CN112928272A - High-nickel ternary cathode material doped with aliovalent ions and preparation method and application thereof - Google Patents
High-nickel ternary cathode material doped with aliovalent ions and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides an aliovalent ion doped high-nickel ternary positive electrode material and a preparation method and application thereof, wherein the chemical formula of the aliovalent ion doped high-nickel ternary positive electrode material is Li1+ kNixCoyMzM’aO2In the formula, k is more than or equal to-0.1 and less than or equal to 0.1, x is more than or equal to 0.5 and less than 1, y is more than 0 and less than 1, z is more than 0 and less than 1, a is more than 0 and less than or equal to 0.1, and x + y + z + a is more than 0.5 and less than or equal to 1.1; m is Al or Mn, and M' is one or more elements which are doped to be divalent, tetravalent, pentavalent or hexavalent cations. The invention is beneficial to high nickel ternary through the doping of the heterovalent ionsThe stability of the oxygen skeleton of the anode material improves the cycle performance of the anode material; meanwhile, after the heterovalent ions are doped, the effect of reducing the primary particle size of the high-nickel ternary cathode material particles is achieved, the rate performance is favorably improved, the synergistic effect is generated, and the electrochemical performance of the material is greatly improved.
Description
Technical Field
The invention relates to the technical field of power batteries, in particular to a high-nickel ternary positive electrode material doped with aliovalent ions, and a preparation method and application thereof.
Background
Along with the increasing and worsening international energy environment of living standard of people, the endurance mileage and the safety requirement of the electric automobile are also gradually increased, and people need a power lithium ion battery with high energy density, safety, low cost and environmental adaptability urgently to ensure the practicability of the electric automobile.
The anode material, one of the most critical technical problems of the lithium ion battery, is a decisive factor of the energy density, the service life and the safety of the whole battery system. Li [ Ni ] formed by partial doping of Co and Al/Mn instead of NixCoyMz]O2High nickel ternary materials (NCA/NCM), which are receiving much attention due to their high specific capacity, high energy density and low cost, are considered to be one of the best anode material candidates for high energy density lithium ion batteries.
However, the system material also exists as a candidate material of a high-energy lithium ion batteryThese problems are: firstly, during the high-temperature synthesis process due to Ni3+Is unstable and is easily reduced to Ni2+And due to Li+ 
And Ni2+ 
And the resulting Li+/Ni2+Mixed discharge, which causes difficulty in solid phase diffusion of lithium ions and increases the polarization of the material; secondly, due to the easily reducible Ni4+Particularly in a highly delithiated state, the surface of the cathode material is easy to generate side reaction with electrolyte to generate an electrochemical inert layer, and the diffusion of lithium ions is inhibited along with the generation of impurity phases such as a spinel phase and a rock salt phase, and meanwhile, the safety performance is reduced along with the loss of oxygen in the bulk material; in addition, in the lithium desorption process, the corrosion of the electrolyte to the material is further increased due to the generation of micro-cracks inside the secondary particles caused by multi-phase transformation, and the surface resistance is further increased. The combination of these problems leads to a dramatic drop in electrochemical performance and an increasingly important safety concern.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an aliovalent ion doped high-nickel ternary positive electrode material and a preparation method and application thereof.
The invention adopts the following technical scheme:
the invention provides an aliovalent ion doped high-nickel ternary positive electrode material, which has a chemical formula of Li1+kNixCoyMzM’aO2，
In the formula, k is more than or equal to-0.1 and less than or equal to 0.1, x is more than or equal to 0.5 and less than 1, y is more than 0 and less than 1, z is more than 0 and less than 1, a is more than 0 and less than or equal to 0.1, and x + y + z + a is more than 0.5 and less than or equal to 1.1;
m is Al or Mn, and M' is one or more elements which are doped to be divalent, tetravalent, pentavalent or hexavalent cations.
