CN113540436A - Tungsten ion doped high nickel gradient ternary positive electrode material and preparation method thereof - Google Patents

Tungsten ion doped high nickel gradient ternary positive electrode material and preparation method thereof Download PDF

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CN113540436A
CN113540436A CN202110646970.9A CN202110646970A CN113540436A CN 113540436 A CN113540436 A CN 113540436A CN 202110646970 A CN202110646970 A CN 202110646970A CN 113540436 A CN113540436 A CN 113540436A
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nickel
cobalt
manganese
tungsten
solution
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童汇
余荣天
喻万景
丁治英
田庆华
郭学益
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Central South University
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    • H—ELECTRICITY
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • H—ELECTRICITY
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    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract

A tungsten ion doped high nickel gradient ternary cathode material is spherical particles, nickel element is reduced in gradient from the inside of the particles to the surface, manganese element is increased in gradient from the inside of the particles to the surface, cobalt element is uniformly distributed in the cathode material particles, and tungsten element is doped on the surfaces of the particles. The preparation method comprises the following steps: pumping the low-nickel-cobalt-manganese mixed salt solution into the high-nickel-cobalt mixed salt solution, continuously pumping the mixed solution into a reaction kettle filled with an ammonia water solution, heating and introducing protective gas, adjusting the ammonia concentration and the pH value, stirring for coprecipitation reaction, stirring and aging, filtering, washing, drying, mixing with a lithium source and a tungsten source, grinding, and sintering to obtain the ternary cathode material. According to the invention, through the gradient structure of the material and the doping of tungsten ions, the material structure is stabilized, the ionic conductivity of the material is improved, the electrochemical polarization of the material in the charging and discharging processes is reduced, and the performance and the stability of the nickel ternary material can be greatly improved through the synergistic effect of the gradient structure and the doping of tungsten ions.

Description

Tungsten ion doped high nickel gradient ternary positive electrode material and preparation method thereof
Technical Field
The invention belongs to the field of battery materials, and particularly relates to a tungsten ion doped high-nickel gradient ternary positive electrode material and a preparation method thereof.
Background
The layered nickel cobalt lithium manganate ternary material is one of the most promising positive electrode materials, and is currently used in the field of electric vehicles on a large scale. However, the low nickel ternary material such as nickel cobalt manganese 111 can only reach the reversible capacity of about 160mAh/g, and the market demand is difficult to meet. In order to increase the specific capacity of the ternary material, the most effective method is to increase the nickel content, such as nickel-cobalt-manganese 811 ternary material, which can release the specific capacity of more than 200mAh/g at most. However, compared with the low-nickel ternary material, the high-nickel ternary material has the defects of unstable structure and poor cycle and rate performance due to excessively high nickel content on the surface, so that further research is needed.
The patent document with publication number CN110518219A discloses a core-shell structure high nickel gradient nickel-cobalt-manganese-aluminum quaternary positive electrode material and a preparation method thereof, wherein the method comprises the steps of controlling the addition sequence of salt solutions of four elements of nickel, cobalt, manganese and aluminum and a precipitator to form a gradient and a core-shell structure, and mixing and sintering the gradient and the precipitant with a lithium source to obtain the core-shell structure high nickel gradient nickel-cobalt-manganese-aluminum quaternary positive electrode material. The preparation method needs to replace the precipitator in the process, the operation is complex, and the coprecipitation reaction is more difficult to control due to the operation of replacing the precipitator and the addition of the aluminum salt.
