount of other elements can be doped to improve the cycle performance and rate capability of the ternary cathode material. The prepared ternary cathode material with the hollow interior is beneficial to shortening the transmission path of lithium ions, improving the diffusion speed of the lithium ions, increasing the contact area with electrolyte and improving the ion transmission efficiency.
Disclosure of Invention
The invention aims to provide a ternary cathode material and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention on the product level is as follows:
a ternary positive electrode material with chemical formula LiNixCoyMnzMkZr1-x-y-z-kO2M element is one or more of La, Al, W, Y, Eu and B; wherein x is more than or equal to 0.4 and less than 0.6, y is more than 0.1 and less than 0.6, z is more than 0.1 and less than 0.6, k is more than 0.004 and less than 0.008, and 1-x-y-z-k is more than 0.001 and less than 0.004.
The relevant content in the above technical solution is explained as follows:
1. in the scheme, D50 is 3.5-4.5 um, and the particle size radius distance is 0.75 < (D90-D10)/D502Less than 0.95 and a tap density of 1.15 to 1.45g/cm3The specific surface area is 1.0 to 2.8m2/g。
In order to achieve the purpose, the technical scheme adopted by the invention in the aspect of the method is as follows:
a preparation method of a ternary cathode material comprises the following steps:
preparing a mixed salt solution of Ni, Co, Mn, zirconium salt and M elements, wherein the zirconium salt is one or more of zirconium sulfate, zirconium nitrate and zirconium chloride;
preparing a sodium hydroxide or potassium hydroxide solution with the molar concentration of 8-10 mol/L as a precipitator;
preparing an ammonia water solution with the molar concentration of 1.5-3.5 mol/L as a complexing agent;
step two, keeping the stirring of the reaction kettle started, introducing mixed gas with the flow of 200-400L/h, stopping introducing the mixed gas when the oxygen content in the bottom liquid in the reaction kettle reaches 10-60 mg/L, and continuously adding the mixed salt solution, the precipitator and the complexing agent in the step one into the reaction kettle at the flow rate of 100-400 mL/min respectively for coprecipitation reaction; continuously introducing nitrogen or inert gas in the reaction process, wherein the flow rate is 200-400L/h, the pH value in the reaction kettle is maintained at 11.45-12.45, the reaction temperature is maintained at 50-70 ℃, and the rotating speed of the reaction kettle is 400-600 r/min;
flowing the overflow of the reaction kettle to a thickener, controlling the solid content in the reaction kettle to be 22-28%, and when the granularity D50 of the material in the reaction kettle grows to 2.8-3.4 um, the granularity radial distance reaches 0.65 < (D90-D10)/D502Less than 0.75, and stopping reaction when the interior is a loose honeycomb structure; obtaining a ternary precursor after filter pressing, washing and drying;
and step three, mixing the ternary precursor prepared in the step two with lithium salt, then carrying out heating reaction, cooling to room temperature after the reaction is finished, and crushing and screening to obtain the ternary cathode material.
The relevant content in the above technical solution is explained as follows:
1. in the scheme, in the step one, the total molar concentration of Ni, Co and Mn in the mixed salt solution is 1.8-2.4 mol/L.
2. In the scheme, in the second step, the mixed gas is a mixture of oxygen and nitrogen, and the volume ratio of the oxygen to the nitrogen is 1.5: 1-2.5: 1.
3. In the scheme, in the third step, the molar ratio of the ternary precursor to the lithium salt is 0.82-0.95.
4. In the scheme, in the third step, the mixed material of the ternary precursor and the lithium salt is placed in a muffle furnace, heated to 720-760 ℃ at the heating rate of 3 ℃/min and then reacted for 6 hours, heated to 870-900 ℃ at the heating rate of 10 ℃/min and then reacted for 50-150 minutes, then cooled to 780-830 ℃ at the cooling rate of 10 ℃/min and reacted for 8-14 hours, and finally naturally cooled to room temperature.
