CN109336193B - Multi-element in-situ co-doped ternary material precursor and preparation method and application thereof - Google Patents

Multi-element in-situ co-doped ternary material precursor and preparation method and application thereof Download PDF

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CN109336193B
CN109336193B CN201811225811.6A CN201811225811A CN109336193B CN 109336193 B CN109336193 B CN 109336193B CN 201811225811 A CN201811225811 A CN 201811225811A CN 109336193 B CN109336193 B CN 109336193B
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闫东伟
赵宜男
吴志坚
谷丰宏
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Singular Beijing Technology Co ltd
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Abstract

The invention discloses a multi-element in-situ co-doped ternary material precursor and a preparation method and application thereof. The chemical formula of the precursor is as follows: (Ni)xCoyMnz)1‑a‑cMaNc(OH)2+kWherein 0.65<x≤0.9，0<y≤1/3，0<z is less than or equal to 1/3, x + y + z is 1, a is less than or equal to 0.0001 and less than or equal to 0.01, and c is less than or equal to 0.0001 and less than or equal to 0.01; the radius of the doped ion M is close to that of the lithium ion and is selected from Mg2+、Zr4+、Nb5+、Ta4+、In3+、Sc3+、Y3+、Ce4+、Gd3+One or more of; the radius of the doped ion N is close to that of metal ions of manganese and cobalt in the ternary material and is selected from Ti4+、W6+One or more of them. In the process of preparing the ternary material precursor, the invention introduces two types of metal ions with different ionic radiuses in situ, so that the doped metal ions are uniformly distributed in the precursor phase, and the uniform mixing at the atomic level is realized. Two types of metal ions with different radiuses are doped at different positions, and the parameters of unit cells are cooperatively changed, so that a lithium ion transmission channel can be enlarged, and the ternary material can keep a good lattice structure, thereby obtaining the ternary material with excellent electrochemical performance.

Description

Multi-element in-situ co-doped ternary material precursor and preparation method and application thereof
Technical Field
The invention belongs to the technical field of lithium ion battery electrode materials, and particularly relates to a multi-element in-situ co-doped ternary material precursor, a preparation method thereof and application thereof in preparation of a ternary cathode material of a lithium ion battery.
Background
The currently commonly used and well developed lithium ion battery positive electrode material is mainly lithium cobaltate (LiCoO)2) Lithium nickelate and lithium manganate (Li)xMn2O4) Lithium iron phosphate (LiFePO)4) And the like, a great deal of basic research is carried out at home and abroad, and the industrialization is basically realized. Compared with the traditional positive electrode material, the layered lithium nickel cobalt manganese oxide positive electrode material (hereinafter referred to as ternary material or NCM) better combines the advantages of lithium cobaltate, lithium nickelate and lithium manganateThe three-element synergistic effect ensures that the comprehensive performance of the compound is better than that of any single-component compound. The lithium ion battery anode material has the advantages of high specific capacity, stable cycle performance, relatively low cost, good safety performance and the like, and is proved to be an ideal anode material of a power battery.
However, the ternary materials also have some problems to overcome: (1) the crystal structure of the material is unstable, and the crystal structure is easy to change in the charging and discharging processes; (2) the surface structure of the material is unstable, and the compatibility of the material and electrolyte is poor due to LiPF6The electrolyte contains HF corrosion electrode material to dissolve transition metal ions; (3) ni2+Radius and Li+Radius are similar, so Ni2+Is very soluble in Li+Mutual occupation, leading to the occurrence of cation-mixed phenomenon, Ni2+In Li+The layer not only reduces the specific discharge capacity but also hinders Li+The disordered state of the structure directly deteriorates the electrochemical performance of the material; (4) the thermal stability of the ternary material is poor; (5) the compacted density of the material needs to be further increased.
In response to the above problems, researchers have utilized elemental doping to improve the performance of ternary materials. The metal cation doping is a common method for improving the electrochemical performance of the ternary material, and the common doping cation has Zn2+、Zr2+、Al3+、Ti4+、V5 +、Mo6+And the like, doping the ions into the crystal lattice of the material causes lattice defects, or increases the interlayer spacing, or stabilizes the crystal structure of the material, so that the electrochemical performance of the material is improved. For example, in the patent with the application number of cn201410110848.x, rare earth oxide and a ternary material precursor are subjected to ball milling, and then, a rare earth doped ternary material is obtained through three times of sintering; patent application No. CN201510672398 discloses one-step sintering Ca2+The preparation method of the doped ternary material comprises the step of grinding and sintering nickel, cobalt, manganese and calcium compounds and lithium salt to prepare the ternary material. The patent with the application number of CN201710121639.9 discloses a method for preparing Al by utilizing a sol-gel method3+、Zr2+、Ti4+And the like.
It is well known that in ternary materials, there are currently recognized a total of five cations of different valency and radius: li+(radius:
Figure BDA0001835837080000021
)、Ni2+(radius:
Figure BDA0001835837080000022
)、Ni3+(radius:
Figure BDA0001835837080000023
)、Mn4+(radius:
Figure BDA0001835837080000024
)、Co3+(radius:
Figure BDA0001835837080000025
) (ii) a Of these five cations, there are two types of cations according to the size of the ionic radius: one is Li with larger and close cation radius+And Ni2 +The other is a transition metal ion Ni with a small and close ionic radius3+、Mn4+、Co3+。
On one hand, the method for doping and modifying the ternary material is difficult to ensure that the doped ions are uniformly distributed in the ternary material bulk phase; on the other hand, the single introduction of one kind of ion, or the introduction of a plurality of kinds of ions with similar ionic radii, results in disproportionate change of unit cell parameters of the ternary material, which causes lattice deformity, and it is difficult to ensure that the performance of the ternary material is greatly improved or enhanced.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of a multielement in-situ co-doped ternary precursor and application of the multielement in-situ co-doped ternary precursor in preparation of a ternary cathode material of a lithium ion battery. The multi-element in-situ co-doping is that two types of metal cations with different ionic radii are added simultaneously in the process of preparing a ternary precursor by adopting a chemical coprecipitation method, so that the two types of metal cations with different ionic radii are uniformly distributed in a precursor body phase. Further, the ternary precursor is mixed with a lithium source for sintering, so that the modified ternary cathode material with excellent rate capability and cycle performance is obtained.
In order to achieve the purpose, the invention adopts the following technical scheme:
the chemical formulas of the multi-element in-situ co-doped ternary material precursor and the ternary material are respectively (Ni)xCoyMnz)1-a-cMaNc(OH)2+kAnd Li (Ni)xCoyMnz)1-a-cMaNcO2(ii) a The radius of the metal ion M in the chemical formula is close to that of lithium ion, and the metal ion M is selected from Mg2+、Zn2+、Zr4+、Nb5+、Ta4+、In3+、Sc3+、Y3+、Ce4+、Gd3+One or more of; radius of metal ion N and transition metal ion (Mn) in ternary Material4+、Co3+) Has a radius close to that of Al3+、Ti4+、Ge4+、W6+、V5+One or more of them. Wherein x is not less than 1/3 and not more than 0.9 and 0<y≤1/3，0<z is less than or equal to 0.4, x + y + z is 1, a is less than or equal to 0.0001 and less than or equal to 0.01, c is less than or equal to 0.0001 and less than or equal to 0.01, and the value of k is determined by the valence of the metal ions M and N and the doping amounts a and c.