The patent document with publication number CN107895793A discloses a preparation method of a tungsten-doped boride-coated lithium battery cathode material, which comprises dissolving a tungsten source in water, spraying the solution into a mixed raw material of a ternary precursor and a lithium source in a spraying manner, stirring for a period of time, evaporating to dryness to obtain a dried material, loading the dried material into a sagger, roasting for a period of time to obtain a tungsten-doped ternary cathode material, adding a metal boride into the tungsten-doped ternary cathode material, stirring uniformly, and sintering at a certain temperature to obtain the tungsten-doped boride-coated lithium battery cathode material. In the method, complicated steps such as spraying, stirring, evaporating and the like are added in the actual operation, a tungsten source needs to be dissolved in water in advance, the ternary material is easy to damage in the subsequent boride coating process, the production time, the cost and the uncertainty are greatly increased, and the large-scale production is difficult to popularize.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects and shortcomings in the background technology and provides a tungsten ion doped high-nickel gradient ternary cathode material and a preparation method thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the ternary cathode material is a nickel-cobalt-manganese ternary cathode material, the nickel-cobalt-manganese ternary cathode material is spherical particles, the content of nickel element is reduced in a gradient manner from the inside to the surface of the cathode material particles, the content of manganese element is increased in a gradient manner from the inside to the surface of the cathode material particles, the cobalt element is uniformly distributed in the cathode material particles, and the tungsten element is doped on the surface of the cathode material particles.
According to the invention, the tungsten ion doped modified high-nickel gradient ternary cathode material is adopted, and the addition of the tungsten ions can change the surface energy of the microstructure of the material, so that the anisotropy on different surfaces of the material is increased, the shape of primary particles is changed, the shape of the primary particles is changed from a relatively thick rice grain shape to a slender needle shape, the specific surface area is greatly increased, the diffusion path of lithium ions is shortened, and the diffusion coefficient of the lithium ions is increased. Tungsten ions enter into crystal lattices of the ternary material, the original valence state balance of the material is broken, part of trivalent nickel ions are converted into divalent nickel ions, and the proportion of the divalent nickel ions is increased, so that the charge and discharge capacity of the material is improved, the polarization of the tungsten ions in the charge and discharge process can be inhibited, and the cycle stability of the material is greatly improved.
Preferably, the average particle size of the tungsten ion doped high nickel gradient ternary cathode material particles is 10-15 μm; the molecular formula of the tungsten ion doped high nickel gradient ternary cathode material is Li (Ni)0.8Co0.1Mn0.1)xW1-xO2Wherein 0.97<x<1。
As a general inventive concept, the present invention also provides a preparation method of the above tungsten ion doped high nickel gradient ternary cathode material, comprising the following steps:
(1) pumping the low-nickel-cobalt-manganese mixed salt solution into the high-nickel-cobalt mixed salt solution, stirring to form a mixed solution, continuously pumping the mixed solution into a reaction kettle filled with an ammonia water solution, heating, introducing a protective gas, adjusting the ammonia concentration and the pH value in the reaction kettle, and simultaneously stirring to perform a coprecipitation reaction to obtain a solution containing a precursor material; the concentration of nickel ions in the low-nickel-cobalt-manganese mixed salt solution is lower than that in the high-nickel-cobalt mixed salt solution;
(2) stirring and aging the solution containing the precursor material obtained in the step (1), filtering, washing and drying to obtain a nickel-cobalt-manganese hydroxide precursor;
(3) and (3) mixing and grinding the nickel-cobalt-manganese hydroxide precursor obtained in the step (2) with a lithium source and a tungsten source, and then performing two-stage sintering in an oxidizing atmosphere to obtain the tungsten ion doped high-nickel gradient ternary cathode material.
In the preparation method, preferably, the total molar concentration of nickel, cobalt and manganese ions in the low-nickel-cobalt-manganese mixed salt solution is 0.3-3.0 mol/L, and the molar ratio of nickel, cobalt and manganese is 7:1: 2; if the total molar concentration of the nickel, cobalt and manganese ions is too low, the precipitation time is long, and the production is not facilitated, and if the total molar concentration of the nickel, cobalt and manganese ions is too high, the pH value in the reaction process is not facilitated to be controlled, and the sedimentation effect is not good.
The total molar concentration of nickel ions and cobalt ions in the nickelic nickel-cobalt mixed salt solution is 0.3-3.0 mol/L, and the molar ratio of nickel ions to cobalt ions is 9: 1. If the total molar concentration of nickel and cobalt is too low, the precipitation time is long, which is not favorable for production, and if the total molar concentration of nickel and cobalt ions is too high, the pH value in the reaction process is not favorable for control, and the precipitation effect is not good.
