CN113651373A - Anode material with uniform porous structure and preparation method thereof - Google Patents

Anode material with uniform porous structure and preparation method thereof Download PDF

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CN113651373A
CN113651373A CN202111215454.7A CN202111215454A CN113651373A CN 113651373 A CN113651373 A CN 113651373A CN 202111215454 A CN202111215454 A CN 202111215454A CN 113651373 A CN113651373 A CN 113651373A
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porous structure
uniform porous
cobalt
cathode material
nickel
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赵田
罗依梦
王天伟
万传恒
牛宏刚
栗晓静
徐云军
文万超
陈丹凤
尹正中
程迪
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Henan Kelong New Energy Co ltd
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Abstract

The invention discloses a cathode material with a uniform porous structure, which is in a uniform porous structure, wherein secondary particles D50 are 2-15um, and the porosity of the cathode material is 1.5% -5%. The preparation method comprises the following steps: synthesizing a nickel-cobalt-manganese oxalate precursor with a compact structure by adopting a coprecipitation method, mixing the oxalate precursor with the compact structure and a metal oxide doped with elements, and presintering to obtain a doped nickel-cobalt-manganese oxide precursor with a uniform porous structure; uniformly mixing a doped nickel-cobalt-manganese oxide precursor with a uniform porous structure with a lithium salt, sintering for the first time, mixing with a coating compound, and sintering for the second time to finally obtain the doped and coated nickel-cobalt-manganese lithium anode material with the uniform porous structure. The method has the advantages of simple process, low cost and obvious performance improvement, and the prepared nickel cobalt lithium manganate positive electrode material with a uniform porous structure still has excellent rate performance and output power under the condition of low cobalt content.

Description

Anode material with uniform porous structure and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a positive electrode material with a uniform porous structure and a preparation method thereof.
Background
In recent years, with the batch application of lithium ion batteries in start and stop systems for hybrid electric vehicles and 48V vehicles, the requirements on the rate and power performance of the lithium ion batteries in the market are higher and higher. The nickel cobalt lithium manganate ternary material is widely applied to the field of power batteries due to the advantages of higher capacity and energy density, excellent cycle performance, reliable safety performance, low toxicity and the like.
In order to improve the rate and power performance of the lithium ion battery, one of the fast and effective methods is to improve the cobalt content in the nickel cobalt lithium manganate ternary positive electrode material, but cobalt is a relatively rare strategic metal and is expensive, and if the cobalt content in the positive electrode material is improved, the cost of the positive electrode material is greatly increased. Therefore, on the premise of not increasing the cobalt content, the capacity and the energy density of the cathode material are improved, and the cost control is facilitated.
Many studies have been made in recent years to improve the rate and power performance of lithium ion batteries by changing the structure of a cathode material or a precursor thereof. Most of nickel cobalt lithium manganate positive electrode materials commercialized in the current market are of a solid structure, and are usually prepared by adopting a hydroxide nickel cobalt manganese precursor of the solid structure, the solid structure enables a lithium ion transmission path to be long, and the positive electrode material is not fully contacted with an electrolyte, so that the large-rate charge-discharge performance and the power performance are insufficient. In addition, although the cathode material with a shell outside and a hollow structure inside prepared by a template method or a core oxidation method, such as patents CN201310469896.3, CN201911291031.6, CN202110433232.6, etc., has a large specific surface area, so that the contact between the cathode material and an electrolyte is enhanced, and the rate and power performance of the cathode material can be improved to a certain extent, the cathode material with a hollow structure is easy to collapse during preparation or use due to the difference between the internal structure and the external structure, and has low tap density and compaction density, low particle strength, and easy breakage of cathode material particles during rolling of a pole piece, so that the structure of the cathode material is damaged, and the electrical performance of the cathode material is affected. For the porous structure, many data have been reported, for example, patents CN202010881538.3, CN202010968022.2, CN202110130621.1, etc., have developed a positive electrode material with a porous structure, but the pores inside the material are concentrated in the core to form a large pore, similar to a hollow structure, and the same structural problems exist.