5. In the above scheme, the chemical formula of the ternary cathode material is LiNixCoyMnzMkZr1-x-y-z-kO2M element is one or more of La, Al, W, Y, Eu and B; wherein x is more than or equal to 0.4 and less than 0.6, y is more than 0.1 and less than 0.6, z is more than 0.1 and less than 0.6, k is more than 0.004 and less than 0.008, and 1-x-y-z-k is more than 0.001 and less than 0.004.
6. In the scheme, the D50 of the ternary cathode material is 3.5-4.5 um, and the particle size radius distance is 0.75 < (D90-D10)/D502Less than 0.95 and a tap density of 1.15 to 1.45g/cm3The specific surface area is 1.0-2.8 m2/g。
7. In the above scheme, in the third step, the lithium salt may be lithium hydroxide or lithium carbonate, and the heating reaction may be performed by introducing air into a muffle furnace. Muffle furnaces are an optional type of conventional calcination equipment.
The working principle and the advantages of the invention are as follows:
1. according to the invention, one or more of Zr, La, Al, W, Y, Eu and B elements are added in the process of preparing the ternary precursor, so that the doped elements are uniformly distributed on the atomic layer, the interlayer spacing of the ternary cathode material is increased, and the transmission speed of lithium ions is improved.
2. When the ternary precursor is prepared, introducing mixed gas of oxygen and nitrogen, wherein the flow rate is 200-400L/h, the volume ratio of the oxygen to the nitrogen is 1.5: 1-2.5: 1, and the introduction of the mixed gas is suspended when the oxygen content in a bottom liquid in a reaction kettle reaches 10-60 mg/L. The oxidation of the ternary precursor in the initial stage of the reaction can be ensured by quantitatively controlling the oxygen content in the base solution, primary particles are refined, and the interior of the micro-oxidized ternary precursor has a loose honeycomb structure. In addition, the volume ratio of the oxygen to the nitrogen is required to be within the range of the ratio, and the oxygen content in the base solution is too low below the range, so that the honeycomb structure is not favorably formed; if the content is higher than the range, the peroxidation phenomenon can occur, so that the product is too loose and easy to break.
3. When the ternary cathode material is prepared, a mixed material of a ternary precursor and a lithium salt is placed in a muffle furnace, heated to 720-760 ℃ at a heating rate of 3 ℃/min and then reacted for 6 hours, the ternary precursor is gradually oxidized and dehydrated to form an oxide in the process, the lithium salt is converted from a solid state to a molten state, and the lithium salt slowly enters a loose honeycomb structure in the ternary precursor through pores on the surface of the ternary precursor; heating to 870-900 ℃ at a heating rate of 10 ℃/min, reacting for 50-150 min, accelerating the reaction rate of lithium salt and oxide by a rapid heating mode, and simultaneously rapidly dissolving and shrinking the loose honeycomb structure at 870-900 ℃ to form a ternary cathode material with a hollow interior; and then reducing the temperature to 780-830 ℃ at a cooling rate of 10 ℃/min for reacting for 8-14 hours, and finally naturally cooling to room temperature to obtain a product, wherein rapid cooling can prevent the shrinkage of an internal hollow structure and the agglomeration among secondary spherical particles of the ternary cathode material due to too long heating time in a high-temperature section, and the crystallinity of the ternary cathode material can be improved and the electrochemical performance of the material can be improved by continuously reacting for a period of time at 780-830 ℃.
4. The D50 of the ternary anode material prepared by the invention is 3.5-4.5 um, and the granularity diameter distance is 0.75 < (D90-D10)/D502Less than 0.95 and a tap density of 1.15 to 1.45g/cm3The specific surface area is 1.0-2.8 m2(ii) in terms of/g. The smaller D50 is beneficial to shortening the lithium ion transmission path, the narrower granularity pitch can improve the consistency of the product, the moderate specific surface area can increase the contact area of the ternary cathode material and the electrolyte, and the rate capability is improved.