Preferably, in the step (1), the feeding time of the low-nickel-cobalt-manganese mixed salt solution pumped into the high-nickel-cobalt mixed salt solution is 35 to 45 hours, and the mixed solution of the low-nickel-cobalt-manganese mixed salt solution and the high-nickel-cobalt mixed salt solution is continuously fed into the reaction kettle at the same time.
In the above preparation method, preferably, in the step (1), the protective gas is a nitrogen atmosphere or an argon atmosphere; adjusting the ammonia concentration in the reaction kettle to be 0.4-0.6 mol/L by using ammonia water with the mass concentration of 25-28%; adjusting the pH value in the reaction kettle by using a hydroxide precipitator solution with the concentration of 1.0-7.0 mol/L to keep the pH value at 10-12; the molar concentration of the hydroxide precipitant solution is 1.5-3 times of the total molar concentration of the metal ions in the low-nickel-cobalt-manganese mixed salt solution; the hydroxide precipitator is one or two of sodium hydroxide and potassium hydroxide. The concentration of the hydroxide precipitant is 1.0-7.0 mol/L, if the molar concentration of the hydroxide precipitant solution is too high, the complexation of metal ions is not facilitated, and if the molar concentration of the hydroxide precipitant solution is too low, the pH value of the reaction solution is difficult to be effectively controlled.
In the preparation method, preferably, in the step (1), the temperature of the coprecipitation reaction is 40-60 ℃, and the stirring speed in the reaction process is 800-1200 r/min; in the step (2), the aging time is 10-14 hours.
In the preparation method, preferably, in the step (3), the molar ratio of the total moles of nickel, cobalt and manganese elements in the nickel-cobalt-manganese hydroxide precursor to the molar ratio of lithium elements in the lithium source is 1: 1.03-1.08; the molar ratio of the total mole of nickel, cobalt and manganese elements in the nickel-cobalt-manganese hydroxide precursor to the mole of tungsten in the tungsten source is 1: 0.001-0.03.
In the above preparation method, preferably, the lithium source is one or both of lithium hydroxide monohydrate and lithium carbonate; the tungsten source is one or two of tungsten trioxide and tungsten disulfide;
the low-nickel-cobalt-manganese mixed salt solution is a mixed solution of soluble nickel salt, soluble cobalt salt and soluble manganese salt;
the nickelic nickel-cobalt mixed salt solution is a mixed solution of soluble nickel salt and soluble cobalt salt;
the soluble nickel salt is one or more of nickel sulfate, nickel nitrate and nickel acetate; the soluble cobalt salt is one or more of cobalt sulfate, cobalt nitrate, cobalt acetate or cobalt chloride; the soluble manganese salt is one or more of manganese sulfate, manganese nitrate, manganese acetate or manganese chloride.
In the above preparation method, preferably, in the step (3), the oxidizing atmosphere is an air atmosphere or an oxygen atmosphere; the two-stage sintering is to sinter the mixture for 3 to 5 hours at 400 to 500 ℃ and then sinter the mixture for 10 to 14 hours at 650 to 850 ℃.
In the preparation method, preferably, in the step (3), the heating rate of the two-stage sintering is 3-8 ℃/min. If the temperature rise rate is too fast, it is difficult to ensure sufficient reaction of the material, and if the temperature rise rate is too slow, it is not favorable for industrial production.
Compared with the prior art, the invention has the advantages that:
(1) aiming at the defect that the surface of a high-nickel ternary material is unstable, firstly, a low-nickel high-manganese surface is constructed by a gradient material, so that side reactions caused by high-nickel-content elements on the surface are reduced, the problem of unstable surface structure of the material is solved by high-manganese content, then, tungsten ion doping is carried out, the microstructure energy of the surface of the material is changed, the growth of primary particles is more ordered, the size of the primary particles is also shrunk, the ionic conductivity is favorably improved, and the surface structure of the material is further stabilized; the existence of the tungsten-oxygen bond ensures that the high-nickel ternary material is not easy to generate irreversible phase change during high delithiation, and the high-valence tungsten ions are doped, so that the content of divalent nickel is increased, and the capacity of the high-nickel ternary material is improved to a certain extent.
