CN112803023B - Lanthanum-zirconium-codoped high-nickel ternary cathode material and preparation method and application thereof - Google Patents

Lanthanum-zirconium-codoped high-nickel ternary cathode material and preparation method and application thereof Download PDF

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CN112803023B
CN112803023B CN202011622770.1A CN202011622770A CN112803023B CN 112803023 B CN112803023 B CN 112803023B CN 202011622770 A CN202011622770 A CN 202011622770A CN 112803023 B CN112803023 B CN 112803023B
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张震
范文俊
廖纪军
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South China University of Technology SCUT
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Abstract

本发明公开了一种镧锆共掺杂的高镍三元正极材料及其制备方法和应用。本发明的高镍三元正极材料为核壳结构，其由内向外依次包括镧锆共掺杂钴镍锰酸锂和镍锂酸镧包覆层；所述镧锆共掺杂钴镍锰酸锂的化学式为Li(Ni0.6Co0.2Mn0.2)1‑x‑yLaxZryO2，其中，0<x<0.03，0<y<0.03。本发明的高镍三元正极材料的制备方法包括以下步骤：1)进行镍、钴和锰的共沉淀，得到前驱体悬浮液；2)在前驱体悬浮液中制备碳酸镧，得到碳酸镧包覆的前驱体；3)对碳酸镧包覆的前驱体进行锂和锆的掺杂。本发明的高镍三元正极材料在高截止电压下长周期循环性能优异、倍率性能优异，且制备简单，适合大规模工业生产。

Figure 202011622770

The invention discloses a lanthanum-zirconium co-doped high-nickel ternary positive electrode material and a preparation method and application thereof. The high-nickel ternary positive electrode material of the present invention has a core-shell structure, which sequentially includes lanthanum zirconium co-doped cobalt nickel manganate and lanthanum nickel lithium manganate coating layers from inside to outside; the lanthanum zirconium co-doped cobalt nickel manganese acid The chemical formula of lithium is Li(Ni 0.6 Co 0.2 Mn 0.2 ) 1‑x‑y La x Zry O 2 , wherein 0<x<0.03 and 0<y<0.03. The preparation method of the high-nickel ternary positive electrode material of the present invention comprises the following steps: 1) co-precipitating nickel, cobalt and manganese to obtain a precursor suspension; 2) preparing lanthanum carbonate in the precursor suspension to obtain a lanthanum carbonate package 3) Doping the lanthanum carbonate-coated precursor with lithium and zirconium. The high-nickel ternary positive electrode material of the present invention has excellent long-cycle cycle performance and excellent rate performance under high cut-off voltage, is simple to prepare, and is suitable for large-scale industrial production.

Figure 202011622770

Description

Lanthanum-zirconium-codoped high-nickel ternary cathode material and preparation method and application thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lanthanum-zirconium co-doped high-nickel ternary cathode material and a preparation method and application thereof.
Background
High nickel ternary positive electrode material (LiNi)xCoyMn(1-x-y)O2，x>0.5) has higher energy density and working voltage and longer cycle life, is environment-friendly, and is widely applied to the field of lithium ion power batteries at present. To meet the requirements of power batteries, ternary positiveThe nickel content in the pole material is constantly increasing, which is advantageous for obtaining higher energy densities and for reducing costs (cobalt is toxic and has a very limited reserve on earth, being more expensive than nickel). However, as the content of nickel in the ternary positive electrode material increases, a series of problems also arise: 1) the problem of lithium-nickel mixed discharge: li+And Ni2+The ionic radius of the lithium-nickel ternary positive electrode material is very close, and the electrochemical performance of the high-nickel ternary positive electrode material is poor due to mixed lithium-nickel discharging easily; 2) lithium remaining on the surface of the high-nickel ternary cathode material reacts with carbon dioxide and water in the air to generate lithium carbonate and lithium hydroxide, so that high-temperature ballooning causes the cycle performance of the high-nickel ternary cathode material to be reduced; 3) side reactions between the electrodes and the electrolyte during cycling can increase polarization phenomena and interfacial resistance in the battery and further damage the electrode surface structure, resulting in poor battery performance; 4) the high-nickel ternary cathode material is easy to degrade in structure under high cut-off voltage and is easy to change phase in the charging and discharging process.