A multi-element in-situ co-doped ternary material precursor and a preparation method and application thereof comprise the following steps:
(1) preparing a metal salt solution: soluble nickel salt, manganese salt, cobalt salt, M salt corresponding to a doping element M and N salt corresponding to a doping element N are mixed according to a molar ratio of Ni: co: mn: m: n ═ x: y: z: a: c preparing an aqueous solution, and finally preparing the metal salt solution A with the concentration sum of all metal ions of 0.1-3 mol/L.
(2) Preparing a precipitator: soluble alkali is used as a precipitator, and a proper amount of soluble alkali is dissolved in pure water to prepare an alkali solution B with the concentration of 1-8 mol/L.
(3) Preparing a complexing agent: ammonia water is used as a complexing agent, a proper amount of strong ammonia water is taken, a proper amount of pure water is added, and an ammonia water solution C of 2-12mol/L is prepared.
(4) Preparation of ternary precursor (Ni) by chemical coprecipitation methodxCoyMnz)1-a-cMaNc(OH)2+k: and (3) pumping the metal salt solution A prepared in the step (1), the alkali solution B prepared in the step (2) and the ammonia water solution C prepared in the step (3) into a stirring reaction kettle simultaneously, and carrying out chemical precipitation reaction under the protection of inert gas. After the reaction is finished, aging, centrifuging, washing and drying are carried out to obtain the micrometer spherical multi-element co-doped modified ternary precursor (Ni)xCoyMnz)1-a-cMaNc(OH)2+k。
(5) Ternary cathode material Li (Ni)xCoyMnz)1-a-cMaNcO2The preparation of (1): co-doping the multi-element in-situ precursor (Ni) prepared in the step (4)xCoyMnz)1-a-cMaNc(OH)2+kThe method is used for preparing the ternary material of the lithium ion battery. According to the ternary material chemical formula Li (Ni)xCoyMnz)1-a-cMaNcO2The molar ratio of each element in the precursor (Ni) is weighed according to the proper amount prepared in the step (4)xCoyMnz)1-a-cMaNc(OH)2+kAnd a lithium source; fully mixing, placing in a high-temperature sintering furnace, calcining at high temperature in an oxidizing atmosphere, naturally cooling, crushing, screening and deironing to obtain the metal cation M and N co-doped modified ternary cathode material Li (Ni)xCoyMnz)1-a-cMaNcO2。
The multi-element in-situ co-doped ternary material precursor and the preparation method and application thereof are characterized in that in the step (1), the nickel salt, the manganese salt and the cobalt salt are respectively one or more of sulfate, chloride and nitrate corresponding to metal ions.
The multi-element in-situ co-doped ternary material precursor and the preparation method and the application thereof are characterized in that the doping element M in the step (1) is metal ion Mg2+、Zn2+、Zr4+、Nb5+、Ta4+、In3+、Sc3+、Y3+、Ce4+、Gd3+One or more of; the soluble M salt is metal ion Mg2+、Zn2+、Zr4+、Nb5+、Ta4+、In3+、Sc3+、Y3+、Ce4+、Gd3+The corresponding soluble sulfate, chloride, nitrate, oxalate or other corresponding soluble salt.
The multi-element in-situ co-doped ternary material precursor and the preparation method and the application thereof are characterized in that the doping element N in the step (1) is metal ion Al3+、Ti4+、Ge4+、W4+、V5+One or more of; the N salt is metal ion Al3+、Ti4+、Ge4+、W6+、V5+Respectively corresponding to one of sulfate, chloride, nitrate or other corresponding soluble salts.
According to the multi-element in-situ co-doped ternary material precursor and the preparation method and application thereof, the total concentration of metal ions in the metal salt solution A in the step (1) is 0.1-3mol/L, and preferably, the total concentration of all metal ions is 1-2 mol/L.
The multi-element in-situ co-doped ternary material precursor and the preparation method and application thereof are characterized in that the precipitator in the step (2) is one or more of sodium hydroxide, potassium hydroxide or lithium hydroxide; the concentration of the precipitant solution is 1-8mol/L, and preferably, the concentration of the precipitant is 4-6 mol/L.
The multi-element in-situ co-doped ternary material precursor and the preparation method and application thereof are characterized in that the complexing agent in the step (3) is ammonia water, and the concentration of the complexing agent is 2-12 mol/L; preferably, the concentration of the complexing agent is 6-10 mol/L.
The preparation method of the multi-element in-situ co-doped modified ternary cathode material comprises the step (4) of preparing a ternary precursor (Ni) by using a chemical coprecipitation methodxCoyMnz)1-a-cMaNc(OH)2+kThe inert gas is one of nitrogen or argon; in the coprecipitation reaction, the stirring speed is 100-800rpm, the heating temperature is controlled to be 40-80 ℃, and the pH value is controlled to be 9-12; preferably, the inert gas is nitrogen, the stirring speed is 200-600rpm, the heating temperature is controlled to be 50-80 ℃, and the pH value is controlled to be 10-11.
The multi-element in-situ co-doped ternary material precursor and the preparation method and application thereof are characterized in that the lithium source in the step (5) is one of lithium carbonate, lithium hydroxide and lithium acetate containing lithium element. The lithium source is excessive by 2-10% according to the stoichiometric ratio, namely lithium ions and precursor (Ni) in the lithium sourcexCoyMnz)1-a-cMaNc(OH)2+kThe molar ratio of the medium metal ions is (1.02-1.1): 1; preferably, the lithium source is in excess of 3% to 5%, i.e., lithium ions and precursors (Ni) in the lithium sourcexCoyMnz)1-a-cMaNc(OH)2+kThe molar ratio of the metal ions in the solution is (1.03-1.05): 1.
The multi-element in-situ co-doped ternary material precursor and the preparation method and the application thereof are characterized in that the high-temperature sintering in the step (6) is carried out in the air or oxygen atmosphere, the sintering temperature is 650-1100 ℃, the heating speed is 1-5 ℃/min, and the sintering time is 10-30 h; preferably, the sintering temperature is 750-.
Compared with the prior art, the invention has the following beneficial effects:
1. in the process of preparing the ternary material precursor by adopting a coprecipitation method, the multi-element co-doped modified ternary cathode material prepared by the invention introduces the doped metal ions in situ, so that the doped metal ions are uniformly distributed in the precursor phase, and uniform mixing at an atomic level is realized, thereby obtaining the ternary material precursor with higher material activity and higher tap density.
2. The invention adopts an in-situ doping method to selectively introduce two types of metal ions with different radiuses: one class of dopant metal ions has a radius comparable to or close to that of lithium ions and the other class of dopant metal ions has a radius comparable to or close to that of transition metal ions in the ternary material. In the high-temperature sintering process, two types of doping elements are more quickly and uniformly blended into the crystal lattice of the ternary material to be doped at different positions, and the crystal cell parameters are cooperatively changed, so that the lithium ion transmission channel can be enlarged, and the ternary material can keep a good crystal lattice structure, thereby preparing the ternary cathode material with excellent cycle performance and rate capability.
3. In the process of preparing the ternary precursor, various doped metal ions are introduced in situ, so that the preparation process is greatly shortened, the production efficiency is improved, and the method is easy for large-scale industrial production.
Drawings
FIG. 1: EXAMPLE 1 ternary precursor (Ni)0.6Co0.2Mn0.2)0.993Zr0.003Al0.004(OH)2.01Scanning electron micrographs of the samples.