(2) According to the invention, through the gradient structure of the material and the doping of tungsten ions, the material structure is stabilized, the ionic conductivity of the material is improved, the electrochemical polarization of the material in the charging and discharging processes is reduced, and the performance and the stability of the nickel ternary material can be greatly improved through the synergistic effect of the gradient structure and the doping of tungsten ions.
(3) The tungsten ion doped modified high-nickel gradient ternary cathode material has high stable cycle performance and excellent rate performance, the material is assembled into a battery, the first discharge specific capacity reaches 201mAh/g and the current density reaches 200mA/g under the conditions that the charge-discharge voltage is 2.7-4.3V and the current density is 20mA/g, the first discharge specific capacity reaches 184.2mAh/g, after 100 cycles of circulation, the discharge specific capacity reaches 184.8mAh/g, capacity loss is basically avoided, after 300 cycles of circulation, the discharge specific capacity reaches 171mAh/g, the capacity retention rate reaches 92.8%, and the capacity can be kept at 160mAh/g under the current density of 2A/g.
(4) The method has simple process, simplifies the operation of the reaction of the coprecipitation method, reduces the failure rate of the final product reaching the qualified requirement caused by the defective rate of each step, and can improve the adverse effect of the ternary material caused by the interface problem to a greater extent by doping and modifying the adopted gradient structure material and the tungsten ions; compared with the existing industrial synthesis method of the ternary material, although the gradient structure design and the tungsten ion doping are added, only the charging mode needs to be changed in the synthesis process, the ternary material is synthesized from the production of the precursor to the subsequent lithium mixing sintering, the production equipment does not need to be added, the additional production step is not needed, the raw material cost is low, and the method is suitable for industrial production.
Drawings
FIG. 1 is an SEM image of a Ni-Co-Mn hydroxide precursor of example 1 according to the invention;
FIG. 2 is an XRD pattern of the tungsten ion doped high nickel gradient ternary material of example 1 of the present invention;
FIG. 3 is a SEM image comparing the gradient ternary material of tungsten ion doped high nickel with the gradient ternary material of undoped high nickel in the embodiment 1 of the present invention;
FIG. 4 is a comparison of discharge cycle curves of a cell assembled from a ternary material with a gradient of tungsten ion doped high nickel and a ternary material with an undoped high nickel gradient according to example 1 of the present invention;
FIG. 5 is a comparison of the rate performance curves of a cell assembled from a tungsten ion doped high nickel gradient ternary material and an undoped high nickel gradient ternary material according to example 1 of the present invention;
FIG. 6 is a comparison of discharge cycle curves of a battery assembled by a tungsten ion doped high nickel gradient ternary material and a tungsten ion doped high nickel ternary material with a non-gradient structure in example 2 of the present invention;
fig. 7 is a discharge cycle graph of a cell assembled by the tungsten ion doped high nickel gradient ternary material in example 3 of the present invention.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
The nitrogen, argon or oxygen used in the invention is high-purity gas with the purity of more than or equal to 99.99 percent.
Example 1:
the invention relates to a tungsten ion doped high nickel gradient ternary cathode material, the molecular formula of which is Li (Ni)0.8Co0.1Mn0.1)0.99W0.01O2The nickel-cobalt-manganese ternary positive electrode material is spherical particles with the average particle size of 12 mu m, the content of nickel element is reduced in a gradient manner from the inside to the surface of the positive electrode material particles, the content of manganese element is increased in a gradient manner from the inside to the surface of the positive electrode material particles, cobalt element is uniformly distributed in the positive electrode material particles, and tungsten element is doped on the surface of the positive electrode material particles.