At present, the ternary cathode material is doped by metal ions and non-metal ions to improve the cycle stability and the structural stability of the ternary cathode material, but the actual effect is mostly more general, and many problems caused by the increase of the nickel content in the ternary cathode material cannot be well solved.
Therefore, it is highly desirable to develop a high nickel ternary cathode material with high rate and long cycle performance.
Disclosure of Invention
The invention aims to provide a lanthanum-zirconium co-doped high-nickel ternary cathode material and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
a lanthanum-zirconium-codoped high-nickel ternary cathode material is of a core-shell structure and sequentially comprises a lanthanum-zirconium-codoped cobalt nickel lithium manganate and a lanthanum nickelate coating layer from inside to outside; the chemical formula of the lanthanum-zirconium co-doped cobalt nickel lithium manganate is Li (Ni)0.6Co0.2Mn0.2)1-x-yLaxZryO2Wherein, 0<x<0.03，0<y<0.03。
Preferably, the nickel lithiumLanthanum acid has the chemical formula La2Ni0.5Li0.5O4。
The preparation method of the lanthanum-zirconium co-doped high-nickel ternary cathode material comprises the following steps:
1) dissolving a nickel source, a cobalt source and a manganese source in water, adding a precipitator, and mixing to obtain a precursor suspension;
2) dissolving a lanthanum source and carbonate in water, adding the solution into the precursor suspension, mixing, separating, purifying and drying to obtain a precursor coated by lanthanum carbonate;
3) and mixing and grinding the lanthanum carbonate coated precursor, a lithium source and a zirconium source, and then pre-sintering and sintering to obtain the lanthanum-zirconium co-doped high-nickel ternary cathode material.
Preferably, the preparation method of the lanthanum-zirconium co-doped high-nickel ternary cathode material comprises the following steps:
1) dissolving a nickel source, a cobalt source and a manganese source in water, adding a precipitant solution, and mixing to obtain a precursor suspension;
2) dissolving a lanthanum source and carbonate in water, then dropwise adding the solution into the precursor suspension, mixing, and then filtering, washing and drying to obtain a precursor coated by lanthanum carbonate;
3) and mixing and grinding the lanthanum carbonate coated precursor, a lithium source and a zirconium source, and then pre-sintering and sintering to obtain the lanthanum-zirconium co-doped high-nickel ternary cathode material.
Preferably, the nickel source in step 1) is at least one of nickel acetate, nickel oxalate and nickel nitrate.
Preferably, the cobalt source in step 1) is at least one of cobalt acetate, cobalt oxalate and cobalt nitrate.
Preferably, the manganese source in step 1) is at least one of manganese acetate, manganese oxalate and manganese nitrate.
Preferably, the molar ratio of the nickel source, the cobalt source and the manganese source in the step 1) is 3:1: 1.
Preferably, the precipitating agent in step 1) is at least one of sodium carbonate and sodium oxalate.
Preferably, the mixing time in the step 1) is 12-15 h.
Preferably, the lanthanum source in step 2) is at least one of lanthanum nitrate, lanthanum acetate and lanthanum sulfate.
Preferably, the carbonate in step 2) is at least one of sodium carbonate, potassium carbonate and ammonium carbonate.
Preferably, the mixing time in the step 2) is 2 to 3 hours.
Preferably, the lithium source in step 3) is at least one of lithium carbonate, lithium hydroxide and lithium acetate.
Preferably, the zirconium source in step 3) is at least one of zirconium oxide, zirconyl nitrate and zirconium nitrate.
Preferably, the molar ratio of the lanthanum carbonate-coated precursor, the lithium source and the zirconium source in the step 3) is 1: 1.05-1.09: 0.01.
Preferably, the pre-sintering temperature in the step 3) is 400-500 ℃, and the pre-sintering time is 4-6 h.
Preferably, the temperature rise rate of the pre-sintering in the step 3) is 3 ℃/min to 5 ℃/min.
Preferably, the sintering temperature in the step 3) is 800-900 ℃, and the sintering time is 12-18 h.
A lithium ion battery anode comprises the lanthanum-zirconium co-doped high-nickel ternary anode material.
The preparation method of the lithium ion battery anode comprises the following steps: and mixing the lanthanum-zirconium co-doped high-nickel ternary positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) for pulping, coating the pulp on an aluminum foil, and drying to obtain the lithium ion battery positive electrode.