The research of the invention finds that the heterovalent ion doping has an unexpected effect on the stability of the material structure, and Ni in a phase different from a bulk phase is doped3+After the aliovalent ions are introduced, the nickelic material introduces local electrons or holes in order to maintain an electric center, thereby changing the charge distribution condition of neighboring ions, no matter low valence state ions (Mg) are introduced2+Etc.) or a high valent ion (Ti)4+Etc.), the charge distribution of Ni adjacent to the active ions will change, so that the oxygen skeleton structure of the material can be further stabilized, oxygen loss and phase change in the circulating process are inhibited, the structural stability of the material is improved, and the circulating performance is facilitated. Meanwhile, after the heterovalent ions are doped, the effect of reducing the primary particle size of the high-nickel ternary cathode material particles is achieved, the rate performance is facilitated, an unexpected synergistic effect is generated, and the electrochemical performance of the material is greatly improved.
Preferably, M' is at least one of Mg, Ti, Zr, V, Nb, Mo, W, Ru, Te, Sb, Ta.
Further preferably, M' is Ta and additionally at least one element satisfying the above requirements. The research of the invention finds that when the doping element contains Ta, the electrochemical performance of the doped high-nickel ternary cathode material is more excellent.
More preferably, the effect is better when the doping elements are double doped, i.e. one doping element is Ta and the other doping element is Zr, Mo, W, Ru, V, Sb or Te.
On the basis of the above technical solution, preferably, the molar ratio of Ta in the cathode material is not more than 5%, and the molar ratio of another doping element in the cathode material is not more than 5%, that is, the subscripts of Ta and the other doping element in the chemical formula are both greater than 0 and equal to or less than 0.05.
In a preferred embodiment of the invention, the chemical formula of the aliovalent ion doped high nickel ternary cathode material is LiNi0.88Co0.1Al0.02Ta0.01Zr0.02O2，LiNi0.88Co0.10Al0.02Ta0.01Mo0.005O2，LiNi0.88Co0.10Al0.02Ta0.0 1Te0.02O2，LiNi0.88Co0.10Al0.02Ta0.02W0.01O2Or LiNi0.88Co0.10Al0.02Ta0.02Sb0.01O2。
In the invention, the concentration of M is in a gradient decreasing trend and the concentration of M' is in a gradient decreasing trend from the surface of the high-nickel ternary cathode material doped with the aliovalent ions to the core.
Preferably, the average particle size of the aliovalent ion doped high-nickel ternary cathode material is 0.1-20 μm.
The invention also provides a preparation method of the high-nickel ternary cathode material doped with the aliovalent ions.
The preparation method provided by the invention comprises the following steps: and (3) carrying out solid-phase mixing and coating on a precursor of the matrix high-nickel ternary cathode material and the doping raw material, then mixing with lithium hydroxide monohydrate, and then carrying out two-stage high-temperature heat treatment.
When more than one doping raw material is used, multiple doping raw materials can be added at one time to be mixed and coated with the precursor in a solid phase mode, and can also be added sequentially to be mixed and coated with the precursor in a solid phase mode.
Preferably, the doping raw material is one of a nano oxide, an inorganic salt and an organic salt of M'.
Preferably, the solid-phase mixing coating method is a mechanical mixing method or a wet mixing method.
Preferably, in the two-stage high-temperature heat treatment process, the heat treatment temperature of the first stage is 400-.
The invention also provides application of the high-nickel ternary cathode material doped with the aliovalent ions. Specifically, it can be applied to a lithium ion battery as a positive electrode active material.
The invention also provides a lithium ion battery which comprises a positive electrode, wherein the positive electrode comprises the high-nickel ternary positive electrode material doped with the aliovalent ions.
The invention provides a high-nickel ternary cathode material doped with aliovalent ions, which is beneficial to the stability of an oxygen skeleton of the high-nickel ternary cathode material and improves the cycle performance of the cathode material by doping the aliovalent ions; meanwhile, after the heterovalent ions are doped, the effect of reducing the primary particle size of the high-nickel ternary cathode material particles is achieved, the rate performance is facilitated, an unexpected synergistic effect is generated, and the electrochemical performance of the material is greatly improved.
Drawings
FIG. 1 is a first charge-discharge curve of high nickel ternary positive electrode materials prepared according to examples 1-7 of the present invention and comparative examples;
FIG. 2 is a graph of rate capability of high nickel ternary cathode materials prepared according to examples 1-7 of the present invention and comparative examples;
FIG. 3 is a graph of the cycling performance of the high nickel ternary cathode materials prepared in examples 1-7 of the present invention and comparative examples;
fig. 4 is a graph comparing primary particle sizes of the high nickel ternary cathode materials prepared in examples 2, 4, and 5 of the present invention and a comparative example.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
This example provides a high nickel ternary positive electrode material doped with aliovalent ions, whose chemical formula is LiNi0.88Co0.10Al0.02Ta0.01Ti0.01O2The average particle size was about 10 μm.
