CN113903907A - Preparation method of tungsten-coated and doped single-crystal nickel-rich ternary cathode material - Google Patents

Preparation method of tungsten-coated and doped single-crystal nickel-rich ternary cathode material Download PDF

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CN113903907A
CN113903907A CN202111175709.1A CN202111175709A CN113903907A CN 113903907 A CN113903907 A CN 113903907A CN 202111175709 A CN202111175709 A CN 202111175709A CN 113903907 A CN113903907 A CN 113903907A
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cathode material
ternary cathode
tungsten
crystal nickel
nickel
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CN113903907B (en
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周文政
区丽敏
农盛恒
黄甜甜
黄海富
梁先庆
刘海镇
蓝志强
黄丹
郭进
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Guangxi University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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Abstract

The invention discloses a preparation method of a tungsten-coated and doped single-crystal nickel-rich ternary cathode material, which specifically comprises the following steps: (1) mixing the nickel-cobalt-manganese ternary precursor with a lithium source, calcining, and ball-milling to obtain a single crystal nickel-rich ternary cathode material; (2) and mixing the single-crystal nickel-rich ternary cathode material with a tungsten source, calcining, and cooling to obtain the tungsten-coated and doped single-crystal nickel-rich ternary cathode material. According to the invention, the single coating, the single doping and the random control of both coating and doping of the single crystal nickel-rich ternary cathode material are realized by regulating the consumption of the tungsten source, so that the structural stability of the single crystal nickel-rich ternary cathode material is effectively enhanced, the polarization of the material is reduced, and the lithium ion diffusion dynamics is improved, thereby improving the cycle stability and the rate capability of the battery.

Description

Preparation method of tungsten-coated and doped single-crystal nickel-rich ternary cathode material
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to a preparation method of a tungsten-coated and doped single crystal nickel-rich ternary anode material.
Background
The lithium ion battery has the advantages of small self-discharge, no memory effect, high output voltage, long cycle life, environmental protection and the like, so that the lithium ion battery has a wide development prospect in the field of new energy automobiles. At present, with the rapid development of new energy automobiles, more and more electric automobiles begin to enter the lives of common consumers, so that the demands of people on the endurance mileage and the service life of the electric automobiles are continuously improved. Therefore, it is important to develop lithium ion batteries with higher energy density and cycle life.
The positive electrode material is an important part in the lithium ion battery, and the performance of the positive electrode material is important for the performance of the lithium ion battery, such as the capacity of the positive electrode material determines the upper limit of the capacity of the whole battery. At present, the anode materials in the market mainly comprise lithium cobaltate, lithium manganate, a nickel-cobalt-manganese ternary system and lithium iron phosphate. The above-mentioned conventional positive electrode materials have respective problems with respect to the nickel-cobalt-manganese ternary system. Such as: the cobalt in the lithium cobaltate is expensive and the cost is high; the lithium manganate is unstable in structure in the discharging process, is greatly influenced by temperature, and is easy to cause the performance deterioration of the battery; the lithium iron phosphate has low electric conductivity, small lithium ion diffusion coefficient and poor high-temperature performance. In addition, these lithium transition metal oxides generally have not high enough energy density, and it is difficult to make a breakthrough progress in battery energy density by modifying the composition and structure.
The ternary anode material has the advantages of high specific capacity, long cycle life and the like, so that the ternary anode material becomes a hot material of the anode of the lithium ion battery, but still has many problems to be solved. For example, a large number of grain boundaries exist inside secondary particles of the polycrystalline ternary cathode material, and during the charging and discharging processes of a battery, due to anisotropic lattice change, the grain boundaries of the polycrystalline ternary cathode material are prone to crack, so that microcracks are generated in the secondary particles, and the cycle performance and the thermal stability of the material are reduced. In addition, the surface residual alkali may aggravate side reactions between the active material and the electrolyte during the reaction process, and release gas, affecting the life and safety of the battery.