Disclosure of Invention
In order to solve the problems, the invention provides a cathode material with a uniform porous structure and a preparation method thereof. The uniform porous structure refers to a structure in which pores inside the secondary particles are dispersed throughout the particles. The nickel cobalt lithium manganate positive electrode material with the uniform porous structure has a large specific surface area, enhances the contact between the positive electrode material and electrolyte, is different from a hollow structure, and can support the filling property of the positive electrode material due to the uniform porous structure, so that the particle strength and the true density of the positive electrode material are improved, the multiplying power and the power performance of the positive electrode material are improved while the low-cobalt content and low-cost advantages are ensured, and other electrical properties are also ensured.
The technical scheme of the invention is that the preparation method of the anode material with the uniform porous structure is characterized by comprising the following steps:
(1) synthesizing a nickel-cobalt-manganese oxalate precursor with a compact structure by adopting a coprecipitation method: respectively adding a metal salt solution containing Ni, Co and Mn, an ammonia water solution and oxalic acid or an ammonium oxalate solution into a reaction kettle using pure water as a base solution for reaction; in the reaction process, the temperature is controlled to be 40-60 ℃, the stirring speed is controlled to be 100-1000 r/min, the pH is controlled to be 8-13, and nitrogen is continuously introduced into the reaction kettle; filtering, separating, washing and drying the obtained solid-liquid mixture to obtain the nickel-cobalt-manganese oxalate precursor with the compact structure;
(2) uniformly mixing the nickel-cobalt-manganese oxalate precursor with the compact structure obtained in the step (1) with the metal oxide of the doping element, then pre-sintering, keeping the temperature at 400-700 ℃ for 2-8h, wherein the sintering atmosphere is air, and cooling to obtain a nickel-cobalt-manganese oxide precursor with a doping type uniform porous structure;
(3) uniformly mixing the doped nickel-cobalt-manganese oxide precursor with the uniform porous structure obtained in the step (2) with lithium salt, adopting a one-stage temperature-controlled sintering mode, keeping the temperature at 700-;
(4) and (3) uniformly mixing the doped nickel cobalt lithium manganate with a uniform porous structure obtained in the step (3) with a compound of a coating element, then carrying out secondary sintering, carrying out heat preservation at the temperature of 250-700 ℃ for 4-8h, wherein the sintering atmosphere is air, oxygen or a mixed gas of air and oxygen, and carrying out cooling and sieving to finally obtain the doped and coated nickel cobalt lithium manganate positive electrode material with a uniform porous structure.
Further, the metal salt solution in the step (1) is one or more of sulfate solution, nitrate solution, chloride solution and acetate solution, and the total metal ion concentration in the metal salt solution is 0.05-3 mol/L; the concentration of ammonium ions in the ammonia water solution is 3-6mol/L, and the concentration of oxalate ions in the oxalic acid or ammonium oxalate solution is 1-5 mol/L.
Further, in the step (2), the doping element is one or more of Al, Zr, W, Mg, Ti and Y, and the molar ratio of the doping element to (Ni + Co + Mn) in the oxalate precursor is 0.0001-0.05: 1.
Further, the lithium salt in the step (3) comprises one or more of lithium carbonate, lithium hydroxide, lithium oxalate, lithium nitrate and lithium acetate, wherein the molar ratio of Li to the total metals (Ni + Co + Mn) is 0.95-1.2: 1.
Further, in the step (4), the coating element is one or more of B, Al, Ti and W, and the mass percentage of the coating element in the positive electrode material is 0.05-0.5%.
Further, the compound of the coating element B in the step (4) is H3BO3、B2O3、Li3BO3、LiBO2One or more of them, the compound of the coating element Al is Al2O3、Al（OH）3、LiAlO2One or more of aluminum isopropoxide and TiO as the compound coating the element Ti2One or more of titanium isopropoxide and a compound of the coating element W is WO3、Li2WO4One or more of (a).
The invention also provides the cathode material with the uniform porous structure, which is prepared by the preparation method, the morphology of the cathode material is the uniform porous structure, namely the structure that the pores in the secondary particles are uniformly dispersed in the whole particles, the secondary particles D50 are 2-15um, and the porosity of the cathode material is 1.5% -5%.