The preparation method of the tungsten ion doped high nickel gradient ternary cathode material comprises the following steps:
(1) pumping 2L of low nickel content nickel cobalt manganese solution (mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate, wherein the molar ratio of Ni ions to Co ions and Mn ions is 7:1:2, and the total molar concentration of Ni ions, Co ions and Mn ions is 2.0mol/L) into a container filled with 2L of high nickel content nickel cobalt solution (mixed solution of nickel sulfate and cobalt sulfate, wherein the molar ratio of Ni ions to Co ions is 9:1, and the total molar concentration of Ni ions and Co ions is 2.0mol/L) at a feeding speed of 50mL/h, stirring at normal temperature to form a mixed solution, meanwhile, continuously pumping the mixed solution into a continuous stirring reaction kettle filled with 2L of 0.45mol/L of ammonia water solution at a feeding speed of 100mL/h (the total feeding time is 40 hours), introducing high-purity nitrogen as a protective atmosphere in the reaction kettle, adjusting the temperature in the reaction kettle to be kept at 40 ℃, continuously stirring, simultaneously adjusting the ammonia water concentration of a reaction system to be 0.45mol/L by using 25% ammonia water of mass concentration, adjusting the pH value of the reaction system to be 11.4 by using 5mol/L sodium hydroxide solution, then heating to 50 ℃, carrying out coprecipitation reaction under the continuous stirring of 1000r/min, and obtaining a precursor material solution of nickel-cobalt-manganese hydroxide after the feeding is finished;
(2) keeping the nickel-cobalt-manganese hydroxide precursor material solution obtained in the step (1) at 50 ℃, stirring and aging for 12h, filtering, repeatedly washing the filtrate with deionized water, and drying in a 60 ℃ blast oven for 24h to obtain a nickel-cobalt-manganese hydroxide precursor;
(3) weighing 1g of the nickel-cobalt-manganese hydroxide precursor prepared in the step (2), 0.4901g of lithium hydroxide monohydrate and 0.0258g of tungsten trioxide, grinding, heating to 450 ℃ at the speed of 5 ℃/min in the atmosphere of high-purity oxygen, sintering for 4h, heating to 780 ℃ at the speed of 5 ℃/min, sintering for 12h, and cooling to room temperature to obtain the tungsten ion doped high-nickel gradient ternary cathode material.
Comparative example:
the comparative example is different from example 1 in that tungsten trioxide was not added in step (3), and a ternary material of a gradient structure of undoped tungsten was prepared as a control.
The XRD pattern of the tungsten ion doped high nickel gradient ternary cathode material prepared in the embodiment is shown in figure 1, the layered structure is good, and the synthesized sample is LiNiO of PDF card2(PDF # 85-1966).
An electron micrograph of the nickel-cobalt-manganese hydroxide precursor prepared in this example is shown in fig. 2, and the nickel-cobalt-manganese hydroxide precursor prepared in this example has uniform morphology and uniform particle size, and has an average particle size of 12 μm.
An electron microscope image of the tungsten ion doped high-nickel gradient ternary cathode material prepared in the embodiment and a gradient structure ternary material of a comparative example, which is not doped with tungsten, is shown in fig. 3, wherein secondary particles before and after doping are in a sphere-like shape, and primary particles of the doped material are obviously shrunk, which is beneficial to diffusion of lithium ions.
Weighing 0.80g of the tungsten ion doped high-nickel gradient ternary cathode material prepared in the embodiment, adding 0.1g of acetylene black serving as a conductive agent and 0.1g of PVDF polyvinylidene fluoride serving as a binder, mixing and grinding the materials by taking N-methylpyrrolidone as a solvent, and coating the mixture on the surface of an aluminum foil to prepare a cathode sheet; and then, assembling the metal lithium sheet cathode, the microporous polypropylene diaphragm and the electrolyte into a CR2025 button cell in a closed glove box filled with argon, and carrying out charge and discharge performance test.
As can be seen from FIG. 4, the first discharge specific capacity of the doped high-nickel gradient ternary cathode material of the embodiment can reach as high as 201mAh/g under the conditions that the charge-discharge voltage is 2.7-4.3V and the current density is 20mA/g, and can reach as high as 184.2mAh/g under the conditions that the current density is 200mA/g, the first discharge specific capacity is higher than that of an undoped material, and the cycling stability is also higher.