Compared with the polycrystalline ternary cathode material, the single crystal ternary cathode material system only keeps primary particles, and the structure of the single crystal ternary cathode material system is intrinsically provided with no crystal boundary, so that the formation of micro/nano cracks is effectively relieved, and the single crystal ternary cathode material has better structural integrity, so that the single crystal ternary cathode material has better cycle stability and thermal stability compared with the polycrystalline ternary cathode material, and is widely researched and focused. However, the intrinsic performance enhancement of single crystals relative to polycrystalline ternary positive electrode materials is also relatively limited. In addition, the single crystal ternary cathode material has relatively large primary particle size and long ion diffusion path, so that the multiplying power performance is poor, and the application of the single crystal ternary cathode material in high-power electric vehicles is limited. Therefore, the technical scheme with simple process is developed, the structural stability and the conductivity of the single crystal ternary cathode material are further improved through doping, cladding and the like, and the method has important scientific significance.
At present, the modification method of the ternary cathode material mainly comprises two methods of coating and doping. The surface coating is mainly used as a protective layer to isolate the direct contact between the electrolyte and the active electrode material, so that a series of side reactions are reduced to a great extent, for example, the precipitation of transition metal is reduced, a thinner CEI film is formed, the precipitation of oxygen atoms is reduced, and the like, and the electrochemical stability is improved. And the protective layer can relieve the structural collapse of the active material caused by the volume change generated by lithium removal/lithium insertion in the charging and discharging process. The doping modification can reduce the mixed discharge of cations, improve the stability of a layered structure, widen the diffusion channel of lithium ions and improve the conductivity of the material.
In the existing tungsten source modification technical method for the nickel-rich ternary cathode material, the targeted modification object is a polycrystalline material. And one preparation method only realizes one of single cladding, single doping and cladding and doping, and does not change the parameter details and simultaneously realizes the full coverage of three conditions.
Therefore, the modification of the single crystal nickel-rich ternary cathode material by coordinating and cooperating the coating and doping through reasonable design is a key exploration direction for the modification of the single crystal nickel-rich ternary cathode material at present and in the future.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing a tungsten-coated and doped single crystal nickel-rich ternary cathode material, so as to solve the defects in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a tungsten-coated and doped single-crystal nickel-rich ternary cathode material is characterized in that a modification method of single coating, single doping and both coating and doping of the material is simultaneously realized in one preparation method aiming at the single-crystal nickel-rich ternary cathode material, and specifically comprises the following steps:
(1) mixing the nickel-cobalt-manganese ternary precursor with a lithium source, calcining, and ball-milling to obtain a single crystal nickel-rich ternary cathode material;
(2) and mixing the single-crystal nickel-rich ternary cathode material with a tungsten source, calcining, and cooling to obtain the tungsten-coated and doped single-crystal nickel-rich ternary cathode material.
The preparation method has the beneficial effects that single cladding, single doping and cladding and doping of the single crystal nickel-rich ternary cathode material are simultaneously realized in only one preparation method, so that the rate capability and the cycle performance of the single crystal material are effectively improved. In addition, the preparation method of the invention has the advantages of short preparation time, simple operation process, low cost of selected raw materials, easy obtainment and better performance of the obtained materials than that of a comparison sample.
Further, in the step (1), the chemical formula of the nickel-cobalt-manganese ternary precursor isNi0.6Co0.2Mn0.2(OH)2。
The further technical scheme has the beneficial effect that the nickel-cobalt-manganese ternary precursor selected by the invention can determine the specific ternary proportion for the single crystal nickel-rich ternary cathode material.
Further, in the step (1), the lithium source is at least one of lithium hydroxide, lithium carbonate, lithium oxide, lithium chloride, lithium nitrate and lithium oxalate.
The beneficial effect of adopting the further technical scheme is that a lithium source selection scheme is provided for the preparation of the ternary cathode material and the implementation is preferable.
Further, in the step (1), the molar ratio of Li in the lithium source to Ni + Co + Mn in the nickel-cobalt-manganese ternary precursor is 1 (1.0-1.1).