The embodiment also provides a preparation method of the material, which comprises the following steps:
weighing 1mol of high-nickel ternary positive electrode material precursor (Ni)0.88Co0.10Al0.02(OH)2) 0.005mol nanometer oxide tantalum pentoxide (Ta)2O5) Uniformly coating by adopting a mechanical fusion method to obtain Ni0.88Co0.10Al0.02Ta0.01(OH)2Precursor, then adding 0.01mol of nano titanium dioxide (TiO)2) And continuously adopting a mechanical fusion method to coat uniformly, then carrying out heat treatment at 480 ℃ for 4h in an oxygen atmosphere, and then heating to 750 ℃ for 20h to obtain the high-nickel ternary cathode material doped with the aliovalent ions.
Electrochemical performance was tested as follows:
uniformly mixing a target product with acetylene black serving as a conductive agent and PVDF (polyvinylidene fluoride) serving as a binder according to a mass ratio of 8:1:1, then mixing the mixture with NMP (N-methyl-pyrrolidone) to form slurry with certain viscosity, uniformly coating the slurry on an Al foil, drying the slurry at 80 ℃ for 4 hours, punching into electrode plates with the diameter of 14mm, rolling, and drying at 80 ℃ for 12 hours in vacuum. Transferring the electrode slice into a glove box to be used as a positive plate, taking a metal lithium plate as a negative electrode, taking a Celgard 2400 membrane as a diaphragm and 1mol L of the diaphragm-1LiPF of6(volume ratio: 1: 1)/EC + DEC + DMC as an electrolyte in a glove box (Braun, Germany, O)2And H2O mass fractions are all less than 0.1ppm), and the assembled battery is subjected to charge and discharge test (wuhanjinnuo limited, china) on a CT2001 blue tester at a temperature of 25 ℃ ± 3 ℃.
Electrochemical tests show that the specific capacities of the first charge and the first discharge within the voltage ranges of 0.1C and 2.5-4.3V are 227.5 mAh g and 210.1mAh g respectively-1The first charge-discharge coulombic efficiency was 92.37%, as shown in fig. 1; the specific discharge capacity under the high rate condition (3C) and within the voltage range of 2.5-4.3V is 181.4mAh g-1As shown in fig. 2; the capacity retention rate after 100 cycles under the conditions of 1.0C and 2.5-4.3V is 97.67%, as shown in FIG. 3.
Example 2
This example provides a high nickel ternary positive electrode material doped with aliovalent ions, whose chemical formula is LiNi0.88Co0.10Al0.02Ta0.01Zr0.02O2Is flat and flatThe average particle size was about 10 μm.
The preparation method comprises the following steps:
weighing 1mol of high-nickel ternary positive electrode material precursor (Ni)0.88Co0.10Al0.02(OH)2) 0.005mol nanometer oxide tantalum pentoxide (Ta)2O5) Uniformly coating by adopting a mechanical fusion method to obtain Ni0.88Co0.10Al0.02Ta0.01(OH)2Precursor, then 0.02mol of nano zirconium dioxide (ZrO) is added2) And continuously adopting a mechanical fusion method to coat uniformly, then carrying out heat treatment at 480 ℃ for 4h in an oxygen atmosphere, and then heating to 750 ℃ for 20h to obtain the high-nickel ternary cathode material doped with the aliovalent ions.
Electrochemical performance was tested as in example 1;
electrochemical tests show that the specific capacities of the first charge and the first discharge within the voltage ranges of 0.1C and 2.5-4.3V are 229.3 mAh g and 211.2mAh g respectively-1The first charge-discharge coulombic efficiency was 92.13%, as shown in fig. 1; under the condition of high multiplying power (3C) and within the voltage range of 2.5-4.3V, the specific discharge capacity is 181.6mAh g-1As shown in fig. 2; the capacity retention rate after 100 cycles under the conditions of 1.0C and 2.5-4.3V is 100.05%, as shown in FIG. 3.