FIG. 2: example 1 ternary cathode material Li (Ni)0.6Co0.2Mn0.2)0.993Zr0.003Al0.004O2Scanning electron micrographs of the samples.
FIG. 3: example 1 ternary cathode material Li (Ni)0.6Co0.2Mn0.2)0.993Zr0.003Al0.004O2XRD pattern of the sample.
FIG. 4: example 1 ternary cathode material Li (Ni)0.6Co0.2Mn0.2)0.993Zr0.003Al0.004O2First charge and discharge curves of the samples.
FIG. 5: example 1 ternary cathode material Li (Ni)0.6Co0.2Mn0.2)0.993Zr0.003Al0.004O2Graph of the rate cycle of the sample.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are only for the purpose of the present invention and are not intended to limit the scope of the present invention. It should be understood that various changes and modifications of the present invention may be made by those skilled in the art after reading the present disclosure, and such equivalents may fall within the scope of the present invention as defined by the appended claims.
Example 1:
this example preparation of Zr4+With Al3+Co-doping of modified ternary precursors (Ni)0.6Co0.2Mn0.2)0.993Zr0.003Al0.004(OH)2.01And a ternary cathode material Li (Ni)0.6Co0.2Mn0.2)0.993Zr0.003Al0.004O2The method comprises the following steps:
(1) preparing a metal salt solution: 8.937mol of nickel sulfate hexahydrate, 2.979mol of cobalt sulfate heptahydrate, 2.979mol of manganese sulfate monohydrate, 0.03mol of aluminum sulfate octadecahydrate and 0.045mol of zirconium sulfate tetrahydrate are respectively weighed and dissolved in a proper amount of pure water to prepare 10 liters of salt solution A, and the total metal ion concentration in the salt solution is 1.5 mol/L.
(2) Preparing a precipitator: 40mol of sodium hydroxide is weighed and dissolved in pure water to prepare 10 liters of sodium hydroxide aqueous solution B with the concentration of 4 mol/L.
(3) Preparing a complexing agent: ammonia water is used as a complexing agent, a proper amount of strong ammonia water is taken, a proper amount of pure water is added, and 10 liters of 8mol/L ammonia water solution C is prepared.
(4) Preparation of Zr by chemical coprecipitation method4+With Al3+Co-doping of modified ternary precursors (Ni)0.6Co0.2Mn0.2)0.993Zr0.003Al0.004(OH)2.01: pumping the metal salt solution A prepared in the step (1), the alkali solution B prepared in the step (2) and the ammonia water solution C prepared in the step (3) into a stirring reaction kettle simultaneously, controlling the stirring speed to be 800rpm, the heating temperature to be 50-80 ℃ and the pH value to be 10-12 under the protection of nitrogen, and carrying out chemical precipitation reaction. After the reaction is finished, aging, centrifuging, washing and drying are carried out to obtain Zr4+With Al3+Co-doped ternary precursor (Ni)0.6Co0.2Mn0.2)0.993Zr0.003Al0.004(OH)2.01。
(5) Ternary cathode material Li (Ni)0.6Co0.2Mn0.2)0.993Zr0.003Al0.004O2The preparation of (1): according to the chemical formula of the ternary cathode material Li (Ni)0.6Co0.2Mn0.2)0.993Zr0.003Al0.004O2The molar ratio of each element in (1) was determined by weighing 2mol of precursor (Ni)0.6Co0.2Mn0.2)0.993Zr0.003Al0.004(OH)2.011.015mol of lithium carbonate; and then fully mixing to obtain a mixture of the precursor and lithium carbonate. Placing the mixture in a high-temperature sintering furnace, heating to 860 ℃ at a heating rate of 2 ℃/min in an oxidizing atmosphere, keeping the temperature for 20 hours, stopping heating, and obtaining Zr after natural cooling, crushing, screening and iron removal4+With Al3+Co-doped modified ternary cathode material Li (Ni)0.6Co0.2Mn0.2)0.993Zr0.003Al0.004O2。
Scanning Electron Microscopy (SEM) was used to align the ternary precursor (Ni) of example 10.6Co0.2Mn0.2)0.993Zr0.003Al0.004(OH)2.01And a ternary cathode material Li (Ni)0.6Co0.2Mn0.2)0.993Zr0.003Al0.004O2And performing surface morphology characterization, as shown in figures 1 and 2. As can be seen from FIG. 1, the obtained precursor has a micro-spherical structure, good sphericity, uniform particle size, and a particle size range of 4-8 μm. Each microparticle is composed of a nanosheet, which varies in thickness from a few nanometers to tens of nanometers. As can be seen from FIG. 2, after lithium-doped high-temperature sintering, the ternary cathode material Li (Ni)0.6Co0.2Mn0.2)0.993Zr0.003Al0.004O2Still maintain better spherical particles and have more uniform particle size, most of the particles are about 6 microns, and each micron particle is composed of a single crystal micron sheet with the thickness of 1 micron.
The ternary positive electrode material Li (Ni) prepared in example 1 was subjected to X-ray powder diffractometry0.6Co0.2Mn0.2)0.993Zr0.003Al0.004O2The structural characterization was performed and the results are shown in fig. 3. Diffraction peaks with alpha-NaFeO can be seen2High goodness of fit, no hetero-phase peak, good lamellar structure, I003/I104The value of (A) is 2.05, which indicates that the phenomenon of mutual occupation of divalent nickel and lithium ions is less.
Zr prepared in this example4+With Al3+Co-doped ternary cathode material Li (Ni)0.6Co0.2Mn0.2)0.993Zr0.003Al0.004O2The electrochemical performance test method is as follows:
li (Ni) was added to a sample of the ternary cathode material prepared in this example0.6Co0.2Mn0.2)0.993Zr0.003Al0.004O2Assembling a CR2025 button cell for positive active materials: first, Li (Ni) was added in a mass ratio of 8:1:10.6Co0.2Mn0.2)0.993Zr0.003Al0.004O2Dispersing acetylene black and PVDF in N-methyl pyrrolidone (NMP) to prepare slurry; then, the slurry was coated on an aluminum foil with a blade coater to form an electrode sheet having a thickness of 150 μm, the electrode sheet was dried in a vacuum drying oven at 120 ℃ for 12 hours, and 1cm was punched on the electrode sheet2The negative electrode wafer of (1); the battery is assembled in a glove box filled with high-purity argon, a lithium sheet is taken as a negative electrode, a Celgard2300 polypropylene porous membrane is taken as a diaphragm, and the electrolyte is 1mol/L LiPF6A mixed solution of Ethylene Carbonate (EC)/dimethyl carbonate (DMC) (volume ratio 1: 1). And assembling into a CR2025 button cell, and carrying out electrochemical performance test.
Fig. 4 is a graph of capacity versus voltage for the first charge and discharge of the sample prepared in example 1 at a voltage range of 2.8-4.3V and a current density of 0.1C (1C-180 mA/g). As can be seen from the figure, the first discharge specific capacity is 185.6mAh/g, the first charge specific capacity is 203.8mAh/g, the first efficiency reaches 91.06%, the polarization effect is small, and the electrochemical performance is good.
FIG. 5 is a graph of the rate cycling curves for samples prepared in example 1 at different current densities over a voltage range of 2.8-4.3V. As can be seen from the figure, the discharge capacity of the sample is 128.9mAh/g at the high current density of 5C, when the current density returns to 0.1C, the discharge capacity reaches 179.3mAh/g again, and after the circulation is continued for 130 times, the discharge capacity still has 168.5 mAh/g; the excellent rate capability and cycle performance are shown.