The beneficial effects of adopting the further technical scheme are that the excessive lithium can make up for the loss of lithium in the calcining process, the proper excessive lithium can improve the crystallization degree of the material, reduce the mixed discharging of lithium and nickel, and obtain the ternary cathode material with a better layered structure; however, the particle size is increased and the surface is rough due to the over-high lithium doping amount, so that the insertion and extraction rate of lithium ions is reduced, the conductivity of the anode material is reduced, and the rate capacity is further reduced; moreover, the excessive lithium doping can cause the reaction of residual alkali and electrolyte to release gas, which affects the safety and cycle life of the battery.
Further, in the step (1), the temperature rise rate of the calcination is 2-6 ℃/min, the temperature is 500-1000 ℃, the calcination atmosphere is air and/or oxygen, and the time is 3-15 h.
The further technical scheme has the beneficial effect that the preferable preparation process conditions are provided for many factors such as the heating rate, the heat preservation temperature, the atmosphere, the heat preservation time and the like involved in the stage.
Further, in the step (1), the ball-material ratio of the ball mill is 10:1, the rotation speed is 200-.
The further technical scheme has the beneficial effects that the secondary particles of the ternary cathode material can be effectively dispersed by optimizing the ball milling condition, so that the ideal single crystal ternary cathode material is obtained.
Further, in the step (1), the chemical formula of the single crystal nickel-rich ternary cathode material is as follows: liaNixCoyMn1-x-yO2(ii) a Wherein x is more than or equal to 0.6 and less than 1, y is more than 0 and less than or equal to 0.20, z is more than 0 and less than or equal to 0.20, and x + y + z is 1; a is more than or equal to 0.95 and less than or equal to 1.10.
The further technical scheme has the beneficial effects that the obtained single crystal nickel-rich ternary cathode material with the element proportion range has the advantages of more excellent structural stability, cycle stability, thermal stability and the like.
Further, in the step (2), the tungsten source is at least one of tungsten trioxide, lithium tungstate, sodium tungstate and tungstic acid.
The further technical scheme has the advantages that the optimized tungsten source selected by the invention can stabilize the crystal structure of the anode material, effectively inhibit the occurrence of side reactions and improve the electrochemical performance of the anode material.
Further, in the step (2), the mass of the tungsten source is 0.01-3% of the mass of the mixture of the single crystal nickel-rich ternary cathode material and the tungsten source.
The further technical scheme has the beneficial effects that the single doping, the single cladding or both the doping and the cladding of the single crystal nickel-rich ternary cathode material are realized by regulating and controlling the amount of the tungsten source.
Further, in the step (2), the temperature rise rate of the calcination is 2-6 ℃/min, the temperature is 400-.
The beneficial effect of adopting the further technical scheme is that the tungsten source is successfully modified by optimizing the two-step calcining process conditions to obtain the tungsten-coated and doped monocrystal nickel-rich ternary cathode material.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
1. compared with the traditional method for improving the cycling stability of the material by coating, doping or synergistic modification of the polycrystalline ternary cathode material, the method realizes the modification of the single crystal nickel-rich ternary cathode material by regulating the using amount of the tungsten source, effectively enhances the structural stability of the single crystal nickel-rich ternary cathode material, reduces the polarization of the material, and improves the lithium ion diffusion dynamics, thereby simultaneously improving the cycling stability and the rate capability of the battery.
2. According to the invention, through a simple two-step calcination method, in the same preparation method, the amount of a tungsten source is effectively regulated and controlled, so that not only can single tungsten doping and single tungsten coating of the single crystal nickel-rich ternary cathode material be realized, but also the coating and doping of the single crystal nickel-rich ternary cathode material can be realized, which is a key innovation of the invention and has important significance for the development of ternary cathode materials, especially the modification means of the single crystal nickel-rich ternary cathode material.
3. The preparation method of the tungsten-coated and doped single-crystal nickel-rich ternary cathode material is simple to operate, can obtain the required material only by two-step calcination, has an environment-friendly process, and is suitable for large-scale production.