Example 3
This example provides a high nickel ternary positive electrode material doped with aliovalent ions, whose chemical formula is LiNi0.88Co0.10Al0.02Ta0.02W0.01O2The average particle size was about 10 μm.
The preparation method comprises the following steps:
weighing 1mol of high-nickel ternary positive electrode material precursor (Ni)0.88Co0.10Al0.02(OH)2) 0.01mol of nano-oxide tantalum pentoxide (Ta)2O5) Uniformly coating by adopting a mechanical fusion method to obtain Ni0.88Co0.10Al0.02Ta0.02(OH)2Precursor, then adding 0.01mol of nano tungsten trioxide (WO)3) Continuously adopting a mechanical fusion method to coat uniformly, then carrying out heat treatment for 4h at 480 ℃ in an oxygen atmosphere, and thenAnd heating to 750 ℃ for heat treatment for 20h to obtain the high-nickel ternary cathode material doped with the aliovalent ions.
Electrochemical performance was tested as in example 1;
electrochemical tests show that the first charge and discharge specific capacities of the lithium ion battery are 225.1 mAh g and 207.3mAh g respectively in the voltage ranges of 0.1C and 2.5-4.3V-1The first charge-discharge coulombic efficiency was 92.09%, as shown in fig. 1; under the condition of high multiplying power (3C) and within the voltage range of 2.5-4.3V, the specific discharge capacity is 180.7mAh g-1As shown in fig. 2; the capacity retention rate after 100 cycles under the conditions of 1.0C and 2.5-4.3V is 99.47%, as shown in FIG. 3.
Example 4
This example provides a high nickel ternary positive electrode material doped with aliovalent ions, whose chemical formula is LiNi0.88Co0.10Al0.02Ta0.01Mo0.005O2The average particle size was about 10 μm.
The preparation method comprises the following steps:
weighing 1mol of high-nickel ternary positive electrode material precursor (Ni)0.88Co0.10Al0.02(OH)2) 0.005mol nanometer oxide tantalum pentoxide (Ta)2O5) Uniformly coating by adopting a mechanical fusion method to obtain Ni0.88Co0.10Al0.02Ta0.01(OH)2Adding 0.005mol of nano molybdenum trioxide (MoO) into the precursor3) Uniformly coating by adopting a mechanical fusion method, then carrying out heat treatment at 480 ℃ for 4h in an oxygen atmosphere, and then heating to 750 ℃ for 20h to obtain the high-nickel ternary cathode material doped with the aliovalent ions.
Electrochemical performance was tested as in example 1;
electrochemical tests show that the specific capacities of the first charge and the first discharge within the voltage ranges of 0.1C and 2.5-4.3V are 229.8 mAh g and 212.3mAh g respectively-1The first charge-discharge coulombic efficiency was 92.36%, as shown in fig. 1; under the condition of high multiplying power (3C) and within the voltage range of 2.5-4.3V, the specific discharge capacity is 180.3mAh g-1As shown in fig. 2; the capacity retention rate after 100 cycles under the conditions of 1.0C and 2.5-4.3V is 99.21%, as shown in FIG. 3.
Example 5
This example provides a high nickel ternary positive electrode material doped with aliovalent ions, whose chemical formula is LiNi0.88Co0.10Al0.02Ta0.02Sb0.01O2The average particle size was about 10 μm.
The preparation method comprises the following steps:
weighing 1mol of high-nickel ternary positive electrode material precursor (Ni)0.88Co0.10Al0.02(OH)2) 0.01mol of nano-oxide tantalum pentoxide (Ta)2O5) Uniformly coating by adopting a mechanical fusion method to obtain Ni0.88Co0.10Al0.02Ta0.02(OH)2Precursor, then 0.005mol of nano antimony trioxide (Sb) is added2O3) And continuously adopting a mechanical fusion method to coat uniformly, then carrying out heat treatment at 480 ℃ for 4h in an oxygen atmosphere, and then heating to 750 ℃ for 20h to obtain the high-nickel ternary cathode material doped with the aliovalent ions.