Example 2:
this example uses a ternary cathode material LiNi0.5Co0.2Mn0.3O2(NCM523) as a substrate to prepare Zr4+、Zn2+With Al3 +Co-doped ternary cathode material Li (Ni)0.5Co0.2Mn0.3)0.99Zr0.003Zn0.002Al0.005O2The method comprises the following steps:
(1) preparing a metal salt solution: 9.9mol of nickel sulfate hexahydrate, 3.96mol of cobalt sulfate heptahydrate, 5.94mol of manganese sulfate monohydrate, 0.05mol of aluminum sulfate octadecahydrate, 0.06mol of zirconium sulfate tetrahydrate and 0.04mol of zinc sulfate heptahydrate are respectively weighed and dissolved in a proper amount of pure water to prepare 10 liters of metal salt water solution A, and the total metal ion concentration in the solution is 2.0 mol/L.
(2) Preparing a precipitator: 60mol of sodium hydroxide is weighed and dissolved in pure water to prepare 10 liters of sodium hydroxide aqueous solution B with the concentration of 6 mol/L.
(3) Preparing a complexing agent: ammonia water is used as a complexing agent, a proper amount of strong ammonia water is taken, a proper amount of pure water is added, and 10 liters of 10mol/L ammonia water solution C is prepared.
(4) Preparation of Zr by chemical coprecipitation method4+、Zn2+With Al3+Co-doped ternary Material precursor (Ni)0.5Co0.2Mn0.3)0.99Zr0.003Zn0.002Al0.005(OH)2.011: pumping the metal salt solution A prepared in the step (1), the alkali solution B prepared in the step (2) and the ammonia water solution C prepared in the step (3) into a stirring reaction kettle simultaneously, controlling the stirring speed to be 800rpm, the heating temperature to be 50-80 ℃ and the pH value to be 10-12 under the protection of nitrogen, and carrying out chemical precipitation reaction. After the reaction is finished, aging, centrifuging, washing and drying are carried out to obtain Zr4+、Zn2+And with Al3+Co-doped ternary Material precursor (Ni)0.5Co0.2Mn0.3)0.99Zr0.003Zn0.002Al0.005(OH)2.011。
(5) Ternary cathode material Li (Ni)0.5Co0.2Mn0.3)0.99Zr0.003Zn0.0023Al0.005O2The preparation of (1): according to the chemical formula of the ternary cathode material Li (Ni)0.5Co0.2Mn0.3)0.99Zr0.003Zn0.0023Al0.005O2The molar ratio of each element in the solution is 2mol of precursor Ni0.5Co0.2Mn0.3)0.99Zr0.003Zn0.002Al0.005(OH)2.0111.015mol of lithium carbonate; and then fully mixing to obtain a mixture of the precursor and lithium carbonate. Placing the mixture in a high-temperature sintering furnace, heating to 880 ℃ at a heating rate of 2 ℃/min in an oxidizing atmosphere, keeping for 20 hours, stopping heating, and obtaining metal cation Zr after natural cooling, crushing, screening and iron removal4+、Zn2+With Al3+Co-doped ternary cathode material Li (Ni)0.5Co0.2Mn0.3)0.99Zr0.003Zn0.002Al0.005O2。
Ternary cathode material Li (Ni) was prepared for example 2 in accordance with the method of example 10.5Co0.2Mn0.3)0.99Zr0.003Zn0.002Al0.005O2Electrochemical performance tests were performed.
The result shows that under the conditions of a voltage range of 2.8-4.3V and a current density of 0.1C (1C is 180mA/g), the first discharge capacity is 170.8mAh/g, the first charge capacity is 184.5mAh/g, the first coulombic efficiency reaches 92.6%, after 100 times of circulation, the discharge capacity is 160.2mAh/g, the capacity retention rate is 93.8%, and good electrochemical performance is shown.
Example 3:
this example uses a ternary cathode material LiNi0.6Co0.2Mn0.2O2(NCM622) as matrix for preparing Mg2+、Sc3+、Al3+With Ti4+Co-doped ternary cathode material Li (Ni)0.6Co0.2Mn0.2)0.99Mg0.003Sc0.002Al0.004Ti0.001O 2The method comprises the following steps:
(1) preparing a metal salt solution: 5.94mol of nickel sulfate hexahydrate, 1.98mol of cobalt sulfate heptahydrate, 1.98mol of manganese sulfate monohydrate, 0.03mol of magnesium sulfate, 0.02mol of aluminum sulfate octadecahydrate, 0.01mol of scandium sulfate octahydrate and 0.01mol of titanium tetrachloride are respectively weighed and dissolved in a proper amount of pure water to prepare 10 liters of metal salt aqueous solution A, and the total metal ion concentration in the aqueous solution is 1 mol/L.
(2) Preparing a precipitator: 30mol of sodium hydroxide is weighed and dissolved in pure water to prepare 10 liters of sodium hydroxide aqueous solution B with the concentration of 3 mol/L.
(3) Preparing a complexing agent: ammonia water is used as a complexing agent, a proper amount of strong ammonia water is taken, a proper amount of pure water is added, and 10 liters of 8mol/L ammonia water solution C is prepared.
(4) Chemical coprecipitation method for preparing Mg2+、Sc3+、Al3+With Ti4+Co-doped ternary Material precursor (Ni)0.6Co0.2Mn0.2)0.99Mg0.003Sc0.002Al0.004Ti0.001(OH)2.008: pumping the metal salt solution A prepared in the step (1), the alkali solution B prepared in the step (2) and the ammonia water solution C prepared in the step (3) into a stirring reaction kettle simultaneously, controlling the stirring speed to be 800rpm, the heating temperature to be 50-80 ℃ and the pH value to be 10-12 under the protection of nitrogen, and carrying out chemical precipitation reaction. After the reaction is finished, aging, centrifuging, washing and drying are carried out to obtain Mg2+、Sc3+、Al3+With Ti4+Co-doped ternary Material precursor (Ni)0.6Co0.2Mn0.2)0.99Mg0.003Sc0.002Al0.004Ti0.001(OH)2.008。
(5) Ternary cathode material Li (Ni)0.6Co0.2Mn0.2)0.99Mg0.003Sc0.002Al0.004Ti0.001O2The preparation of (1): according to the chemical formula of the ternary cathode material Li (Ni)0.6Co0.2Mn0.2)0.99Mg0.003Sc0.002Al0.004Ti0.001O2The molar ratio of each element in (1) was determined by weighing 2mol of precursor (Ni)0.6Co0.2Mn0.2)0.99Mg0.003Sc0.002Al0.004Ti0.001(OH)2.0081.015mol of lithium carbonate; and then fully mixing to obtain a mixture of the precursor and lithium carbonate. Placing the prepared mixture in a high-temperature sintering furnace, heating to 860 ℃ at a heating rate of 2 ℃/min in an oxidizing atmosphere, keeping for 20 hours, stopping heating, and obtaining the metal cation Zr after natural cooling, crushing, screening and iron removal4+With Al3+Co-doped ternary cathode material Li (Ni)0.6Co0.2Mn0.2)0.99Mg0.003Sc0.002Al0.004Ti0.001O2。
The ternary positive electrode material Li (Ni) prepared in example 3 was subjected to the method of example 10.6Co0.2Mn0.2)0.99Mg0.003Sc0.002Al0.004Ti0.001O2The samples were tested for electrochemical performance.