Preferably, the preparation method of the lithium ion battery positive electrode comprises the following steps: and mixing the lanthanum-zirconium co-doped high-nickel ternary cathode material, acetylene black and polyvinylidene fluoride according to the mass ratio of 8:1:1 to prepare slurry, coating the slurry on an aluminum foil, and drying to obtain the lithium ion battery cathode.
The invention has the beneficial effects that: the lanthanum-zirconium-codoped high-nickel ternary cathode material has excellent long-period cycle performance and rate performance under high cut-off voltage, is simple in preparation method, is pollution-free, and is suitable for large-scale industrial production.
Specifically, the method comprises the following steps:
1) according to the invention, lanthanum ions and zirconium ions are doped into crystal lattices to serve as columnar ions to stabilize the material structure, so that the c-axis distance is enlarged, and the Li is enhanced+The diffusion capacity of the material is improved, the phase change is inhibited, the structural stability is improved, the direct contact between the material and an electrolyte is avoided by arranging the lanthanum nickelate coating layer, the active material is effectively protected, the cycle performance of the material is improved, the transmission power of the material can be improved by being used as a good conductor of lithium ions, and the material rate performance is well improved, so that the CR2016 type button battery assembled by the lanthanum-zirconium co-doped high-nickel ternary positive electrode material has the capacity retention rate of more than 90% after 150 times of charge and discharge cycles under the current density of 2C (1C is 160mAh/g) of 3.0-4.6V, the capacity of more than 100mAh/g after 500 times of cycles under the current density of 5C, the discharge capacity of more than 140mAh/g under the current density of 10C, and the capacity retention rate of more than 60% after 500 times of cycles;
2) according to the invention, the precursor coated with lanthanum carbonate is prepared by a simple precursor coating and precursor grinding method, so that particles are not easy to agglomerate, the rate capability of the material is improved, a zirconium source is introduced in the process of lithium preparation, and lanthanum-zirconium ion co-doping is realized;
3) the lanthanum source is a dopant source of the high-nickel ternary cathode material and a coating source, particle agglomeration is reduced, a coating layer of an ion good conductor is formed, and transmission of interface electrons can be accelerated, so that the material has good rate performance, the material can be well prevented from being corroded by the outside, the stability of the material structure can be further maintained, the cycle performance of the material is improved, and the synthesized high-nickel ternary cathode material is complete in structure and complete in crystal form; in the process of lithium preparation, zirconium ions can be further doped into the crystal lattice of the material transition metal layer as columnar ions by controlling the amount of the added zirconium source, so that the material structure is stabilized, and the interlayer spacing of the material transition metal layer is further increased by doping the zirconium ions, so that the lithium ions can be conveniently de-intercalated back and forth, and the structural stability of the material can be further improved;
4) the CR2016 type button battery assembled by the lanthanum-zirconium co-doped high-nickel ternary cathode material has high specific capacity, high rate performance and excellent cycle performance, the cycle performance is excellent under high current density, and the service life of the battery is long;
5) the raw materials used in the invention have low price, are easy to obtain, and the preparation method is simple, pollution-free and suitable for large-scale industrial production.
Drawings
Fig. 1 is an XRD pattern of the high nickel ternary positive electrode materials of example 2, comparative example 1, and comparative example 2.
Fig. 2 is a partial enlarged view of XRD patterns of the high nickel ternary positive electrode materials of example 2, comparative example 1, and comparative example 2(2 θ is a segment of 20 ° to 35 °).
Fig. 3 is a partial enlarged view of XRD patterns of the high nickel ternary positive electrode materials of example 2, comparative example 1, and comparative example 2(2 θ is a segment of 17 ° to 20 °).
Fig. 4 is a TEM image of the high nickel ternary positive electrode materials of example 2 and comparative example 1.
FIG. 5 is a graph of the cycling performance of the CR2016 type coin cell of example 2 and comparative example 1 at a current density of 800 mA/g.