Electrochemical performance was tested as in example 1;
electrochemical tests show that the specific capacities of the first charge and the first discharge within the voltage ranges of 0.1C and 2.5-4.3V are 231.6 mAh g and 211.6mAh g respectively-1The first charge-discharge coulombic efficiency was 91.36%, as shown in fig. 1; the specific discharge capacity under the high rate condition (3C) and within the voltage range of 2.5-4.3V is 183.2mAh g-1As shown in fig. 2; the capacity retention rate after 100 cycles under the conditions of 1.0C and 2.5-4.3V is 98.85%, as shown in FIG. 3.
Example 6
This example provides a high nickel ternary positive electrode material doped with aliovalent ions, whose chemical formula is LiNi0.88Co0.10Al0.02Ta0.01Te0.02O2The average particle size was about 10 μm.
The preparation method comprises the following steps:
weighing 1mol of high-nickel ternary positive electrode material precursor (Ni)0.88Co0.10Al0.02(OH)2) 0.005mol nanometer oxide tantalum pentoxide (Ta)2O5) By machinesThe fusion method is used for coating evenly to obtain Ni0.88Co0.10Al0.02Ta0.01(OH)2Adding 0.02mol of nano tellurium trioxide (TeO) into the precursor3) And continuously adopting a mechanical fusion method to coat uniformly, then carrying out heat treatment at 480 ℃ for 4h in an oxygen atmosphere, and then heating to 750 ℃ for 20h to obtain the high-nickel ternary cathode material doped with the aliovalent ions.
Electrochemical performance was tested as in example 1;
electrochemical tests show that the first charge and discharge specific capacities of the lithium ion battery are 232.5 mAh g and 214.4mAh g respectively in the voltage ranges of 0.1C and 2.5-4.3V-1The first charge-discharge coulombic efficiency was 92.22%, as shown in fig. 1; the specific discharge capacity under the high rate condition (3C) and within the voltage range of 2.5-4.3V is 183.2mAh g-1As shown in fig. 2; the capacity retention rate after 100 cycles under the conditions of 1.0C and 2.5-4.3V is 98.66%, as shown in FIG. 3.
Example 7
This example provides a high nickel ternary positive electrode material doped with aliovalent ions, whose chemical formula is LiNi0.88Co0.10Al0.02Ta0.02O2The average particle size was about 10 μm.
The preparation method comprises the following steps:
weighing 1mol of high-nickel ternary positive electrode material precursor (Ni)0.88Co0.10Al0.02(OH)2) 0.01mol of nano-oxide tantalum pentoxide (Ta)2O5) Uniformly coating by adopting a mechanical fusion method to obtain Ni0.88Co0.10Al0.02Ta0.02(OH)2And (3) performing heat treatment on the precursor for 4h at 480 ℃ in an oxygen atmosphere, and then heating to 750 ℃ for 20h to obtain the high-nickel ternary cathode material doped with the aliovalent ions.
Electrochemical performance was tested as in example 1;
electrochemical tests show that the first charge-discharge specific capacities of the lithium ion battery are 233.4 mAh g and 210.6mAh g respectively in voltage ranges of 0.1C and 2.5-4.3V-1The first charge-discharge efficiency is 90.21%, as shown in fig. 1; discharge under high rate condition (3C) and voltage range of 2.5-4.3VSpecific capacity of 177.0mAh g-1As shown in fig. 2; the capacity retention rate after 100 cycles under the conditions of 1.0C and 2.5-4.3V was 95.51%, as shown in FIG. 3.
Comparative example
This comparative example provides an undoped high nickel ternary positive electrode material having the chemical formula LiNi0.88Co0.10Al0.02O2The average particle size was 10 μm.
The preparation method comprises the following steps:
weighing 1mol of high-nickel ternary positive electrode material precursor (Ni)0.88Co0.10Al0.02(OH)2) And 1mol of lithium hydroxide monohydrate, then carrying out heat treatment for 4h at 480 ℃ in an oxygen atmosphere, and then heating to 750 ℃ for 20h to obtain the undoped high-nickel ternary cathode material.
Electrochemical tests show that the specific capacities of the first charge and the first discharge within the voltage ranges of 0.1C and 2.5-4.3V are 231.5 mAh g and 208.3mAh g respectively-1The first charge-discharge coulombic efficiency was 89.99%, as shown in fig. 1; under the condition of high multiplying power (3C) and within the voltage range of 2.5-4.3V, the specific discharge capacity is 174.4mAh g-1As shown in fig. 2; the capacity retention rate after 100 cycles under the conditions of 1.0C and 2.5-4.3V is 84.08%, as shown in FIG. 3.