Test results show that under the conditions of a voltage range of 2.8-4.3V and a current density of 0.1C (1C is 180mA/g), the first discharge capacity is 188.1mAh/g, the first charge capacity is 204.7mAh/g, and the first coulombic efficiency reaches 91.89%; after the cycle of 100 times, the discharge capacity is 175.7mAh/g, the capacity retention rate is 93.4 percent, and good electrochemical performance is shown.
Example 4:
this example uses a ternary cathode material LiNi0.6Co0.2Mn0.2O2(NCM622) as matrix, preparation of Nb5+With Al3+Co-doped ternary cathode material Li (Ni)0.6Co0.2Mn0.2)0.987Nb0.006Al0.007O2The method comprises the following steps:
(1) preparing a metal salt solution: 5.94mol of nickel sulfate hexahydrate, 1.98mol of cobalt sulfate heptahydrate, 1.98mol of manganese sulfate monohydrate, 0.06mol of niobium oxalate hexahydrate and 0.0035mol of aluminum sulfate octadecahydrate are respectively weighed and dissolved in a proper amount of pure water to prepare 10 liters of metal salt aqueous solution A, wherein the total metal ion concentration in the salt solution is 1 mol/L.
(2) Preparing a precipitator: 30mol of sodium hydroxide is weighed and dissolved in pure water to prepare 10 liters of sodium hydroxide aqueous solution B with the concentration of 3 mol/L.
(3) Preparing a complexing agent: ammonia water is used as a complexing agent, a proper amount of strong ammonia water is taken, a proper amount of pure water is added, and 10 liters of 8mol/L ammonia water solution C is prepared.
(4) Preparation of Nb by chemical coprecipitation method5+With Al3+Co-doped ternary Material precursor (Ni)0.6Co0.2Mn0.2)0.987Nb0.006Al0.007(OH)2.025: pumping the metal salt solution A prepared in the step (1), the alkali solution B prepared in the step (2) and the ammonia water solution C prepared in the step (3) into a stirring reaction kettle simultaneously, controlling the stirring speed to be 800rpm, the heating temperature to be 50-80 ℃ and the pH value to be 10-12 under the protection of nitrogen, and carrying out chemical precipitation reaction. After the reaction is finished, aging, centrifuging, washing and drying are carried out to obtain Nb5+And Mo6+Co-doped ternary Material precursor (Ni)0.6Co0.2Mn0.2)0.987Nb0.006Al0.007(OH)2.046。
(5) Ternary cathode material Li (Ni)0.6Co0.2Mn0.2)0.987Nb0.006Al0.007O2The preparation of (1): according to the chemical formula of the ternary cathode material Li (Ni)0.6Co0.2Mn0.2)0.987Nb0.006Al0.007O2The molar ratio of each element in (1) was determined by weighing 2mol of precursor (Ni)0.6Co0.2Mn0.2)0.987Nb0.006Al0.007(OH)2.0251.015mol of lithium carbonate; then mixing thoroughly to obtain the productA mixture of a precursor and lithium carbonate. Placing the mixture in a high-temperature sintering furnace, heating to 860 ℃ at a heating rate of 2 ℃/min in an oxidizing atmosphere, keeping for 20 hours, stopping heating, and naturally cooling, crushing, screening and deironing to obtain the metal cation Nb5+With Al3+Co-doped ternary cathode material Li (Ni)0.6Co0.2Mn0.2)0.987Nb0.006Al0.007O2。
The ternary positive electrode material Li (Ni) prepared in example 4 was subjected to the method of example 10.6Co0.2Mn0.2)0.987Nb0.006Al0.007O2The samples were tested for electrochemical performance.
Test results show that under the conditions of a voltage range of 2.8-4.3V and a current density of 0.1C (1C is 180mA/g), the first discharge capacity is 181.2mAh/g, the first charge capacity is 198.5mAh/g, and the first coulombic efficiency reaches 91.28%; after the cycle of 100 times, the discharge capacity is 172.3mAh/g, the capacity retention rate is 95.08 percent, and good electrochemical performance is shown.
Example 5:
this example uses a ternary cathode material LiNi0.6Co0.2Mn0.2O2(NCM622) as a substrate, In was prepared3+、Ta5+With Al3 +、Ge4+Co-doped ternary cathode material Li (Ni)0.6Co0.2Mn0.2)0.99In0.003Ta0.002Ge0.002Al0.003O 2The method comprises the following steps:
(1) preparing a metal salt solution: 5.94mol of nickel sulfate hexahydrate, 1.98mol of cobalt sulfate heptahydrate, 1.98mol of manganese sulfate monohydrate, 0.015mol of indium sulfate nonahydrate, 0.02mol of potassium heptafluorotantalate, 0.015mol of aluminum sulfate octadecahydrate and 0.02mol of germanium dioxide are respectively weighed and dissolved in a proper amount of pure water to prepare 10 liters of metal salt aqueous solution A, and the total metal ion concentration in the salt solution is 1 mol/L.
(2) Preparing a precipitator: 30mol of sodium hydroxide is weighed and dissolved in pure water to prepare 10 liters of sodium hydroxide aqueous solution B with the concentration of 3 mol/L.
(3) Preparing a complexing agent: ammonia water is used as a complexing agent, a proper amount of strong ammonia water is taken, a proper amount of pure water is added, and 10 liters of 8mol/L ammonia water solution C is prepared.
(4) Preparation of In by chemical coprecipitation method3+、Ta5+With Al3+、Ge4+Co-doped ternary Material precursor (Ni)0.6Co0.2Mn0.2)0.99In0.003Ta0.002Ge0.002Al0.003(OH)2.016: pumping the metal salt solution A prepared in the step (1), the alkali solution B prepared in the step (2) and the ammonia water solution C prepared in the step (3) into a stirring reaction kettle simultaneously, controlling the stirring speed to be 800rpm, the heating temperature to be 50-80 ℃ and the pH value to be 10-12 under the protection of nitrogen, and carrying out chemical precipitation reaction. After the reaction is finished, aging, centrifuging, washing and drying are carried out to obtain In3+、Ta5+And Cr3+、Ge4+Co-doped ternary Material precursor (Ni)0.6Co0.2Mn0.2)0.99In0.003Ta0.002Ge0.002Al 0.003(OH)2.016。
(5) Ternary cathode material Li (Ni)0.6Co0.2Mn0.2)0.99In0.003Ta0.002Ge0.002Al0.003O2The preparation of (1): according to the chemical formula of the ternary cathode material Li (Ni)0.6Co0.2Mn0.2)0.99In0.003Ta0.002Ge0.002Al0.003O2The molar ratio of each element in (1) was determined by weighing 2mol of precursor (Ni)0.6Co0.2Mn0.2)0.99In0.003Ta0.02Ge0.002Al 0.003(OH)2.0161.015mol of lithium carbonate; and then fully mixing to obtain a mixture of the precursor and lithium carbonate. Placing the mixture prepared in the step into a high-temperature sintering furnace, heating to 860 ℃ at a heating rate of 2 ℃/min in an oxidizing atmosphere, keeping for 20 hours, stopping heating, and obtaining the metal after natural cooling, crushing, screening and iron removalCation In3+、Ta5+With Al3+、Ge4+Co-doped ternary cathode material Li (Ni)0.6Co0.2Mn0.2)0.99In0.003Ta0.002Ge0.002Al0.003O2。
The ternary positive electrode material Li (Ni) prepared in example 5 was subjected to the method of example 10.6Co0.2Mn0.2)0.99In0.003Ta0.002Ge0.002Al0.003O2The samples were tested for electrochemical performance.