Further, the chemical general formula of the cathode material is LiaNixCoyMn(1-x-y-z)MzO2@NbOcWherein a is more than or equal to 0.95 and less than or equal to 1.20, x is more than or equal to 0.3 and less than or equal to 0.9, y is more than or equal to 0 and less than or equal to 0.35, z is more than or equal to 0.0001 and less than or equal to 0.05, x + y + z is less than 1, b is more than 0 and less than or equal to 2, and c is more than 0 and less than or equal to 3; m is one or more of Al, Zr, W, Mg, Ti and Y, and N is one or more of B, Al, Ti and W.
The invention has the following beneficial effects:
(1) transition metal ion Ni in comparison with alkaline solution2+、Co2+、Mn2+In oxalate solutionThe precipitation rates are relatively similar, so that the content and the proportion of each element in the precursor can be relatively accurately controlled, and the structural stability of the anode material is greatly improved; compared with hydroxide precursors and carbonate precursors, oxalate in the oxalate precursors has larger molecular weight and is uniformly distributed in the precursors, and the anode material can release a large amount of gas in the high-temperature sintering process, so that uniformly distributed pores are generated in particles, and the anode material is in a uniform porous structure.
(2) By utilizing the characteristic of uniform and porous materials, the additive or lithium salt enters the pores, so that the uniformity of doping, mixing and coating is improved. Through high-temperature sintering, doping elements enter the crystal lattice of the anode material to play a role in stabilizing the material structure, so that the cycling stability, the thermal stability and the like of the material can be improved; the surface of the anode material is coated, so that the side reaction of the material and the electrolyte is reduced, and the storage, the inflation, the multiplying power, the power and other performances of the material can be improved.
(3) The contact area of the anode material with a uniform porous structure and the electrolyte is increased, the lithium ion diffusion path is shortened, and the multiplying power performance and the output power of the material are effectively improved while the advantages of low cobalt content and low cost are ensured.
Drawings
Fig. 1 is a cross section of a positive electrode material prepared in example 1;
fig. 2 is a cross section of the positive electrode material prepared in comparative example 1;
fig. 3 is a distribution of an additive element W in the positive electrode material prepared in example 1;
fig. 4 is a distribution of an additive element W in the positive electrode material prepared in comparative example 1;
fig. 5 is a graph comparing the different rate discharge capacity retention rates of pouch cells of the positive electrode materials prepared in the examples and the comparative example;
fig. 6 is a comparative graph of different condition discharge DCR of pouch cells of the cathode materials prepared in the examples and comparative examples.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
Anode material Li with uniform porous structure1.15Ni0.499Co0.2Mn0.3W0.001O2@Al2O3&B2O3The preparation method comprises the following steps:
synthesis of Ni-Co-Mn oxalate precursor Ni with compact structure by coprecipitation method0.5Co0.2Mn0.3C2O4: preparing a mixed metal salt solution with the total metal ion concentration of 2mol/L by using sulfates containing Ni, Co and Mn, wherein the molar ratio of Ni to Co to Mn is 5:2:3, preparing an ammonia water solution with the ammonium ion concentration of 5mol/L, preparing an ammonium oxalate solution with the oxalate ion concentration of 3mol/L, and then respectively adding the solutions into a reaction kettle using pure water as a base solution for reaction; in the reaction process, the temperature is controlled at 55 ℃, the stirring speed is controlled at 800r/min, the pH is controlled at 10, and nitrogen is continuously introduced into the reaction kettle; filtering, separating, washing and drying the obtained solid-liquid mixture to obtain the precursor Ni of nickel-cobalt-manganese oxalate with compact structure0.5Co0.2Mn0.3C2O4。
Ni oxalate precursor with compact structure0.5Co0.2Mn0.3C2O4And WO3Uniformly mixing, wherein the molar ratio of W to (Ni + Co + Mn) in the oxalate precursor is 0.001:1, then presintering, keeping the temperature at 500 ℃ for 5 hours, taking air as sintering atmosphere, and cooling to obtain the W-doped nickel-cobalt-manganese oxide precursor Ni with a uniform porous structure0.499Co0.2Mn0.3W0.001O。