Drawings
FIG. 1A is a sectional electron micrograph of a ternary precursor secondary particle prepared in example 1 of the present invention;
FIG. 1B is a sectional electron microscope image of secondary particles of the ternary cathode material prepared in example 1 of the present invention;
FIG. 2A is a sectional electron micrograph of a ternary precursor secondary particle prepared in comparative example 1 of the present invention;
FIG. 2B is a sectional electron microscope image of secondary particles of the ternary cathode material prepared in comparative example 1 of the present invention;
FIG. 3A is a sectional electron microscope image of the ternary precursor secondary particle prepared in comparative example 2 of the present invention;
FIG. 3B is a sectional electron micrograph of a ternary cathode material secondary particle prepared in comparative example 2 of the present invention;
FIG. 4 is a sectional electron microscope image of a secondary particle of the ternary cathode material prepared in comparative example 3 of the present invention;
FIG. 5 is a sectional electron microscope image of secondary particles of the ternary cathode material prepared in comparative example 4 of the present invention;
FIG. 6A is a sectional electron microscope image of a secondary particle of a ternary precursor prepared in example 2 of the present invention;
fig. 6B is a sectional electron microscope image of the secondary particles of the ternary cathode material prepared in example 2 of the present invention;
FIG. 7 is a rate performance graph of cells prepared in example 1 and comparative examples 1 to 4 of the present invention, which have a voltage window of 3.0 to 4.3V at 25 ℃ under conditions of discharge current densities of 0.1, 0.2, 0.5, 1, 2 and 5C, respectively;
FIG. 8 is a graph of rate capability of a cell prepared in example 2 of the present invention with a voltage window of 3.0-4.3V at 25 deg.C and discharge current densities of 0.1, 0.2, 0.5, 1, 2, and 5C, respectively.
Detailed Description
The invention is further described with reference to the following figures and examples:
the present disclosure will be described more fully hereinafter with reference to the accompanying drawings, in which embodiments of the disclosure may be shown and described, and which, when modified and varied by the techniques taught herein, can be made by those skilled in the art without departing from the spirit and scope of the disclosure.
As used herein, the term (terms), unless otherwise indicated, shall generally have the ordinary meaning as commonly understood by one of ordinary skill in the art, in this written description and in the claims. Certain words used to describe the disclosure are discussed below or elsewhere in this specification to provide additional guidance to those skilled in the art in describing the disclosure.
Example 1: a preparation method of a ternary cathode material sequentially comprises the following steps:
preparing a mixed salt solution of Ni, Co, Mn, zirconium sulfate and lanthanum sulfate, wherein the total molar concentration of Ni, Co and Mn in the mixed salt solution is 2.0 mol/L, and the molar ratio of Ni, Co, Mn, Zr and La elements is 55:15:29.1:0.7: 0.2;
preparing a sodium hydroxide or potassium hydroxide solution with the molar concentration of 10mol/L as a precipitator;
preparing ammonia water solution with the molar concentration of 1.5mol/L as a complexing agent;
step two, keeping the stirring of the reaction kettle started, introducing a mixed gas of oxygen and nitrogen, wherein the volume ratio of the oxygen to the nitrogen is 2:1, the flow is 300L/h, when the oxygen content in a base solution in the reaction kettle reaches 40mg/L, the introduction of the mixed gas is suspended, and continuously adding the mixed salt solution, the precipitant and the complexing agent in the step one into the reaction kettle at the flow speed of 100-400 mL/min respectively for coprecipitation reaction; continuously introducing nitrogen or inert gas as protective gas in the reaction process, maintaining the pH at 11.45-12.45, maintaining the reaction temperature at 50 ℃, and controlling the rotating speed of the reaction kettle at 550 r/min;
the overflow flows to a thickener, the solid content in the reaction kettle is controlled to be 22-28%, and the particle size D50 of the materials in the reaction kettle grows to 3.1um, and the particle size diameter distance (D90-D10)/D502When the content is 0.70, the interior is of a honeycomb structure, and the reaction is stopped; carrying out filter pressing, washing and drying to obtain a ternary precursor;
step three, mixing the ternary precursor prepared in the step two with lithium salt, wherein the molar ratio of the ternary precursor to the lithium salt is 0.88, introducing air into a muffle furnace for heating reaction, heating to 740 ℃ at the heating rate of 3 ℃/min, reacting for 6 hours, heating to 880 ℃ at the heating rate of 10 ℃/min, reacting for 100 minutes, cooling to 810 ℃ at the cooling rate of 10 ℃/min, reacting for 12 hours, and naturally cooling to room temperatureThe ternary anode material is obtained by crushing and screening, and the chemical formula of the product is LiNi0.55Co0.15Mn0.291La0.002Zr0.007O2D50 is 3.7um, particle size span is 0.89, tap density is 1.25g/cm3Specific surface area of 2.5m2The data can be seen in Table 1.