Drawings
FIG. 1 is a comparative XRD pattern of samples prepared in examples 1-3 and comparative example;
FIG. 2 is a scanning electron micrograph of a sample prepared in comparative example 1;
FIG. 3 is a scanning electron micrograph of a sample prepared in example 2;
FIG. 4 is a HRTEM image and a Fourier transform of selected regions of the sample prepared in comparative example 1;
FIG. 5 is a HRTEM image and a Fourier transform (cladding) image of selected regions of the sample prepared in example 1;
FIG. 6 is a HRTEM image and a Fourier transform image of selected regions (cladding doped lithium-enriching layer) of the sample prepared in example 2;
FIG. 7 is a HRTEM image of a sample prepared in example 3 and a Fourier transform image (doping) of selected regions;
FIG. 8 is a graph showing cycle performance of samples prepared in examples 1 to 3 and comparative example 1 (the capacity curve corresponding to 300 circles is, from top to bottom, example 2, example 1, example 3 and comparative example 1);
FIG. 9 is a graph of rate capability of samples prepared in examples 1-3 and comparative example 1.
Detailed Description
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 only a part of the embodiments of the present invention, and not all 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
A preparation method of a tungsten-coated and/or doped single-crystal nickel-rich ternary cathode material is a modification method for simultaneously realizing single coating, single doping and both coating and doping of the material in one preparation method aiming at the single-crystal nickel-rich ternary cathode material, and specifically comprises the following steps:
(1) 4.7038g of nickel-cobalt-manganese ternary precursor Ni0.6Co0.2Mn0.2(OH)2Mixing with 2.2692g of lithium hydroxide, then placing the mixture into a calcining furnace, heating the mixture to 950 ℃ at the heating rate of 5 ℃/min for calcining for 10h under the oxygen atmosphere, then placing the mixture into a ball mill according to the ball-to-material ratio of 10:1 for ball milling for 1h at the rotating speed of 200r/min to obtain the single crystal nickel-rich ternary cathode material LiNi0.6Co0.2Mn0.2O2；
Wherein Li and Ni-Co-Mn ternary precursor Ni in lithium hydroxide0.6Co0.2Mn0.2(OH)2The molar ratio of Ni, Co and Mn is 1: 1.06;
(2) single crystal nickel-rich ternary positive electrode material LiNi0.6Co0.2Mn0.2O2Mixing with tungsten trioxide, then placing into a calcining furnace, heating to 800 ℃ at the heating rate of 5 ℃/min under the argon atmosphere, calcining for 2h, and cooling with the furnace to obtain the tungsten-coated and doped single crystal nickel-rich ternary cathode material;
wherein the tungsten trioxide is a single crystal nickel-rich ternary cathode material LiNi0.6Co0.2Mn0.2O2The mass of the tungsten trioxide mixture is 0.5 percent.
Example 2
A preparation method of a tungsten-coated and/or doped single-crystal nickel-rich ternary cathode material is a modification method for simultaneously realizing single coating, single doping and both coating and doping of the material in one preparation method aiming at the single-crystal nickel-rich ternary cathode material, and specifically comprises the following steps:
(1) 4.7038g of nickel-cobalt-manganese ternary precursor Ni0.6Co0.2Mn0.2(OH)2Mixing with 2.2692g of lithium hydroxide, then placing the mixture into a calcining furnace, heating the mixture to 950 ℃ at the heating rate of 5 ℃/min for calcining for 10h under the oxygen atmosphere, then placing the mixture into a ball mill according to the ball-to-material ratio of 10:1 for ball milling for 1h at the rotating speed of 200r/min to obtain the single crystal nickel-rich ternary cathode material LiNi0.6Co0.2Mn0.2O2；
Wherein Li and Ni-Co-Mn ternary precursor Ni in lithium hydroxide0.6Co0.2Mn0.2(OH)2The molar ratio of Ni, Co and Mn is 1: 1.06;
(2) single crystal nickel-rich ternary positive electrode material LiNi0.6Co0.2Mn0.2O2Mixing with tungsten trioxide, then placing into a calcining furnace, heating to 800 ℃ at the heating rate of 5 ℃/min under the argon atmosphere, calcining for 2h, and cooling with the furnace to obtain the tungsten-coated and doped single crystal nickel-rich ternary cathode material;
wherein the tungsten trioxide is a single crystal nickel-rich ternary cathode material LiNi0.6Co0.2Mn0.2O21 percent of the mass of the tungsten trioxide mixture.