As can be seen from fig. 5, the tungsten-doped high-nickel gradient ternary cathode material prepared in this embodiment has a better rate capability, and particularly, the capacity can reach 160mAh/g at a current density of 2A/g, which indicates that the material has a better electrochemical performance under a high rate condition, and the specific capacity of the undoped material at each current density is lower than that of the doped material.
Example 2:
the tungsten ion doped high nickel gradient ternary cathode material Li (Ni) of the embodiment0.8Co0.1Mn0.1)0.985W0.015O2The preparation method comprises the following steps:
(1) the process for preparing the precursor of the high-nickel gradient ternary cathode material is the same as the step (1) and the step (2) of the embodiment 1;
(2) after 1g of the prepared nickel-cobalt-manganese hydroxide precursor, 0.4901g of lithium hydroxide monohydrate and 0.0414g of tungsten disulfide are ground, the temperature is raised to 450 ℃ at the rate of 5 ℃/min in the atmosphere of high-purity oxygen, the mixture is sintered for 4h, then the temperature is raised to 750 ℃ at the rate of 5 ℃/min, the mixture is sintered for 12h, and the mixture is cooled to room temperature, so that the tungsten ion doped high-nickel gradient ternary cathode material is obtained, wherein the microstructure and the layered structure of the tungsten ion doped high-nickel gradient ternary cathode material are similar to those in example 1.
A conventional coprecipitation method is adopted to synthesize a precursor of a ternary material with a non-gradient structure, the difference from the embodiment 2 is that in the step (1), nickel, cobalt and manganese are mixed into 2L of mixed solution with the total molar concentration of Ni, Co and Mn of 2mol/L according to the ratio of 8:1:1 by the conventional coprecipitation method, then the mixed solution is directly introduced into a reaction kettle for reaction at the speed of 50mL/h, the rest reaction parameters and conditions are consistent, and then the method which is the same as the embodiment (2) is adopted to synthesize the ternary positive electrode material Li (Ni) with the tungsten ion doped with high nickel and the non-gradient structure (Ni and Ni) and the ternary positive electrode material Li is synthesized0.8Co0.1Mn0.1)0.985W0.015O2。
The positive electrode material prepared in this example and the tungsten ion-doped high-nickel ternary positive electrode material without the non-gradient structure were assembled into a battery by the same method as in example 1, and a charge and discharge performance test was performed, as shown in fig. 6. As can be seen from FIG. 6, when the charging and discharging voltage is 2.7-4.3V and the current density is 20mA/g, the first specific discharge capacity of the gradient tungsten ion doped material prepared in the embodiment is up to 202mAh/g, and the first specific discharge capacity is up to 179.9mAh/g when the current density is 200mA/g, and the capacity retention ratio reaches 91.1% after 300 cycles of charging and discharging; the first discharge specific capacity of the non-gradient tungsten ion doped material is only 194mAh/g under the current density of 20mA/g, the first discharge specific capacity is 175.5mAh/g under the current density of 200mA/g, and the capacity retention rate of 300 cycles of charge-discharge circulation is only 82.0%.
Example 3:
the invention relates to a tungsten ion doped high nickel gradient ternary anode material Li (Ni)0.8Co0.1Mn0.1)0.98W0.02O2The nickel-cobalt-manganese ternary cathode material is a nickel-cobalt-manganese ternary cathode material, the nickel-cobalt-manganese ternary cathode material is in a spherical particle shape with the average particle size of 12 mu m, the content of nickel element is reduced in a gradient manner from the inside to the surface of the cathode material particle, and the content of manganese element is reduced from the cathode material particleThe interior of the material particles is increased in a gradient manner to the surface, the cobalt element is uniformly distributed in the anode material particles, and the tungsten element is doped on the surface of the anode material particles.