Figure 6 is a graph of the cycling performance of the CR2016 type coin cell of example 2 and comparative example 1 at a current density of 1600 mA/g.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
a preparation method of a lanthanum-zirconium co-doped high-nickel ternary cathode material comprises the following steps:
1) dissolving 0.015mol of nickel acetate, 0.005mol of cobalt acetate and 0.005mol of manganese acetate in 25mL of deionized water, dissolving 0.03mol of sodium carbonate in 150mL of deionized water, mixing the two obtained solutions, and stirring for 10 hours to obtain a precursor suspension;
2) dissolving 0.000125mol of lanthanum nitrate and 0.0001875mol of sodium carbonate in 10mL of deionized water, dropwise adding the solution into the precursor suspension obtained in the step 1), stirring for 2 hours after adding, and then filtering, washing and drying to obtain a precursor coated with lanthanum carbonate;
3) mixing 0.02mol of a lanthanum carbonate coated precursor, 0.0214mol of lithium carbonate and 0.0001mol of nano zirconia, grinding, placing in a muffle furnace, heating to 400 ℃ at the heating rate of 3 ℃/min in the air atmosphere, presintering for 5h, sintering for 12h at 800 ℃, and naturally cooling to room temperature to obtain the lanthanum-zirconium co-doped high-nickel ternary cathode material.
0.05g of lanthanum-zirconium co-doped high-nickel ternary cathode material, 0.0062g of acetylene black and 0.0062g of PVDF are mixed and ground, added into 1mL of N-methylpyrrolidone (NMP), magnetically stirred for 2 hours, coated on an aluminum foil to be dried to prepare an electrode, and then metal lithium is used as a counter electrode to be assembled into a CR2016 type button battery in a glove box.
Through tests, the CR2016 type button battery is tested under the conditions of 3.0V-4.6V high-voltage 5C multiplying power, the battery capacity is 165.2mAh/g, the capacity is 89.9mAh/g after 500 cycles, and the capacity retention rate is 54.43%.
Example 2:
a preparation method of a lanthanum-zirconium co-doped high-nickel ternary cathode material comprises the following steps:
1) dissolving 0.015mol of nickel acetate, 0.005mol of cobalt acetate and 0.005mol of manganese acetate in 25mL of deionized water, dissolving 0.03mol of sodium carbonate in 150mL of deionized water, mixing the two obtained solutions, and stirring for 10 hours to obtain a precursor suspension;
2) dissolving 0.000125mol of lanthanum nitrate and 0.0001875mol of sodium carbonate in 10mL of deionized water, dropwise adding the solution into the precursor suspension obtained in the step 1), stirring for 2 hours after adding, and then filtering, washing and drying to obtain a precursor coated with lanthanum carbonate;
3) mixing 0.02mol of lanthanum carbonate coated precursor, 0.0214mol of lithium carbonate and 0.0002mol of nano zirconia, grinding, placing in a muffle furnace, heating to 400 ℃ at the heating rate of 3 ℃/min in the air atmosphere, presintering for 5h, sintering for 12h at 800 ℃, and naturally cooling to room temperature to obtain the lanthanum-zirconium codoped high-nickel ternary cathode material.
Electrodes were prepared and CR2016 type coin cells were assembled according to the method of example 1.
Through tests, the CR2016 type button battery is tested under the conditions of 3.0V-4.6V high-voltage 5C multiplying power, the battery capacity is 164.6mAh/g, the capacity is 101.3mAh/g after 500 cycles, and the capacity retention rate is 61.52%.
Example 3:
a preparation method of a lanthanum-zirconium co-doped high-nickel ternary cathode material comprises the following steps:
1) dissolving 0.015mol of nickel acetate, 0.005mol of cobalt acetate and 0.005mol of manganese acetate in 25mL of deionized water, dissolving 0.03mol of sodium carbonate in 150mL of deionized water, mixing the two obtained solutions, and stirring for 10 hours to obtain a precursor suspension;
2) dissolving 0.000125mol of lanthanum nitrate and 0.0001875mol of sodium carbonate in 10mL of deionized water, dropwise adding the solution into the precursor suspension obtained in the step 1), stirring for 2 hours after adding, and then filtering, washing and drying to obtain a precursor coated with lanthanum carbonate;
3) mixing 0.02mol of a lanthanum carbonate coated precursor, 0.0214mol of lithium carbonate and 0.0004mol of nano zirconia, grinding, placing in a muffle furnace, heating to 400 ℃ at the heating rate of 3 ℃/min in the air atmosphere, presintering for 5h, sintering for 12h at 800 ℃, and naturally cooling to room temperature to obtain the lanthanum-zirconium codoped high-nickel ternary cathode material.
Electrodes were prepared and CR2016 type coin cells were assembled according to the method of example 1.