Example 3
A preparation method of a tungsten-coated and/or doped single-crystal nickel-rich ternary cathode material is a modification method for simultaneously realizing single coating, single doping and both coating and doping of the material in one preparation method aiming at the single-crystal nickel-rich ternary cathode material, and specifically comprises the following steps:
(1) 4.7038g of nickel-cobalt-manganese ternary precursor Ni0.6Co0.2Mn0.2(OH)2Mixing with 2.2692g of lithium hydroxide, then placing the mixture into a calcining furnace, heating the mixture to 950 ℃ at the heating rate of 5 ℃/min for calcining for 10h under the oxygen atmosphere, then placing the mixture into a ball mill according to the ball-to-material ratio of 10:1 for ball milling for 1h at the rotating speed of 200r/min to obtain the single crystal nickel-rich ternary cathode material LiNi0.6Co0.2Mn0.2O2；
Wherein Li and Ni-Co-Mn ternary precursor Ni in lithium hydroxide0.6Co0.2Mn0.2(OH)2The molar ratio of Ni, Co and Mn is 1: 1.06;
(2) single crystal nickel-rich ternary positive electrode material LiNi0.6Co0.2Mn0.2O2Mixing with tungsten trioxide, then placing into a calcining furnace, heating to 800 ℃ at the heating rate of 5 ℃/min under the argon atmosphere, calcining for 2h, and cooling with the furnace to obtain the tungsten-coated and doped single crystal nickel-rich ternary cathode material;
wherein the tungsten trioxide is a single crystal nickel-rich ternary cathode material LiNi0.6Co0.2Mn0.2O21.5 percent of the mass of the tungsten trioxide mixture.
Comparative example 1
The difference from the embodiment 1 is only that 'single crystal nickel-rich ternary cathode material LiNi' is not included0.6Co0.2Mn0.2O2And mixing with tungsten trioxide to obtain the single crystal nickel-rich ternary cathode material.
Performance testing
1. X-ray diffraction (XRD) test
FIG. 1 is a comparative XRD pattern of samples prepared in examples 1-3 and comparative example.
As can be seen from FIG. 1, the samples of comparative example 1 and examples 1-3 are both typical of α -NaFeO2The structure belongs to the space group of R3m, and the samples of examples 1-3 have no diffraction peak detected in other phases. Indicating that WO cannot be detected except for a small amount thereof3The addition of (b) did not change the bulk structure of the entire phase.
2. Scanning electron microscope test
FIG. 2 is a scanning electron micrograph of a sample prepared in comparative example 1, and FIG. 3 is a scanning electron micrograph of a sample prepared in example 2.
As can be seen from fig. 2 and 3 and the refinement analysis of the XRD results, the samples of comparative example 1 and example 2 each have a single crystal structure, and the sample of example 2 has a lithium-rich state.
3. High Resolution Transmission Electron Microscopy (HRTEM) experiments and selected region Fourier transform results
Fig. 4 is an HRTEM and a fourier transform of selected regions of the sample prepared in comparative example 1, fig. 5 is an HRTEM and a fourier transform of selected regions (cladding) of the sample prepared in example 1, fig. 6 is an HRTEM and a fourier transform of selected regions (cladding doped lithium-rich layer) of the sample prepared in example 2, and fig. 7 is an HRTEM and a fourier transform of selected regions (doping) of the sample prepared in example 3.
As can be seen from fig. 4, the outer surface of the particles of the sample of comparative example 1 formed a layer of the rock salt phase. As can be seen from FIGS. 5 to 7, in examples 1 to 3, WO was finely controlled3The addition amounts of the components respectively realize single cladding, doping, cladding and single doping of the single crystal nickel-rich ternary material.