The preparation method of the tungsten ion doped high nickel gradient ternary cathode material comprises the following steps:
(1) pumping 4L of nickel-cobalt-manganese solution with low nickel content (mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate, wherein the molar ratio of Ni ions to Co ions and Mn ions is 7:1:2, and the total molar concentration of Ni ions, Co ions and Mn ions is 2.0mol/L) into a container filled with 4L of nickel-cobalt solution with high nickel content (mixed solution of nickel sulfate and cobalt sulfate, wherein the molar ratio of Ni ions to Co ions is 9:1, and the total molar concentration of Ni ions and Co ions is 2.0mol/L) at a feeding speed of 100mL/h, stirring and mixing at normal temperature, meanwhile, the mixed solution is continuously pumped into a continuous stirring reaction kettle filled with 4L of 0.45mol/L ammonia water solution at the feeding speed of 200mL/h (the feeding time is 40 hours in total), introducing high-purity nitrogen as protective atmosphere in the reaction kettle, adjusting the temperature in the reaction kettle to be kept at 40 ℃ and continuously stirring. Meanwhile, ammonia water with the mass concentration of 25% is used for adjusting the ammonia water concentration of the reaction system to be kept at 0.45mol/L, 5mol/L sodium hydroxide solution is used for adjusting the pH value of the reaction system to 11.4, the temperature is raised to 50 ℃, coprecipitation reaction is carried out under the continuous stirring of 50 ℃ and 1000r/min, and after the feeding is finished, aging is carried out for 12 hours, so as to obtain a precursor material solution of the nickel-cobalt-manganese hydroxide;
(2) keeping the nickel-cobalt-manganese hydroxide precursor material solution obtained in the step (1) at 50 ℃, stirring, aging for 15h, filtering, repeatedly washing the filtrate with deionized water, and drying in a 60 ℃ blast oven for 24h to obtain a nickel-cobalt-manganese hydroxide precursor;
(3) weighing 1g of the nickel-cobalt-manganese hydroxide precursor prepared in the step (2), 0.4901g of lithium hydroxide monohydrate and 0.0387g of tungsten trioxide, grinding, heating to 450 ℃ at the speed of 5 ℃/min in the atmosphere of high-purity oxygen, sintering for 4h, heating to 780 ℃ at the speed of 5 ℃/min, sintering for 12h, and cooling to room temperature to obtain the tungsten ion doped high-nickel gradient ternary cathode material.
A battery was assembled in the same manner as in example 1, and subjected to a charge and discharge performance test, with the results shown in fig. 7. As can be seen from FIG. 7, under the conditions that the charging and discharging voltage is 2.7-4.3V and the current density is 20mA/g, the first specific discharge capacity can reach 197mAh/g, the current density is 200mA/g, the first specific discharge capacity can reach 177mAh/g, and the capacity retention rate reaches 90.5% after 300 cycles of charging and discharging.

Claims (10)

1. The tungsten ion doped high-nickel gradient ternary cathode material is characterized in that the ternary cathode material is a nickel-cobalt-manganese ternary cathode material, the nickel-cobalt-manganese ternary cathode material is spherical and granular, the content of nickel elements is reduced in a gradient manner from the inside to the surface of cathode material granules, the content of manganese elements is increased in a gradient manner from the inside to the surface of the cathode material granules, cobalt elements are uniformly distributed in the cathode material granules, and tungsten elements are doped on the surface of the cathode material granules.
2. The tungsten ion doped high nickel gradient ternary cathode material of claim 1, wherein the mean particle size of the particles of the tungsten ion doped high nickel gradient ternary cathode material is 10-15 μm.