Comparative example 1:
the difference from the embodiment 1 is that: the volume ratio of oxygen to nitrogen in step two was different, the volume ratio of oxygen to nitrogen in comparative example 1 was 0.5:1, and the rest was identical to example 1, and the relevant data are shown in table 1.
Comparative example 2:
the difference from the embodiment 1 is that: in the second step, the oxygen content in the bottom liquid in the reaction kettle is different, the oxygen content in the comparative example 2 reaches 75mg/L, the rest is the same as that in the example 1, and the related data are shown in the table 1.
Comparative example 3:
the difference from the embodiment 1 is that: the heating conditions in the third step are different, in the comparative example 3, the reaction is carried out for 6 hours after the temperature is heated to 740 ℃ at the heating rate of 3 ℃/min, then the reaction is carried out for 100 minutes after the temperature is heated to 850 ℃ at the heating rate of 10 ℃/min, then the reaction is carried out for 12 hours after the temperature is reduced to 810 ℃ at the cooling rate of 10 ℃/min, and finally the reaction is naturally cooled to the room temperature, and relevant data are shown in table 1.
Comparative example 4:
the difference from the embodiment 1 is that: heating conditions in the third step are different, in the comparative example 4, the reaction is carried out for 6 hours after the temperature is heated to 740 ℃ at the heating rate of 3 ℃/min, then the reaction is carried out for 200 minutes after the temperature is heated to 880 ℃ at the heating rate of 10 ℃/min, then the reaction is carried out for 12 hours after the temperature is reduced to 810 ℃ at the cooling rate of 10 ℃/min, and finally the reaction is naturally cooled to the room temperature, wherein relevant data are shown in table 1.
Example 2: a preparation method of a ternary cathode material sequentially comprises the following steps:
preparing a mixed salt solution of Ni, Co, Mn, zirconium sulfate and lanthanum sulfate, wherein the total molar concentration of Ni, Co and Mn in the mixed salt solution is 2.0 mol/L, and the molar ratio of Ni, Co, Mn, Zr and La elements is 46:25:28.2:0.6: 0.2;
preparing a sodium hydroxide or potassium hydroxide solution with the molar concentration of 10mol/L as a precipitator;
preparing ammonia water solution with the molar concentration of 1.5mol/L as a complexing agent;
keeping the stirring of the reaction kettle open, introducing a mixed gas of oxygen and nitrogen, wherein the volume ratio of the oxygen to the nitrogen is 2.2:1, the flow is 300L/h, the introduction of the mixed gas is suspended when the oxygen content in the bottom liquid in the reaction kettle reaches 45mg/L, and continuously adding the mixed salt solution, the precipitator and the complexing agent in the step one into the reaction kettle at the flow rate of 100-400 mL/min respectively for coprecipitation reaction; continuously introducing nitrogen or inert gas as protective gas in the reaction process, maintaining the pH at 11.45-12.45, maintaining the reaction temperature at 55 ℃, and controlling the rotating speed of the reaction kettle at 550 r/min;
overflowing to flow to a concentrating machine, controlling the solid content in the reaction kettle to be 22-28%, and growing the granularity D50 of the materials in the reaction kettle to be 3.3um and the granularity radial distance (D90-D10)/D502When the content is 0.72, the interior is of a honeycomb structure, and the reaction is stopped; carrying out filter pressing, washing and drying to obtain a ternary precursor;
and step three, mixing the ternary precursor prepared in the step two with a lithium salt, wherein the molar ratio of the ternary precursor to the lithium salt is 0.88, introducing air into a muffle furnace for heating reaction, heating to 750 ℃ at the heating rate of 3 ℃/min, reacting for 6 hours, heating to 890 ℃ at the heating rate of 10 ℃/min, reacting for 100 minutes, reducing to 820 ℃ at the cooling rate of 10 ℃/min, reacting for 12 hours, naturally cooling to room temperature, crushing, and screening to obtain the ternary cathode material, wherein the chemical formula of the product is LiNi0.46Co0.25Mn0.282La0.002Zr0.006O2D50 is 3.9um, particle size span is 0.88, tap density is 1.35g/cm3Specific surface area of 2.2m2The data can be seen in Table 1.