4. Cycle and rate performance testing
Samples prepared in examples 1-3 and comparative example 1 are respectively assembled with a metal lithium sheet and the like to form a button cell, and the cycling performance and the rate performance of the button cell are tested in a voltage interval of 2.8-4.4V. The results are shown in Table 1 and FIGS. 8-9.
Wherein, FIG. 8 is a graph of cycle performance of samples obtained in examples 1-3 and comparative example 1 (the capacity curve corresponding to 300 circles is, from top to bottom, example 2, example 1, example 3 and comparative example 1), and FIG. 9 is a graph of rate performance of samples obtained in examples 1-3 and comparative example 1.
TABLE 1 button cell Performance test results
Figure BDA0003295469220000091
As can be seen from Table 1 and FIG. 8, the capacity retention rate of the tungsten-coated and doped single crystal nickel-rich ternary cathode material prepared in examples 1-3 is higher than that of comparative example 1 after the tungsten-coated and doped single crystal nickel-rich ternary cathode material is cycled for 300 times under the current density of 1C within the voltage range of 2.8-4.4V. Among them, example 2 is the best example, and the capacity retention rate after 300 cycles is improved by 31.2% compared with comparative example 1.
The tests show that the cycle performance stability of the tungsten-coated and doped single crystal nickel-rich ternary cathode material prepared by the invention is obviously improved.
As can be seen from FIG. 9, the high rate discharge capacities of the samples of examples 1 to 3 were all higher than that of comparative example 1. Among them, example 2 is the best example, the 10C high rate capacity is as high as 147.5mAh/g, which is 8.1% higher than the 10C high rate capacity of comparative example 1.
The cycling stability and the rate performance show that the method has obvious effect and improves the electrochemical performance of the anode material. Among them, the lithium-rich state in which the elimination of lithium-nickel mixed emission is achieved while cladding doping represents the most excellent electrochemical performance.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. A preparation method of a tungsten-coated and doped single-crystal nickel-rich ternary cathode material is characterized in that aiming at the single-crystal nickel-rich ternary cathode material, a modification method of single coating, single doping and coating and doping of the material is realized simultaneously in only one preparation method, and the method specifically comprises the following steps:
(1) mixing the nickel-cobalt-manganese ternary precursor with a lithium source, calcining, and ball-milling to obtain a single crystal nickel-rich ternary cathode material;
(2) and mixing the single-crystal nickel-rich ternary cathode material with a tungsten source, calcining, and cooling to obtain the tungsten-coated and doped single-crystal nickel-rich ternary cathode material.
2. The method for preparing the tungsten-coated and doped single-crystal nickel-rich ternary cathode material according to claim 1, wherein in the step (1), the chemical formula of the nickel-cobalt-manganese ternary precursor is Ni0.6Co0.2Mn0.2(OH)2。
3. The method for preparing the tungsten-coated and doped single-crystal nickel-rich ternary cathode material according to claim 1, wherein in the step (1), the lithium source is at least one of lithium hydroxide, lithium carbonate, lithium oxide, lithium chloride, lithium nitrate and lithium oxalate.
4. The method for preparing the tungsten-coated and doped single-crystal nickel-rich ternary cathode material according to any one of claims 1 to 3, wherein in the step (1), the molar ratio of Li in the lithium source to Ni + Co + Mn in the nickel-cobalt-manganese ternary precursor is 1 (1.0-1.1).
5. The method as claimed in claim 1, wherein in step (1), the temperature rise rate of the calcination is 2-6 ℃/min, the temperature is 500-1000 ℃, the calcination atmosphere is air and/or oxygen, and the time is 3-15 h.
6. The method as claimed in claim 1, wherein in the step (1), the ball-to-material ratio of the ball mill is 10:1, the rotation speed is 200-.