3. The preparation method of the tungsten ion doped high nickel gradient ternary cathode material according to any one of claims 1 to 2, characterized by comprising the following steps:
(1) pumping the low-nickel-cobalt-manganese mixed salt solution into the high-nickel-cobalt mixed salt solution, stirring to form a mixed solution, continuously pumping the mixed solution into a reaction kettle filled with an ammonia water solution, heating, introducing a protective gas, adjusting the ammonia concentration and the pH value in the reaction kettle, and simultaneously stirring to perform a coprecipitation reaction to obtain a solution containing a precursor material; the concentration of nickel ions in the low-nickel-cobalt-manganese mixed salt solution is lower than that in the high-nickel-cobalt mixed salt solution;
(2) stirring and aging the solution containing the precursor material obtained in the step (1), filtering, washing and drying to obtain a nickel-cobalt-manganese hydroxide precursor;
(3) and (3) mixing and grinding the nickel-cobalt-manganese hydroxide precursor obtained in the step (2) with a lithium source and a tungsten source, and then performing two-stage sintering in an oxidizing atmosphere to obtain the tungsten ion doped high-nickel gradient ternary cathode material.
4. The preparation method according to claim 3, wherein the total molar concentration of nickel, cobalt and manganese ions in the low-nickel-cobalt-manganese mixed salt solution is 0.3-3.0 mol/L, and the molar ratio of nickel, cobalt and manganese is 7:1: 2;
the total molar concentration of nickel ions and cobalt ions in the nickelic nickel-cobalt mixed salt solution is 0.3-3.0 mol/L, and the molar ratio of nickel ions to cobalt ions is 9: 1.
5. The preparation method of claim 3, wherein in the step (1), the feeding time of the low-nickel-cobalt-manganese mixed salt solution pumped into the high-nickel-cobalt mixed salt solution is 35 to 45 hours, and the mixed solution of the low-nickel-cobalt-manganese mixed salt solution and the high-nickel-cobalt mixed salt solution is continuously fed into the reaction kettle within the same feeding time.
6. The method according to claim 3, wherein in the step (1), the protective gas is nitrogen or argon;
adjusting the ammonia concentration in the reaction kettle by using ammonia water with the mass concentration of 25-28% to keep the ammonia concentration at 0.4-0.6 mol/L:
adjusting the pH value in the reaction kettle by using a hydroxide precipitator solution with the concentration of 1.0-7.0 mol/L to keep the pH value at 10-12; the molar concentration of the hydroxide precipitant solution is 1.5-3 times of the total molar concentration of the metal ions in the low-nickel-cobalt-manganese mixed salt solution; the hydroxide precipitator is one or two of sodium hydroxide and potassium hydroxide.
7. The preparation method according to any one of claims 3 to 6, wherein in the step (1), the temperature of the coprecipitation reaction is 40 to 60 ℃, and the stirring speed during the reaction is 800 to 1200 r/min;
in the step (2), the aging time is 10-14 hours.
8. The preparation method according to any one of claims 3 to 6, wherein in the step (3), the molar ratio of the total moles of the nickel, cobalt and manganese elements in the nickel-cobalt-manganese hydroxide precursor to the molar ratio of the lithium element in the lithium source is 1:1.03 to 1.08; the molar ratio of the total mole of nickel, cobalt and manganese elements in the nickel-cobalt-manganese hydroxide precursor to the mole of tungsten in the tungsten source is 1-0.97: 0.001-0.03.
9. The method according to any one of claims 3 to 6, wherein the lithium source is one or both of lithium hydroxide monohydrate and lithium carbonate; the tungsten source is one or two of tungsten trioxide and tungsten disulfide;
the low-nickel-cobalt-manganese mixed salt solution is a mixed solution of soluble nickel salt, soluble cobalt salt and soluble manganese salt;
the nickelic nickel-cobalt mixed salt solution is a mixed solution of soluble nickel salt and soluble cobalt salt;
the soluble nickel salt is one or more of nickel sulfate, nickel nitrate and nickel acetate; the soluble cobalt salt is one or more of cobalt sulfate, cobalt nitrate, cobalt acetate or cobalt chloride; the soluble manganese salt is one or more of manganese sulfate, manganese nitrate, manganese acetate or manganese chloride.
10. The production method according to any one of claims 3 to 6, wherein in the step (3), the oxidizing atmosphere is an air atmosphere or an oxygen atmosphere; the two-stage sintering is to sinter the mixture for 3 to 5 hours at 400 to 500 ℃ and then sinter the mixture for 10 to 14 hours at 650 to 850 ℃.
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