Test results show that under the conditions of a voltage range of 2.8-4.3V and a current density of 0.1C (1C is 180mA/g), the first discharge capacity is 188.5mAh/g, the first charge capacity is 206.8mAh/g, and the first coulombic efficiency reaches 91.15%; after the cycle of 100 times, the discharge capacity is 178.7mAh/g, the capacity retention rate is 94.8 percent, and the electrochemical performance is good.
Example 6:
this example uses a ternary cathode material LiNi0.6Co0.2Mn0.2O2(NCM622) as a substrate, preparation of Y3+、Ce4+、Gd3+And V5+、W6+Co-doped ternary cathode material Li (Ni)0.6Co0.2Mn0.2)0.99Y0.002Ce0.002Gd0.002V0.002W0.002O 2The method comprises the following steps:
(1) preparing a metal salt solution: 5.94mol of nickel sulfate hexahydrate, 1.98mol of cobalt sulfate heptahydrate, 1.98mol of manganese sulfate monohydrate, 0.01mol of yttrium sulfate octahydrate, 0.02mol of cerium sulfate tetrahydrate, 0.01mol of gadolinium sulfate octahydrate, 0.02mol of cerium sulfate tetrahydrate, 0.02mol of ammonium metavanadate and 0.02mol of ammonium tungstate are respectively weighed and dissolved in a proper amount of pure water to prepare 10 liters of metal salt aqueous solution A, wherein the total metal ion concentration in the salt solution is 1 mol/L.
(2) Preparing a precipitator: 30mol of sodium hydroxide is weighed and dissolved in pure water to prepare 10 liters of sodium hydroxide aqueous solution B with the concentration of 3 mol/L.
(3) Preparing a complexing agent: ammonia water is used as a complexing agent, a proper amount of strong ammonia water is taken, a proper amount of pure water is added, and 10 liters of 8mol/L ammonia water solution C is prepared.
(4) Preparation of Y by chemical coprecipitation method3+、Ce4+、Gd3+And V5+、W6+Co-doped ternary Material precursor (Ni)0.6Co0.2Mn0.2)0.99Y0.002Ce0.002Gd0.002V0.002W0.002(OH)2.022: pumping the metal salt solution A prepared in the step (1), the alkali solution B prepared in the step (2) and the ammonia water solution C prepared in the step (3) into a stirring reaction kettle simultaneously, controlling the stirring speed to be 800rpm, the heating temperature to be 50-80 ℃ and the pH value to be 10-12 under the protection of nitrogen, and carrying out chemical precipitation reaction. After the reaction is finished, aging, centrifuging, washing and drying are carried out to obtain Y3+、Ce4+、Gd3+And V5+、W6+Co-doped ternary Material precursor (Ni)0.6Co0.2Mn0.2)0.99Y0.002Ce0.002Gd0.002V0.002W0.002(OH)2.022。
(5) Ternary cathode material Li (Ni)0.6Co0.2Mn0.2)0.99Y0.002Ce0.002Gd0.002V0.002W0.002O 2The preparation of (1): according to the chemical formula of the ternary cathode material Li (Ni)0.6Co0.2Mn0.2)0.99Y0.002Ce0.002Gd0.002V0.002W0.002O 2The molar ratio of each element in the solution is 2mol of precursor Li (Ni)0.6Co0.2Mn0.2)0.99Y0.002Ce0.002Gd0.002V0.002W0.002(OH)2.0221.015mol of lithium carbonate; then fully mixing to obtain a mixture of the precursor and lithium carbonate; placing the mixture in a high-temperature sintering furnace, heating to 860 ℃ at a heating rate of 2 ℃/min in an oxidizing atmosphere, keeping for 20h, stopping heating, and naturally cooling, crushing, screening and deironing to obtain the metalCation Y3+、Ce4+、Gd3+And V5+、W6+Co-doped ternary cathode material Li (Ni)0.6Co0.2Mn0.2)0.99Y0.002Ce0.002Gd0.002V0.002W0.002O2。
The ternary positive electrode material Li (Ni) prepared in example 6 was subjected to the method of example 10.6Co0.2Mn0.2)0.99Y0.002Ce0.002Gd0.002V0.002W0.002O2The samples were tested for electrochemical performance.
Test results show that under the conditions of a voltage range of 2.8-4.3V and a current density of 0.1C (1C is 180mA/g), the first discharge capacity is 180.6mAh/g, the first charge capacity is 203.1mAh/g, and the first coulombic efficiency reaches 88.92%; after the cycle of 100 times, the discharge capacity is 166.1mAh/g, the capacity retention rate is 91.97 percent, and good electrochemical performance is shown.
Example 7:
this example uses a ternary cathode material LiNi0.8Co0.1Mn0.1O2(NCM811) as a substrate to prepare Zr4+With Al3+Co-doped ternary cathode material, Li (Ni)0.8Co0.1Mn0.1)0.993Zr0.003Al0.004O2The method comprises the following steps:
(1) preparing a metal salt solution: 7.944mol of nickel sulfate hexahydrate, 0.993mol of cobalt sulfate heptahydrate, 0.993mol of manganese sulfate monohydrate, 0.02mol of aluminum sulfate octadecahydrate and 0.03mol of zirconium sulfate tetrahydrate are respectively weighed and dissolved in a proper amount of pure water to prepare 10 liters of metal salt water solution A, and the total metal ion concentration in the salt solution is 1 mol/L.
(2) Preparing a precipitator: 30mol of sodium hydroxide is weighed and dissolved in pure water to prepare 10 liters of sodium hydroxide aqueous solution B with the concentration of 3 mol/L.
(3) Preparing a complexing agent: ammonia water is used as a complexing agent, a proper amount of strong ammonia water is taken, a proper amount of pure water is added, and 10 liters of 8mol/L ammonia water solution C is prepared.
(4) Preparation of Zr by chemical coprecipitation method4+With Al3+Co-doped ternary Material precursor (Ni)0.8Co0.1Mn0.1)0.993Zr0.003Al0.004(OH)2.01: pumping the metal salt solution A prepared in the step (1), the alkali solution B prepared in the step (2) and the ammonia water solution C prepared in the step (3) into a stirring reaction kettle simultaneously, controlling the stirring speed to be 800rpm, the heating temperature to be 50-80 ℃ and the pH value to be 10-12 under the protection of nitrogen, and carrying out chemical precipitation reaction. After the reaction is finished, aging, centrifuging, washing and drying are carried out to obtain Zr4+With Al3+Co-doped ternary Material precursor (Ni)0.8Co0.1Mn0.1)0.993Zr0.003Al0.004(OH)2.01。
(5) Ternary cathode material Li (Ni)0.8Co0.1Mn0.1)0.993Zr0.003Al0.004O2The preparation of (1): according to the chemical formula of the ternary cathode material Li (Ni)0.8Co0.1Mn0.1)0.993Zr0.003Al0.004O2The molar ratio of each element in (1) was determined by weighing 2mol of precursor (Ni)0.8Co0.1Mn0.1)0.993Zr0.003Al0.004(OH)2.012.05mol of lithium hydroxide; and then fully mixing to obtain a mixture of the precursor and the lithium hydroxide. Placing the mixture in a high-temperature sintering furnace, heating to 760 ℃ at a heating rate of 2 ℃/min in an oxidizing atmosphere, keeping for 20 hours, stopping heating, and obtaining metal cation Zr after natural cooling, crushing, screening and iron removal4+With Al3+Co-doped ternary cathode material Li (Ni)0.8Co0.1Mn0.1)0.993Zr0.003Al0.004O2。
The ternary positive electrode material Li (Ni) prepared in example 7 was subjected to the method of example 10.8Co0.1Mn0.1)0.993Zr0.003Al0.004O2The samples were tested for electrochemical performance.