Through tests, the CR2016 type button battery is tested under the conditions of 3.0V-4.6V high-voltage 5C multiplying power, the battery capacity is 162.3mAh/g, the capacity is 80.3mAh/g after 500 cycles, and the capacity retention rate is 49.45%.
Example 4:
a preparation method of a lanthanum-zirconium co-doped high-nickel ternary cathode material comprises the following steps:
1) dissolving 0.015mol of nickel acetate, 0.005mol of cobalt acetate and 0.005mol of manganese acetate in 25mL of deionized water, dissolving 0.03mol of sodium carbonate in 150mL of deionized water, mixing the two obtained solutions, and stirring for 10 hours to obtain a precursor suspension;
2) dissolving 0.000075mol of lanthanum nitrate and 0.0001125mol of sodium carbonate in 10mL of deionized water, then dropwise adding the solution into the precursor suspension obtained in the step 1), stirring for 2h after adding, and then filtering, washing and drying to obtain a precursor coated by lanthanum carbonate;
3) mixing 0.02mol of lanthanum carbonate coated precursor, 0.0214mol of lithium carbonate and 0.0002mol of nano zirconia, grinding, placing in a muffle furnace, heating to 400 ℃ at the heating rate of 3 ℃/min in the air atmosphere, presintering for 5h, sintering for 12h at 800 ℃, and naturally cooling to room temperature to obtain the lanthanum-zirconium codoped high-nickel ternary cathode material.
Electrodes were prepared and CR2016 type coin cells were assembled according to the method of example 1.
Through tests, the CR2016 type button battery is tested under the conditions of 3.0V-4.6V high-voltage 5C multiplying power, the battery capacity is 163.3mAh/g, the capacity is 77.7mAh/g after 500 cycles, and the capacity retention rate is 47.56%.
Example 5:
a preparation method of a lanthanum-zirconium co-doped high-nickel ternary cathode material comprises the following steps:
1) dissolving 0.015mol of nickel acetate, 0.005mol of cobalt acetate and 0.005mol of manganese acetate in 25mL of deionized water, dissolving 0.03mol of sodium carbonate in 150mL of deionized water, mixing the two obtained solutions, and stirring for 10 hours to obtain a precursor suspension;
2) 0.000175mol of lanthanum nitrate and 0.0002625mol of sodium carbonate are dissolved in 10mL of deionized water, then the solution is dripped into the precursor suspension obtained in the step 1), the solution is stirred for 2 hours after the addition, and then the solution is filtered, washed and dried to obtain a precursor coated by lanthanum carbonate;
3) mixing 0.02mol of lanthanum carbonate coated precursor, 0.0214mol of lithium carbonate and 0.0002mol of nano zirconia, grinding, placing in a muffle furnace, heating to 400 ℃ at the heating rate of 3 ℃/min in the air atmosphere, presintering for 5h, sintering for 12h at 800 ℃, and naturally cooling to room temperature to obtain the lanthanum-zirconium codoped high-nickel ternary cathode material.
Electrodes were prepared and CR2016 type coin cells were assembled according to the method of example 1.
Through tests, the CR2016 type button battery is tested under the conditions of 3.0V-4.6V high voltage and 5C multiplying power, the battery capacity is 157.3mAh/g, the capacity is 42.2mAh/g after 500 cycles, and the capacity retention rate is 26.80%.
Comparative example 1:
a preparation method of a high-nickel ternary cathode material comprises the following steps:
1) dissolving 0.015mol of nickel acetate, 0.005mol of cobalt acetate and 0.005mol of manganese acetate in 25mL of deionized water, dissolving 0.03mol of sodium carbonate in 150mL of deionized water, mixing the two obtained solutions, and stirring for 12 hours to obtain a precursor suspension;
2) mixing 0.02mol of precursor and 0.0214mol of lithium carbonate, grinding, placing in a muffle furnace, heating to 400 ℃ at the heating rate of 3 ℃/min in the air atmosphere, presintering for 5h, sintering at 800 ℃ for 12h, and naturally cooling to room temperature to obtain the high-nickel ternary cathode material (LiNi)0.6Co0.2Mn0.2O2)。
Electrodes were prepared and CR2016 type coin cells were assembled according to the method of example 1.