Mixing a W-doped nickel-cobalt-manganese oxide precursor Ni with a uniform porous structure0.499Co0.2Mn0.3W0.001Uniformly mixing O and lithium carbonate, wherein the molar ratio of Li to total metal (Ni + Co + Mn) is 1.15:1, performing heat preservation at 900 ℃ for 10 hours in a one-stage temperature-controlled sintering mode in the sintering atmosphere of air, and crushing after cooling to obtain W-doped lithium nickel cobalt manganese oxide Li with a uniform porous structure1.15Ni0.499Co0.2Mn0.3W0.001O2。
Mixing W-doped nickel cobalt lithium manganate Li with uniform porous structure1.15Ni0.499Co0.2Mn0.3W0.001O2With Al2O3And H3BO3Uniformly mixing, wherein the mass percentages of Al and B in the positive electrode material are respectively 0.1% and 0.1%, then carrying out secondary sintering, keeping the temperature at 500 ℃ for 5h, taking air as the sintering atmosphere, cooling and sieving to finally obtain the W-doped and Al-and B-coated lithium nickel cobalt manganese oxide positive electrode material Li with a uniform porous structure1.15Ni0.499Co0.2Mn0.3W0.001O2@Al2O3&B2O3。
Example 2
Anode material Li with uniform porous structure1.1Ni0.545Co0.15Mn0.30Mg0.002Ti0.002Y0.001O2@WO3The preparation method comprises the following steps:
synthesis of Ni-Co-Mn oxalate precursor Ni with compact structure by coprecipitation method0.55Co0.15Mn0.30C2O4: preparing a mixed metal salt solution with the total metal ion concentration of 2mol/L by using sulfate containing Ni, Co and Mn, wherein the molar ratio of Ni to Co to Mn is 55:15:30, preparing an ammonia water solution with the ammonium ion concentration of 5mol/L, preparing an oxalic acid solution with the oxalate ion concentration of 3mol/L, and then respectively adding the solution into a reaction kettle using pure water as a base solution for reaction; in the reaction process, the temperature is controlled at 50 ℃, the stirring speed is controlled at 600r/min, the pH is controlled at 11, and nitrogen is continuously introduced into the reaction kettle; filtering, separating, washing and drying the obtained solid-liquid mixture to obtain the precursor Ni of nickel-cobalt-manganese oxalate with compact structure0.55Co0.15Mn0.30C2O4。。
Ni oxalate precursor with compact structure0.55Co0.15Mn0.30C2O4And MgO, TiO2、Y2O3、Mixing uniformly, wherein Mg, Ti and Y are mixed with (Ni + Co + Mn) in oxalate precursorThe mol ratio is 0.002:1, 0.002:1 and 0.001:1 respectively, then presintering is carried out, the temperature is kept for 4 hours at 600 ℃, the sintering atmosphere is air, and the temperature is reduced to obtain the Ni-Co-Mn oxide precursor Ni doped with Mg, Ti and Y and having a uniform porous structure0.545Co0.15Mn0.30Mg0.002Ti0.002Y0.001O。
Preparing a Ni-Co-Mn oxide precursor Ni of a uniform porous structure doped with Mg, Ti and Y0.545Co0.15Mn0.30Mg0.002Ti0.002Y0.001Uniformly mixing O and lithium carbonate, wherein the molar ratio of Li to total metals (Ni + Co + Mn) is 1.10:1, performing heat preservation at 850 ℃ for 12 hours in a one-stage temperature-controlled sintering mode in the sintering atmosphere of air, and crushing after cooling to obtain the Li-Ni-Co-Mn-Li lithium doped with Mg, Ti and Y and having a uniform porous structure1.1Ni0.545Co0.15Mn0.30Mg0.002Ti0.002Y0.001O2。
Doping Mg, Ti and Y-doped nickel cobalt lithium manganate Li with uniform porous structure1.1Ni0.545Co0.15Mn0.30Mg0.002Ti0.00 2Y0.001O2With WO3Uniformly mixing, wherein the mass percent of W in the positive electrode material is 0.3%, then carrying out secondary sintering, keeping the temperature at 600 ℃ for 5h, taking air as the sintering atmosphere, cooling and sieving to finally obtain the Mg, Ti, Y and W-doped nickel cobalt lithium manganate positive electrode material Li with a uniform porous structure1.1Ni0.545Co0.15Mn0.30Mg0.002Ti0.002Y0.001O2@WO3。
Example 3
Anode material Li with uniform porous structure1.08Ni0.598Co0.1Mn0.3Zr0.002O2@Al2O3&WO3The preparation method comprises the following steps:
synthesis of Ni-Co-Mn oxalate precursor Ni with compact structure by coprecipitation method0.6Co0.1Mn0.3C2O4: preparing a mixed metal salt solution with the total metal ion concentration of 2mol/L by using sulfates containing Ni, Co and Mn, wherein the molar ratio of Ni to Co to Mn is 6:1:3, preparing an ammonia water solution with the ammonium ion concentration of 5mol/L, preparing an ammonium oxalate solution with the oxalate ion concentration of 3mol/L, and then respectively adding the solutions into a reaction kettle using pure water as a base solution for reaction; in the reaction process, the temperature is controlled at 55 ℃, the stirring speed is controlled at 700r/min, the pH is controlled at 12, and nitrogen is continuously introduced into the reaction kettle; filtering, separating, washing and drying the obtained solid-liquid mixture to obtain the precursor Ni of nickel-cobalt-manganese oxalate with compact structure0.6Co0.1Mn0.3C2O4。
Ni oxalate precursor with compact structure0.6Co0.1Mn0.3C2O4And ZrO2Uniformly mixing, wherein the molar ratio of Zr to (Ni + Co + Mn) in the oxalate precursor is 0.002:1, presintering, keeping the temperature at 550 ℃ for 6 hours in the sintering atmosphere of air, and cooling to obtain the Zr-doped Ni-Co-Mn oxide precursor Ni with a uniform porous structure0.598Co0.1Mn0.3Zr0.002O。
Precursor Ni of Zr-doped nickel-cobalt-manganese oxide with uniform porous structure0.598Co0.1Mn0.3Zr0.002Uniformly mixing O and lithium carbonate, wherein the molar ratio of Li to total metal (Ni + Co + Mn) is 1.08:1, performing heat preservation at 800 ℃ for 12 hours in a one-stage temperature-controlled sintering mode in the sintering atmosphere of air, and crushing after cooling to obtain Zr-doped lithium nickel cobalt manganese oxide Li with a uniform porous structure1.08Ni0.598Co0.1Mn0.3Zr0.002O2。
The Zr-doped nickel cobalt lithium manganate Li with uniform porous structure1.08Ni0.598Co0.1Mn0.3Zr0.002O2With Al2O3And WO3Uniformly mixing, wherein Al and W account for 0.1 percent and 0.5 percent respectively by mass in the anode material, then carrying out secondary sintering, keeping the temperature at 450 ℃ for 8 hours in the sintering atmosphere of air, cooling and sieving,finally obtaining Zr-doped Ni-Co-Mn acid lithium anode material Li with Al and W-coated uniform porous structure1.08Ni0.598Co0.1Mn0.3Zr0.002O2@Al2O3&WO3。
Comparative example 1
Comparative example 1 is a cathode material Li of a solid structure, compared with examples1.15Ni0.499Co0.2Mn0.3W0.001O2@Al2O3&B2O3The preparation method comprises the following steps:
synthesis of Ni-Co-Mn hydroxide precursor Ni with compact structure by coprecipitation method0.5Co0.2Mn0.3（OH）2: preparing a mixed metal salt solution with the total metal ion concentration of 2mol/L by using sulfate containing Ni, Co and Mn, wherein the molar ratio of Ni to Co to Mn is 5:2:3, preparing an ammonia water solution with the ammonium ion concentration of 5mol/L, preparing a sodium hydroxide solution with the concentration of 2mol/L, and then respectively adding the solution into a reaction kettle using pure water as a base solution for reaction; in the reaction process, the temperature is controlled at 50 ℃, the stirring speed is controlled at 700r/min, the pH is controlled at 11.5, and nitrogen is continuously introduced into the reaction kettle; filtering, separating, washing and drying the obtained solid-liquid mixture to obtain the precursor Ni of the nickel-cobalt-manganese hydroxide with the compact structure0.5Co0.2Mn0.3（OH）2。
The other steps are the same as example 1, namely Ni is a precursor of Ni-Co-Mn hydroxide with compact structure0.5Co0.2Mn0.3（OH）2With additives WO3Uniformly mixing, wherein the molar ratio of W to (Ni + Co + Mn) in the hydroxide precursor is 0.001:1, and then presintering to obtain the W-doped compact-structure Ni-Co-Mn oxide precursor Ni0.499Co0.2Mn0.3W0.001O, mixing with lithium carbonate to perform primary sintering to obtain W-doped lithium nickel cobalt manganese oxide Li with compact structure1.15Ni0.499Co0.2Mn0.3W0.001O2Finally, with additive Al2O3And H3BO3Mixing and carrying out secondary sintering to finally obtain W-doped and Al-and B-coated lithium nickel cobalt manganese oxide positive electrode material Li with compact structure1.15Ni0.499Co0.2Mn0.3W0.001O2@Al2O3&B2O3。
Physical and chemical indexes and electrical property evaluation of the cathode materials in examples and comparative examples
The obtained cathode material was evaluated for profile morphology and porosity, uniformity of added elements, rate capability and power capability in the following manner
(1) Profile morphology and porosity
Cutting the anode material by an argon ion planishing instrument, and shooting the appearance by a field emission electron microscope; the cross-section SEM was processed with Image J software to calculate porosity.