Test results show that under the conditions of a voltage range of 2.8-4.3V and a current density of 0.1C (1C is 200mA/g), the first discharge capacity is 216.2mAh/g, the first charge capacity is 238.6mAh/g, and the first coulombic efficiency reaches 90.61%; after the cycle of 100 times, the discharge capacity is 198.9mAh/g, the capacity retention rate is 92.0 percent, and the electrochemical performance is good.
Example 8:
this example uses a ternary cathode material LiNi0.8Co0.1Mn0.1O2(NCM811) as a substrate to prepare Zr4+With Al3+Co-doped ternary cathode material, Li (Ni)0.8Co0.1Mn0.1)0.99Zr0.008Al0.002O2The method comprises the following steps:
(1) preparing a metal salt solution: 7.92mol of nickel sulfate hexahydrate, 0.99mol of cobalt sulfate heptahydrate, 0.99mol of manganese sulfate monohydrate, 0.01mol of aluminum sulfate octadecahydrate and 0.08mol of zirconium sulfate tetrahydrate are respectively weighed and dissolved in a proper amount of pure water to prepare 10 liters of metal salt water solution A, wherein the total metal ion concentration in the salt solution is 1 mol/L.
(2) Preparing a precipitator: 30mol of sodium hydroxide is weighed and dissolved in pure water to prepare 10 liters of sodium hydroxide aqueous solution B with the concentration of 3 mol/L.
(3) Preparing a complexing agent: ammonia water is used as a complexing agent, a proper amount of strong ammonia water is taken, a proper amount of pure water is added, and 10 liters of 8mol/L ammonia water solution C is prepared.
(4) Preparation of Zr by chemical coprecipitation method4+With Al3+Co-doped ternary Material precursor (Ni)0.8Co0.1Mn0.1)0.99Zr0.008Al0.002(OH)2.018: pumping the metal salt solution A prepared in the step (1), the alkali solution B prepared in the step (2) and the ammonia water solution C prepared in the step (3) into a stirring reaction kettle simultaneously, controlling the stirring speed to be 800rpm, the heating temperature to be 50-80 ℃ and the pH value to be 10-12 under the protection of nitrogen, and carrying out chemical precipitation reaction. After the reaction is finished, aging, centrifuging, washing and drying are carried out to obtain Zr4+With Al3+Co-doped ternary Material precursor (Ni)0.8Co0.1Mn0.1)0.99Zr0.008Al0.002(OH)2.018。
(5) Ternary cathode material Li (Ni)0.8Co0.1Mn0.1)0.99Zr0.008Al0.002O2The preparation of (1): according to the chemical formula of the ternary cathode material Li (Ni)0.8Co0.1Mn0.1)0.99Zr0.008Al0.002O2The molar ratio of each element in (1) was determined by weighing 2mol of precursor (Ni)0.8Co0.1Mn0.1)0.99Zr0.008Al0.002(OH)2.0182.05mol of lithium hydroxide; and then fully mixing to obtain a mixture of the precursor and lithium carbonate. Then, placing the mixture in a high-temperature sintering furnace, heating to 750 ℃ at a heating rate of 2 ℃/min in an oxidizing atmosphere, keeping for 20 hours, stopping heating, and obtaining the metal cation Zr after natural cooling, crushing, screening and iron removal4+With Al3+Co-doped ternary cathode material Li (Ni)0.8Co0.1Mn0.1)0.99Zr0.008Al0.002O2。
The ternary positive electrode material Li (Ni) prepared in example 8 was subjected to the method of example 10.8Co0.1Mn0.1)0.99Zr0.008Al0.002O2The samples were tested for electrochemical performance.
Test results show that under the conditions of a voltage range of 2.8-4.3V and a current density of 0.1C (1C is 180mA/g), the first discharge capacity is 215.7mAh/g, the first charge capacity is 235.1mAh/g, and the first coulombic efficiency reaches 91.75%; after the cycle of 100 times, the discharge capacity is 200.6mAh/g, the capacity retention rate is 93.0 percent, and the electrochemical performance is good.
Example 9:
this example uses a ternary cathode material LiNi0.85Co0.05Mn0.1O2As a substrate, Zr was prepared4+With Al3+Co-doped ternary cathode material Li (Ni)0.85Co0.05Mn0.1)0.98Zr0.01Al0.01O2The method comprises the following steps:
(1) preparing a metal salt solution: respectively weighing 8.33mol of nickel sulfate hexahydrate, 0.49mol of cobalt sulfate heptahydrate, 0.98mol of manganese sulfate monohydrate, 0.005mol of aluminum sulfate octadecahydrate and 0.01mol of zirconium sulfate tetrahydrate, dissolving in a proper amount of pure water to prepare 10 liters of metal salt water solution A, wherein the total metal ion concentration in the salt solution is 1 mol/L.
(2) Preparing a precipitator: 30mol of sodium hydroxide is weighed and dissolved in pure water to prepare 10 liters of sodium hydroxide aqueous solution B with the concentration of 3 mol/L.
(3) Preparing a complexing agent: ammonia water is used as a complexing agent, a proper amount of strong ammonia water is taken, a proper amount of pure water is added, and 10 liters of 8mol/L ammonia water solution C is prepared.
(4) Preparation of Zr by chemical coprecipitation method4+With Al3+Co-doped ternary Material precursor (Ni)0.85Co0.05Mn0.1)0.98Zr0.01Al0.01(OH)2.03: pumping the metal salt solution A prepared in the step (1), the alkali solution B prepared in the step (2) and the ammonia water solution C prepared in the step (3) into a stirring reaction kettle simultaneously, controlling the stirring speed to be 800rpm, the heating temperature to be 50-80 ℃ and the pH value to be 10-12 under the protection of nitrogen, and carrying out chemical precipitation reaction. After the reaction is finished, aging, centrifuging, washing and drying are carried out to obtain Zr4+With Al3+Co-doped ternary Material precursor (Ni)0.85Co0.05Mn0.1)0.98Zr0.01Al0.01(OH)2.03。
(5) Ternary cathode material Li (Ni)0.85Co0.05Mn0.1)0.98Zr0.01Al0.01O2The preparation of (1): according to the chemical formula of the ternary cathode material Li (Ni)0.85Co0.05Mn0.1)0.98Zr0.01Al0.01O2The molar ratio of each element in (1) was determined by weighing 2mol of precursor (Ni)0.85Co0.05Mn0.1)0.98Zr0.01Al0.01(OH)2.032.06mol of lithium hydroxide; then fully mixing to obtainTo a mixture of precursor and lithium carbonate. Then, placing the mixture in a high-temperature sintering furnace, heating to 740 ℃ at a heating rate of 2 ℃/min in an oxidizing atmosphere, keeping for 20 hours, stopping heating, and obtaining the metal cation Zr after natural cooling, crushing, screening and iron removal4+With Al3+Co-doped ternary cathode material Li (Ni)0.85Co0.05Mn0.1)0.98Zr0.01Al0.01O2。。
The ternary positive electrode material Li (Ni) prepared in example 9 was subjected to the method of example 10.85Co0.05Mn0.1)0.98Zr0.01Al0.01O2The samples were tested for electrochemical performance.