Through tests, the CR2016 type button battery is tested under the conditions of 3.0V-4.6V high-voltage 2C multiplying power, the battery capacity is 161.5mAh/g, the capacity is 45.6mAh/g after 150 cycles, and the capacity retention rate is 28.23%.
Comparative example 2:
a lanthanum-doped high-nickel ternary cathode material is prepared by the following steps:
1) dissolving 0.015mol of nickel acetate, 0.005mol of cobalt acetate and 0.005mol of manganese acetate in 25mL of deionized water, dissolving 0.03mol of sodium carbonate in 150mL of deionized water, mixing the two obtained solutions, and stirring for 10 hours to obtain a precursor suspension;
2) dissolving 0.000125mol of lanthanum nitrate and 0.0001875mol of sodium carbonate in 10mL of deionized water, dropwise adding the solution into the precursor suspension obtained in the step 1), stirring for 2 hours after adding, and then filtering, washing and drying to obtain a precursor coated with lanthanum carbonate;
3) mixing 0.02mol of lanthanum carbonate coated precursor and 0.0214mol of lithium carbonate, grinding, placing in a muffle furnace, heating to 400 ℃ at the heating rate of 3 ℃/min in the air atmosphere, presintering for 5h, sintering at 800 ℃ for 12h, and naturally cooling to room temperature to obtain the lanthanum-doped high-nickel ternary cathode material.
Electrodes were prepared and CR2016 type coin cells were assembled according to the method of example 1.
Through tests, the CR2016 type button battery is tested under the high-voltage 2C multiplying power of 3.0V-4.6V, the battery capacity is 165.9mAh/g, the capacity is 58.7mAh/g after 150 cycles, and the capacity retention rate is 35.30%.
Comparative example 3:
a zirconium-doped high-nickel ternary cathode material is prepared by the following steps:
1) dissolving 0.015mol of nickel acetate, 0.005mol of cobalt acetate and 0.005mol of manganese acetate in 25mL of deionized water, dissolving 0.03mol of sodium carbonate in 150mL of deionized water, mixing the two solutions, and stirring for 12 hours to obtain a precursor suspension;
2) mixing 0.02mol of precursor and 0.0214mol of nano zirconia, grinding, placing in a muffle furnace, heating to 400 ℃ at the heating rate of 3 ℃/min in the air atmosphere, presintering for 5h, sintering at 800 ℃ for 12h, and naturally cooling to room temperature to obtain the zirconium-doped high-nickel ternary cathode material.
Electrodes were prepared and CR2016 type coin cells were assembled according to the method of example 1.
Through tests, the CR2016 type button battery is tested under the conditions of 3.0V-4.6V high-voltage 2C multiplying power, the battery capacity is 157.6mAh/g, the capacity is 69.0mAh/g after 150 cycles, and the capacity retention rate is 43.79%.
And (3) performance testing:
1) XRD patterns of the lanthanum-zirconium-codoped high-nickel ternary cathode material of example 2, the high-nickel ternary cathode material of comparative example 1, and the lanthanum-doped high-nickel ternary cathode material of comparative example 2 are shown in fig. 1, and partial enlarged views of the XRD patterns are shown in fig. 2 (a section of 20 ° to 35 °) and fig. 3 (a section of 17 ° to 20 °).
As can be seen from FIGS. 1 to 3: peaks corresponding to card PDF #52-1671, namely La, appeared in XRD of the lanthanum-zirconium co-doped high-nickel ternary cathode material of example 2 and the lanthanum-doped high-nickel ternary cathode material of comparative example 22Ni0.5Li0.5O4The position of the (003) peak of the lanthanum zirconium co-doped high nickel ternary cathode material of example 2 was shifted to a lower angle, indicating that both lanthanum and zirconium were successfully doped into the lattice of the high nickel ternary cathode material.
2) Transmission Electron Microscope (TEM) images of the lanthanum zirconium-codoped high nickel ternary cathode material of example 2 and the high nickel ternary cathode material of comparative example 1 are shown in fig. 4 (a in fig. 4 is the high nickel ternary cathode material of comparative example 1, b is a partial enlarged view corresponding thereto, c is the lanthanum zirconium-codoped high nickel ternary cathode material of example 2, and d is a partial enlarged view corresponding thereto).
As can be seen from fig. 4: the lanthanum-zirconium co-doped high-nickel ternary cathode material of example 2 has a clearly visible coating layer on the surface through lanthanum-zirconium co-modification, while the high-nickel ternary cathode material of comparative example 1 has a smooth surface without any coating layer due to non-modification.