(2) Uniformity of additive elements
And (4) performing surface scanning on the added elements in the anode material by using an energy spectrometer.
(3) Rate capability
The obtained positive electrode material is made into an 604062 type soft package battery, the soft package battery is conventionally formed after being prepared, the formed battery is subjected to different-rate discharge tests at room temperature, the charging rates are unified to be 1C, the discharging rates are respectively 1C, 3C, 5C, 7C and 10C, and the discharging capacity retention rates at different rates are calculated.
(4) Power performance
The obtained positive electrode material is made into an 604062 type soft package battery, the soft package battery is conventionally formed after being prepared, and the formed battery is subjected to discharge DCR test at normal temperature and low temperature respectively: after 1C is fully charged at normal temperature, discharging to 50% SOC at 1C, standing for 1h, then discharging for 10s at 20C, then discharging to 10% SOC, and standing for 1h, then discharging for 10s at 10C; after 1C is fully charged at normal temperature, discharging to 50% SOC at 1C, and then standing in an oven at the low temperature of-20 ℃ for 2h and then performing 5C pulse for 10 s; and calculating DCR under different conditions, wherein the calculation formula is DCR = (standing end voltage-voltage after pulse discharge)/pulse current.
Evaluation of
As can be seen from fig. 1 and 2, the cross-sectional morphology of the cathode material prepared in example 1 is uniform and porous, and the porosity is 2.11%; the cross-sectional morphology of the cathode material prepared in comparative example 1 was dense, and the porosity was 0.54%.
As can be seen from fig. 3 and 4, the distribution of the additive element W in the positive electrode material prepared in example 1 was uniform, whereas the distribution of the additive element W in the positive electrode material prepared in comparative example 1 was not uniform as in example 1, and the local element content was high.
TABLE 1 discharge capacity and retention at different rates
Figure 619915DEST_PATH_IMAGE002
As can be seen from table 1 and fig. 5, compared with the cathode material with the solid structure of comparative example 1, the cathode material with uniform and porous structure obtained by the preparation method of embodiment 1 of the present invention has better rate discharge performance and higher retention rate of large rate discharge capacity; even though the cobalt content of the uniform porous cathode materials obtained by the preparation methods of the embodiments 2 and 3 is reduced, the rate performance is close to the level of the cathode material with the solid structure of the comparative example 1.
TABLE 2 discharging DCR
Figure 474739DEST_PATH_IMAGE004
As can be seen from table 2 and fig. 6, compared with the cathode material of the solid structure of the comparative example 1, the DCR of the uniform porous cathode material obtained by the preparation method of the embodiment 1 of the present invention is significantly reduced at different SOCs and temperatures, i.e. the power performance is better; even though the cobalt content of the uniform porous cathode materials obtained by the preparation methods of the embodiments 2 and 3 is reduced, the DCR at different SOC and temperature is still lower than that of the cathode material with the solid structure of the comparative example 1, namely the power performance is not reduced.
It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features related to the embodiments of the present invention described above may be combined with each other as long as they do not conflict with each other. In addition, the above embodiments are only some embodiments of the present invention, not all embodiments, and all other embodiments obtained by those skilled in the art based on the embodiments of the present invention without any creative work belong to the protection scope of the present invention.