Table 1 shows the sample particle size data for example 1 and various comparative examples.
Figure 19238DEST_PATH_IMAGE002
Comparing the data in table 1 for example 1 and the comparative examples shows that: the volume ratio of oxygen to nitrogen and the oxygen content in the base solution had no effect on the particle size D50 of the ternary precursor under otherwise identical conditions. In addition, after the ternary precursor is prepared into a corresponding cathode material, D50 of the ternary precursor tends to become larger, which is mainly related to the larger primary particles after the ternary precursor is calcined.
FIGS. 1A to 1B are views of the ternary precursor Ni prepared in example 10.55Co0.15Mn0.291La0.002Zr0.007(OH)2And a ternary positive electrode material LiNi0.55Co0.15Mn0.291La0.002Zr0.007O2The sectional electron microscope image of the secondary particles shows that the interior of the precursor is in a loose honeycomb structure, and after high-temperature heat treatment, the loose honeycomb structure is melted and recrystallized to form a wall with a certain thickness, and the interior of the wall is changed into a hollow structure. The hollow structure is beneficial to increasing the contact area with the electrolyte and improving the rate capability; the wall thickness provides a relatively stable structure that prevents structural collapse during cycling.
The effect of the precursor and the corresponding positive electrode material prepared in the comparative example 1 (fig. 2A to 2B) and the comparative example 2 (fig. 3A to 3B) is not reached to the effect of the example 1, which shows that the volume ratio of oxygen to nitrogen and the oxygen content in the bottom liquid in the reaction kettle influence the morphology of the precursor and the corresponding positive electrode material.
Comparative example 3 (fig. 4) shows a cross-sectional electron microscope of secondary particles of a ternary cathode material, and the hollow structure inside is no longer apparent because the calcination temperature is lower than that of example 1.
Comparative example 4 (fig. 5) shows that when the sintering time is 100min at a calcination temperature of 880 c, the interior has a hollow structure with a gap in the wall, and thus the calcination time cannot be too long.
FIGS. 6A-6B are the ternary precursor Ni prepared in example 20.46Co0.25Mn0.282La0.002Zr0.006(OH)2And a ternary positive electrode material LiNi0.46Co0.25Mn0.282La0.002Zr0.006O2The sectional electron microscope image of the secondary particles shows that the interior of the precursor is in a loose honeycomb structure, and the interior of the prepared cathode material is in a hollow structure.
FIG. 7 shows LiNi, which is a positive electrode material prepared in each of example 1, comparative example 2, comparative example 3, and comparative example 40.55Co0.15Mn0.291La0.002Zr0.007O2Compared with the multiplying power performance, the multiplying power performance with hollow interior and uniform and complete wall thickness is the best, which is consistent with the appearance analysis.
FIG. 8 is a ternary cathode material LiNi prepared in example 20.46Co0.25Mn0.282La0.002Zr0.006O2As can be seen from the graph, the discharge capacities were 166, 165, 162, 159, 155, 148 and 163mAh/g under the conditions of the charge and discharge current densities of 0.1, 0.2, 0.5, 1, 2 and 5C, respectively. The discharge capacity of the ternary cathode material is reduced with the increase of the charge and discharge current density, and when the charge and discharge current density returns to the initial 0.1C, the discharge capacity returns to the initial level, and the good reversible performance of the ternary cathode material is shown.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered in the protection scope of the present invention.