7. The method for preparing the tungsten-coated and doped single-crystal nickel-rich ternary cathode material according to claim 1, wherein in the step (1), the chemical formula of the single-crystal nickel-rich ternary cathode material is as follows: liaNixCoyMn1-x-yO2(ii) a Wherein x is more than or equal to 0.6 and less than 1, y is more than 0 and less than or equal to 0.20, z is more than 0 and less than or equal to 0.20, and x + y + z is 1; a is more than or equal to 0.95 and less than or equal to 1.10.
8. The method for preparing the tungsten-coated and doped single-crystal nickel-rich ternary cathode material as claimed in claim 1, wherein in the step (2), the tungsten source is at least one of tungsten trioxide, lithium tungstate, sodium tungstate and tungstic acid.
9. The method for preparing the tungsten-coated and doped single-crystal nickel-rich ternary cathode material according to claim 1 or 8, wherein in the step (2), the mass of the tungsten source is 0.01-3% of the mass of the mixture of the single-crystal nickel-rich ternary cathode material and the tungsten source.
10. The method as claimed in claim 1, wherein in step (2), the temperature-raising rate of the calcination is 2-6 ℃/min, the temperature is 400-900 ℃, the calcination atmosphere is argon, and the time is 1-5 h.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114665073A (en) * 2022-03-15 2022-06-24 远景动力技术(江苏)有限公司 Tungsten-containing positive electrode active material, electrochemical device, and electronic device
CN114784238A (en) * 2022-04-07 2022-07-22 华鼎国联电池材料有限公司 Lithium-containing oxide-coated ternary positive electrode material and preparation method thereof
CN114975935A (en) * 2022-06-02 2022-08-30 长沙理工大学 Tungsten-modified high-nickel ternary lithium ion battery positive electrode material and preparation method thereof
CN116314746A (en) * 2023-02-09 2023-06-23 广东邦普循环科技有限公司 Coated lithium-sodium composite ternary positive electrode material and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180183045A1 (en) * 2016-12-28 2018-06-28 Sichuan FuHua New Energy High-Tech Co., LTD. High-voltage ternary positive electrode material for lithium-ion battery and preparation method thereof
CN109742336A (en) * 2018-12-07 2019-05-10 北京理工大学 A kind of surface layer coats the tertiary cathode material and preparation method of tungstate lithium and doping W
CN112186138A (en) * 2019-07-02 2021-01-05 湖南杉杉新能源有限公司 W-containing high-nickel ternary positive electrode material and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180183045A1 (en) * 2016-12-28 2018-06-28 Sichuan FuHua New Energy High-Tech Co., LTD. High-voltage ternary positive electrode material for lithium-ion battery and preparation method thereof
CN109742336A (en) * 2018-12-07 2019-05-10 北京理工大学 A kind of surface layer coats the tertiary cathode material and preparation method of tungstate lithium and doping W
CN112186138A (en) * 2019-07-02 2021-01-05 湖南杉杉新能源有限公司 W-containing high-nickel ternary positive electrode material and preparation method thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114665073A (en) * 2022-03-15 2022-06-24 远景动力技术(江苏)有限公司 Tungsten-containing positive electrode active material, electrochemical device, and electronic device
CN114784238A (en) * 2022-04-07 2022-07-22 华鼎国联电池材料有限公司 Lithium-containing oxide-coated ternary positive electrode material and preparation method thereof
CN114784238B (en) * 2022-04-07 2023-09-05 华鼎国联电池材料有限公司 Ternary positive electrode material coated by lithium-containing oxide and preparation method thereof
CN114975935A (en) * 2022-06-02 2022-08-30 长沙理工大学 Tungsten-modified high-nickel ternary lithium ion battery positive electrode material and preparation method thereof
CN114975935B (en) * 2022-06-02 2024-02-13 长沙理工大学 Tungsten-modified high-nickel ternary lithium ion battery positive electrode material and preparation method thereof
CN116314746A (en) * 2023-02-09 2023-06-23 广东邦普循环科技有限公司 Coated lithium-sodium composite ternary positive electrode material and preparation method thereof
CN116314746B (en) * 2023-02-09 2024-03-12 广东邦普循环科技有限公司 Coated lithium-sodium composite ternary positive electrode material and preparation method thereof

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