Claims (8)

1. The preparation method of the cathode material with the uniform porous structure is characterized by comprising the following steps of:
(1) synthesizing a nickel-cobalt-manganese oxalate precursor with a compact structure by adopting a coprecipitation method: respectively adding a metal salt solution containing Ni, Co and Mn, an ammonia water solution and oxalic acid or an ammonium oxalate solution into a reaction kettle using pure water as a base solution for reaction; in the reaction process, the temperature is controlled to be 40-60 ℃, the stirring speed is controlled to be 100-1000 r/min, the pH is controlled to be 8-13, and nitrogen is continuously introduced into the reaction kettle; filtering, separating, washing and drying the obtained solid-liquid mixture to obtain the nickel-cobalt-manganese oxalate precursor with the compact structure;
(2) uniformly mixing the nickel-cobalt-manganese oxalate precursor with the compact structure obtained in the step (1) with the metal oxide of the doping element, then pre-sintering, keeping the temperature at 400-700 ℃ for 2-8h, wherein the sintering atmosphere is air, and cooling to obtain a nickel-cobalt-manganese oxide precursor with a doping type uniform porous structure;
(3) uniformly mixing the doped nickel-cobalt-manganese oxide precursor with the uniform porous structure obtained in the step (2) with lithium salt, adopting a one-stage temperature-controlled sintering mode, keeping the temperature at 700-;
(4) and (3) uniformly mixing the doped nickel cobalt lithium manganate with a uniform porous structure obtained in the step (3) with a compound of a coating element, then carrying out secondary sintering, carrying out heat preservation at the temperature of 250-700 ℃ for 4-8h, wherein the sintering atmosphere is air, oxygen or a mixed gas of air and oxygen, and carrying out cooling and sieving to finally obtain the doped and coated nickel cobalt lithium manganate positive electrode material with a uniform porous structure.
2. The method for preparing a cathode material with a uniform porous structure according to claim 1, wherein the metal salt solution in the step (1) is one or more of a sulfate solution, a nitrate solution, a chloride solution and an acetate solution, and the total metal ion concentration in the metal salt solution is 0.05-3 mol/L; the concentration of ammonium ions in the ammonia water solution is 3-6mol/L, and the concentration of oxalate ions in the oxalic acid or ammonium oxalate solution is 1-5 mol/L.
3. The method for preparing the cathode material with the uniform porous structure according to claim 2, wherein the doping element in the step (2) is one or more of Al, Zr, W, Mg, Ti and Y, and the molar ratio of the doping element to Ni + Co + Mn in the oxalate precursor is 0.0001-0.05: 1.
4. The method according to claim 3, wherein the lithium salt in step (3) comprises one or more of lithium carbonate, lithium hydroxide, lithium oxalate, lithium nitrate and lithium acetate, and the molar ratio of Li to the total metals Ni + Co + Mn is 0.95-1.2: 1.
5. The method for preparing the cathode material with the uniform porous structure according to claim 4, wherein the coating element in the step (4) is one or more of B, Al, Ti and W, and the mass percentage of the coating element in the cathode material is 0.05-0.5%.
6. The method according to claim 5, wherein the compound of the coating element B in the step (4) is H3BO3、B2O3、Li3BO3、LiBO2One or more of them, the compound of the coating element Al is Al2O3、Al（OH）3、LiAlO2One or more of aluminum isopropoxide and TiO as the compound coating the element Ti2One or more of titanium isopropoxide and a compound of the coating element W is WO3、Li2WO4One or more of (a).
7. A cathode material with a uniform porous structure, which is prepared by the preparation method of any one of claims 1 to 6, wherein the morphology of the cathode material is a uniform porous structure, namely a structure in which pores inside secondary particles are uniformly dispersed in the whole particles, the secondary particles D50 are 2-15um, and the porosity of the cathode material is 1.5% -5%.
8. The cathode material with a uniform porous structure according to claim 7, wherein the cathode material has a chemical formula of LiaNixCoyMn(1-x-y-z)MzO2@NbOcWherein a is more than or equal to 0.95 and less than or equal to 1.20, x is more than or equal to 0.3 and less than or equal to 0.9, y is more than or equal to 0 and less than or equal to 0.35, z is more than or equal to 0.0001 and less than or equal to 0.05, x + y + z is less than 1, b is more than 0 and less than or equal to 2, and c is more than 0 and less than or equal to 3; m is one or more of Al, Zr, W, Mg, Ti and Y, and N is one or more of B, Al, Ti and W.
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