Claims (9)

1. A ternary positive electrode material characterized in that: has the chemical formula LiNixCoyMnzMkZr1-x-y-z-kO2M element is one or more of La, Al, W, Y, Eu and B; wherein x is more than or equal to 0.4 and less than 0.6, y is more than 0.1 and less than 0.6, z is more than 0.1 and less than 0.6, k is more than 0.004 and less than 0.008, and 1-x-y-z-k is more than 0.001 and less than 0.004.
2. The ternary positive electrode material according to claim 1, characterized in that: d50 is 3.5-4.5 um, and the particle size radius is 0.75 < (D90-D10)/D502Less than 0.95 and the tap density of 1.15 to 1.45g/cm3The specific surface area is 1.0 to 2.8m2/g。
3. A preparation method of a ternary cathode material is characterized by comprising the following steps: the method comprises the following steps:
preparing a mixed salt solution of Ni, Co, Mn, zirconium salt and M elements, wherein the zirconium salt is one or more of zirconium sulfate, zirconium nitrate and zirconium chloride;
preparing a sodium hydroxide or potassium hydroxide solution with the molar concentration of 8-10 mol/L as a precipitator;
preparing an ammonia water solution with the molar concentration of 1.5-3.5 mol/L as a complexing agent;
step two, keeping the stirring of the reaction kettle open, introducing mixed gas with the flow of 200-400L/h, stopping introducing the mixed gas when the oxygen content in the bottom liquid in the reaction kettle reaches 10-60 mg/L, and continuously adding the mixed salt solution, the precipitator and the complexing agent in the step one into the reaction kettle at the flow rate of 100-400 mL/min respectively for coprecipitation reaction; continuously introducing nitrogen or inert gas in the reaction process, wherein the flow rate is 200-400L/h, the pH value in the reaction kettle is maintained at 11.45-12.45, the reaction temperature is maintained at 50-70 ℃, and the rotating speed of the reaction kettle is 400-600 r/min;
flowing the overflow of the reaction kettle to a thickener, controlling the solid content in the reaction kettle to be 22-28%, and when the granularity D50 of the material in the reaction kettle grows to 2.8-3.4 um, the granularity radial distance reaches 0.65 < (D90-D10)/D502Less than 0.75, and stopping reaction when the interior is a loose honeycomb structure; obtaining a ternary precursor after filter pressing, washing and drying;
and step three, mixing the ternary precursor prepared in the step two with lithium salt, then carrying out heating reaction, cooling to room temperature after the reaction is finished, and crushing and screening to obtain the ternary cathode material.
4. The production method according to claim 3, characterized in that: in the first step, the total molar concentration of Ni, Co and Mn in the mixed salt solution is 1.8-2.4 mol/L.
5. The production method according to claim 3, characterized in that: in the second step, the mixed gas is a mixture of oxygen and nitrogen, and the volume ratio of the oxygen to the nitrogen is 1.5: 1-2.5: 1.
6. The production method according to claim 3, characterized in that: in the third step, the molar ratio of the ternary precursor to the lithium salt is 0.82-0.95.
7. The production method according to claim 3, characterized in that: in the third step, the mixed material of the ternary precursor and the lithium salt is placed in a muffle furnace, heated to 720-760 ℃ at the heating rate of 3 ℃/min and then reacted for 6 hours, heated to 870-900 ℃ at the heating rate of 10 ℃/min and then reacted for 50-150 minutes, then cooled to 780-830 ℃ at the cooling rate of 10 ℃/min and reacted for 8-14 hours, and finally naturally cooled to room temperature.
8. The production method according to claim 3, characterized in that: the chemical formula of the ternary cathode material is LiNixCoyMnzMkZr1-x-y-z-kO2M element is one or more of La, Al, W, Y, Eu and B; wherein x is more than or equal to 0.4 and less than 0.6, y is more than 0.1 and less than 0.6, z is more than 0.1 and less than 0.6, k is more than 0.004 and less than 0.008, and 1-x-y-z-k is more than 0.001 and less than 0.004.
9. The method of claim 8, wherein: the D50 of the ternary anode material is 3.5-4.5 um, and the granularity diameter distance is 0.75 < (D90-D10)/D502Less than 0.95 and a tap density of 1.15 to 1.45g/cm3The specific surface area is 1.0-2.8 m2/g。
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