Test results show that under the conditions of a voltage range of 2.8-4.3V and a current density of 0.1C (1C is 180mA/g), the first discharge capacity is 220.6mAh/g, the first charge capacity is 239.2mAh/g, and the first coulombic efficiency reaches 92.1%; after the cycle of 100 times, the discharge capacity is 206.7mAh/g, the capacity retention rate is 93.7 percent, and the electrochemical performance is good.
In summary, the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (15)

1. A multi-element in-situ co-doped ternary material precursor has the chemical formula: (Ni)xCoyMnz)1-a-cMaNc(OH)2+kWherein 0.65<x≤0.9，0<y≤1/3，0<z is less than or equal to 1/3, x + y + z is 1, a is less than or equal to 0.0001 and less than or equal to 0.01, and c is less than or equal to 0.0001 and less than or equal to 0.01; the doped metal ion M in the chemical formula is selected from Y3+、Ce4+、Gd3+One or more of; radius of doped metal ion N and transition metal ion Mn in ternary material4+、Co3+Has a radius close to that of Ti4+、W6+One or more kinds of ions, the value of k is determined by the combined valence and doping amount of the metal ions M and N。
2. The preparation method of the multi-element in-situ co-doped ternary material precursor of claim 1, comprising the following steps:
(1) preparing a metal salt solution: soluble nickel salt, manganese salt, cobalt salt, M salt corresponding to a doping element M and N salt corresponding to a doping element N are mixed according to a molar ratio of Ni: co: mn: m: n ═ x: y: z: a: c preparing an aqueous solution, and finally preparing a metal salt solution A with the concentration sum of all metal ions of 0.1-3 mol/L;
(2) preparing a precipitator: taking soluble alkali as a precipitator, dissolving a proper amount of soluble alkali in pure water, and preparing an alkali solution B with the concentration of 1-8 mol/L;
(3) preparing a complexing agent: ammonia water is used as a complexing agent, a proper amount of strong ammonia water is taken, a proper amount of pure water is added, and an ammonia water solution C of 2-12mol/L is prepared;
(4) preparation of ternary precursor (Ni) by chemical coprecipitation methodxCoyMnz)1-a-cMaNc(OH)2+k: pumping the metal salt solution A prepared in the step (1), the alkali solution B prepared in the step (2) and the ammonia water solution C prepared in the step (3) into a stirring reaction kettle simultaneously, and carrying out chemical precipitation reaction under the protection of inert gas; after the reaction is finished, aging, centrifuging, washing and drying are carried out to obtain the micrometer spherical multi-element co-doped modified ternary precursor (Ni)xCoyMnz)1-a-cMaNc(OH)2+k。
3. The method for preparing the multi-element in-situ co-doped ternary material precursor according to claim 2, wherein the nickel salt, the manganese salt and the cobalt salt in the step (1) are respectively one or more of sulfate, chloride and nitrate corresponding to each metal ion; in the step (1), the doping element M is a metal ion Y3+、Ce4+、Gd3+One or more of; the soluble M salt is metal ion Y3+、Ce4+、Gd3+Soluble sulfate and chloride salts corresponding to the aboveOne or more of nitrate, oxalate or other corresponding soluble salts; in the step (1), the doping element N is metal ion Ti4+、W4+One or more of; the N salt is metal ion Ti4+、W6+Respectively corresponding to one or more of sulfate, chloride, nitrate or other corresponding soluble salts.
4. The method for preparing the multi-element in-situ co-doped ternary material precursor according to claim 2 or 3, wherein the total concentration of metal ions in the metal salt solution A in the step (1) is 0.1-3 mol/L.
5. The method for preparing the multi-element in-situ co-doped ternary material precursor according to claim 2, wherein the total concentration of metal ions in the metal salt solution A in the step (1) is 1-2 mol/L.
6. The preparation method of the multi-element in-situ co-doped ternary material precursor according to claim 2, wherein the precipitant is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide in the step (2), and the concentration of the precipitant solution is 1-8 mol/L; in the step (3), the complexing agent is ammonia water, and the concentration of the complexing agent is 2-12 mol/L.
7. The preparation method of the multi-element in-situ co-doped ternary material precursor according to claim 2 or 6, wherein the concentration of the precipitant solution in the step (2) is 4-6 mol/L; the concentration of the complexing agent in the step (3) is 6-10 mol/L.
8. The method for preparing the multi-element in-situ co-doped ternary material precursor according to claim 2, wherein the inert gas in the step (4) is one of nitrogen and argon; in the coprecipitation reaction, the stirring speed is 100-800rpm, the heating temperature is controlled to be 40-80 ℃, and the pH value is controlled to be 9.5-12.
9. The method for preparing a multi-element in-situ co-doped ternary material precursor as claimed in claim 2 or 8, wherein the inert gas in the step (4) is nitrogen, the stirring speed is 200-600rpm, the heating temperature is controlled to be 50-80 ℃, and the pH value is controlled to be 10-11; after the chemical coprecipitation reaction in the step (4) is finished, aging, centrifuging, washing and drying are carried out to obtain the precursor ((Ni) of the multi-element in-situ co-doped ternary materialxCoyMnz)1-a-cMaNc(OH)2+k。
10. Use of the multi-element in-situ co-doped ternary material precursor according to claim 1 or 2, wherein the multi-element in-situ co-doped ternary material precursor (Ni) is prepared by using a chemical reaction methodxCoyMnz)1-a-cMaNc(OH)2+kThe method is used for preparing the ternary cathode material of the lithium ion battery.
11. The method for preparing the ternary cathode material of the lithium ion battery according to claim 10, wherein the multielement in-situ co-doped ternary material precursor (Ni) is utilizedxCoyMnz)1-a-cMaNc(OH)2+kMixing the lithium ion source and a lithium source according to a certain stoichiometric ratio, placing the mixture in a high-temperature sintering furnace, carrying out high-temperature calcination in an oxidizing atmosphere, and naturally cooling, crushing, screening and deironing the mixture to obtain the multielement co-doped modified lithium ion battery ternary cathode material Li (Ni)xCoyMnz)1-a-cMaNcO2。
12. The method according to claim 11, wherein the lithium source is one of lithium carbonate, lithium hydroxide, and lithium acetate containing lithium element; lithium ion and precursor (Ni) in the lithium sourcexCoyMnz)1-a-cMaNc(OH)2+kMolar ratio of medium metal ions1 is (1.02-1.1).
13. The method of claim 12, wherein the lithium source includes lithium ions and a precursor (Ni)xCoyMnz)1-a-cMaNc(OH)2+kThe molar ratio of the metal ions in the solution is (1.03-1.05): 1.
14. The method as claimed in claim 11, wherein the high temperature sintering is performed in air or oxygen atmosphere, the sintering temperature is 650-.
15. The method as claimed in claim 14, wherein the high-temperature sintering temperature is 750-.
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