From the results, the method is favorable for stabilizing the oxygen skeleton of the high-nickel ternary cathode material and improving the cycle performance of the high-nickel ternary cathode material by doping the aliovalent ions, particularly by double doping Ta and another element. The 100-cycle capacity retention rate of the doped modified high-nickel ternary cathode material can reach 100.05 percent, and the 100-cycle capacity retention rate of the comparative example is only 84.08 percent.
In addition, through the doping of the aliovalent ions, the fusion and growth among crystals are effectively inhibited in the high-temperature roasting process due to the larger ion diffusion energy barrier, so that the smaller primary particle size is realized, as shown in fig. 4, the solid-phase diffusion path of lithium ions is favorably shortened, the lithium ion diffusion rate is improved, and the higher rate performance is realized, for example, compared with the comparative example 2, the first discharge specific capacity is increased from 210.6mAh g-1Increased to 211.2mAh g-1And the specific discharge capacity at 3C is 177mAh g-1Increased to 181.4mAh g-1。
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The high nickel ternary positive electrode material doped with the heterovalent ions is characterized by having a chemical formula
Li1+kNixCoyMzM’aO2，
In the formula, k is more than or equal to-0.1 and less than or equal to 0.1, x is more than or equal to 0.5 and less than 1, y is more than 0 and less than 1, z is more than 0 and less than 1, a is more than 0 and less than or equal to 0.1, and x + y + z + a is more than 0.5 and less than or equal to 1.1;
m is Al or Mn, and M' is one or more elements which are doped to be divalent, tetravalent, pentavalent or hexavalent cations.
2. The aliovalent ion doped high nickel ternary positive electrode material according to claim 1, characterized in that M' is at least one of Mg, Ti, Zr, V, Nb, Mo, W, Ru, Te, Sb, Ta.
3. The aliovalent ion doped high nickel ternary positive electrode material according to claim 1 or 2, characterized in that M' is Ta and additionally at least one satisfying element.
4. The aliovalent ion doped high nickel ternary positive electrode material according to claim 3, characterized in that the molar proportion of Ta in the positive electrode material is not more than 5%.
5. The aliovalent ion doped high nickel ternary positive electrode material according to claim 3 or 4, characterized in that M' is Ta and one of Zr, Mo, W, Te, Ru, V, Sb.
6. The aliovalent ion-doped high-nickel ternary positive electrode material according to claim 5, characterized in that the aliovalent ion-doped high-nickel ternary positive electrode material has the chemical formula LiNi0.88Co0.1Al0.02Ta0.01Zr0.02O2，LiNi0.88Co0.10Al0.0 2Ta0.01Mo0.005O2，LiNi0.88Co0.10Al0.02Ta0.01Te0.02O2，LiNi0.88Co0.10Al0.02Ta0.02W0.01O2Or LiNi0.88Co0.10Al0.02Ta0.02Sb0.01O2。
7. The aliovalent ion-doped high-nickel ternary cathode material according to any one of claims 1 to 6, wherein the concentration of M tends to decrease in a gradient manner and the concentration of M' tends to decrease in a gradient manner in a direction from the surface to the core of the aliovalent ion-doped high-nickel ternary cathode material.
8. The method for preparing the aliovalent ion doped high-nickel ternary cathode material according to any one of claims 1 to 7, characterized by comprising the following steps:
and (3) carrying out solid-phase mixing and coating on a precursor of the matrix high-nickel ternary cathode material and the doping raw material, then mixing with lithium hydroxide monohydrate, and then carrying out two-stage high-temperature heat treatment.
9. The method for preparing the aliovalent ion doped high-nickel ternary cathode material according to claim 8, wherein the doping raw material is one of a nano oxide, an inorganic salt and an organic salt of M';
and/or in the two-stage high-temperature heat treatment process, the heat treatment temperature of the first stage is 400-800 ℃, the heat treatment time is 3-10h, the heat treatment temperature of the second stage is 650-900 ℃, and the heat treatment time is 10-30 h.
10. A lithium ion battery comprising a positive electrode, wherein the positive electrode comprises the aliovalent ion-doped high-nickel ternary positive electrode material according to any one of claims 1 to 7.
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