3) The cycling performance of the CR2016 type coin cells of example 2 and comparative example 1 at a current density of 800mA/g is shown in figure 5.
As can be seen from fig. 5: the capacity retention rate of the CR2016 type coin cell of example 2 after 500 cycles at a current density of 800mA/g was much higher than that of the CR2016 type coin cell of comparative example 1.
4) The cycling performance of the CR2016 type coin cell of example 2 and comparative example 1 at a current density of 1600mA/g is shown in figure 6.
As can be seen from fig. 6: the capacity retention rate of the CR2016 type button cell of example 2 after 500 cycles at a current density of 1600mA/g is much higher than that of the CR2016 type button cell of comparative example 1.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (9)

1. The preparation method of the lanthanum-zirconium-codoped high-nickel ternary cathode material is characterized in that the lanthanum-zirconium-codoped high-nickel ternary cathode material is of a core-shell structure and sequentially comprises a lanthanum-zirconium-codoped cobalt nickel lithium manganate and a lanthanum nickelate coating layer from inside to outside; the chemical formula of the lanthanum-zirconium co-doped cobalt nickel lithium manganate is Li (Ni)0.6Co0.2Mn0.2)1-x-yLaxZryO2Wherein, 0<x<0.03，0<y<0.03, the preparation method comprises the following steps:
1) dissolving a nickel source, a cobalt source and a manganese source in water, adding a precipitator, and mixing to obtain a precursor suspension;
2) dissolving a lanthanum source and carbonate in water, adding the solution into the precursor suspension, mixing, separating, purifying and drying to obtain a precursor coated by lanthanum carbonate;
3) mixing and grinding a lanthanum carbonate coated precursor, a lithium source and a zirconium source, and then pre-sintering and sintering to obtain a lanthanum-zirconium co-doped high-nickel ternary cathode material;
wherein the molar ratio of the lanthanum carbonate-coated precursor, the lithium source and the zirconium source in the step 3) is 1: 1.05-1.09: 0.01.
2. the preparation method of the lanthanum-zirconium-codoped high-nickel ternary cathode material according to claim 1, characterized by comprising the following steps of: the nickel source in the step 1) is at least one of nickel acetate, nickel oxalate and nickel nitrate; the cobalt source in the step 1) is at least one of cobalt acetate, cobalt oxalate and cobalt nitrate; the manganese source in the step 1) is at least one of manganese acetate, manganese oxalate and manganese nitrate.
3. The preparation method of the lanthanum-zirconium co-doped high-nickel ternary cathode material as claimed in claim 1 or 2, wherein the preparation method comprises the following steps: the precipitator in the step 1) is at least one of sodium carbonate and sodium oxalate.
4. The preparation method of the lanthanum-zirconium co-doped high-nickel ternary cathode material according to claim 1, characterized by comprising the following steps: and 2) the lanthanum source is at least one of lanthanum nitrate, lanthanum acetate and lanthanum sulfate.
5. The preparation method of the lanthanum-zirconium co-doped high-nickel ternary cathode material as claimed in any one of claims 1, 2 and 4, characterized in that: and 2) the carbonate is at least one of sodium carbonate, potassium carbonate and ammonium carbonate.
6. The preparation method of the lanthanum-zirconium co-doped high-nickel ternary cathode material according to claim 1, characterized by comprising the following steps: the lithium source in the step 3) is at least one of lithium carbonate, lithium hydroxide and lithium acetate; and 3) the zirconium source is at least one of zirconium oxide, zirconyl nitrate and zirconium nitrate.
7. The preparation method of the lanthanum-zirconium co-doped high-nickel ternary cathode material as claimed in any one of claims 1, 2, 4 and 6, characterized in that: the pre-sintering temperature in the step 3) is 400-500 ℃, and the pre-sintering time is 4-6 h.
8. The preparation method of the lanthanum-zirconium co-doped high-nickel ternary cathode material as claimed in any one of claims 1, 2, 4 and 6, characterized in that: the sintering temperature in the step 3) is 800-900 ℃, and the sintering time is 12-18 h.
9. The use of the high-nickel ternary cathode material prepared by the method of any one of claims 1 to 8 for the preparation of a lithium ion battery.
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