CN115159593A - Element-doped and cobalt-in-situ-coated precursor material, preparation method thereof and positive electrode material - Google Patents

Element-doped and cobalt-in-situ-coated precursor material, preparation method thereof and positive electrode material Download PDF

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CN115159593A
CN115159593A CN202211080028.1A CN202211080028A CN115159593A CN 115159593 A CN115159593 A CN 115159593A CN 202211080028 A CN202211080028 A CN 202211080028A CN 115159593 A CN115159593 A CN 115159593A
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王小玮
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Abstract

The invention belongs to the technical field of lithium ion battery materials, and mainly discloses an element-doped and cobalt-in-situ-coated precursor material and a preparation method thereof. Element doped and cobalt in-situ coated precursor material with chemical formula of Ni x Co y Mn z M p (OH) 2 @Co(OH) 2 M is a doping element;doping elements in the precursor material are circularly distributed in a low-concentration-high-concentration-low-concentration-high-low-concentration mode from inside to outside, and doping areas of the doping elements on the innermost layer and the outermost layer of the precursor material are low-concentration doping areas; cobalt is deposited on the surface of the precursor through a coprecipitation process to form a cobalt coating layer. By controlling the flow of the salt solution of the doping elements, the cyclic distribution of the doping elements in the precursor material in a 'low concentration-high concentration-low concentration' manner from inside to outside can be obtained. Gradient doping and in-situ coating are realized in one step in the preparation stage of the precursor, no additional process is needed, the precursor material with excellent quality can be obtained, and the economic benefit is greatly improved.

Description

Element-doped and cobalt-in-situ-coated precursor material, preparation method thereof and positive electrode material
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to an element-doped and cobalt-in-situ-coated precursor material and a preparation method thereof.
Background
Lithium ion batteries are widely used in the fields of portable electronic devices, power automobiles, aerospace, and the like because of their high energy density and long cycle life. Wherein, the high nickel ternary positive electrode material (LiNi) x Co y Mn z O 2 NCM, ni is more than or equal to 0.7) is concerned due to higher energy density and lower cost, but the structure stability is poor, the surface side reaction is severe, and the further development and application of the compound are seriously hindered. Therefore, modification studies of high-nickel ternary positive electrode materials are indispensable. The precursor is used as a front-end product of the anode material and has a critical influence on the performance of the anode material.
Disclosure of Invention
One of the objectives of the present invention is to provide an element-doped and cobalt-in-situ coated precursor material and a preparation method thereof.
The second objective of the present invention is to provide a positive electrode material having both high energy density and high stability.
In order to achieve the above object, the present invention provides the following specific technical solutions.
Firstly, the invention provides an element-doped and cobalt in-situ-coated precursor material, wherein the chemical formula of the precursor material is Ni x Co y Mn z M p (OH) 2 @Co(OH) 2 Wherein x is more than or equal to 0.7 and less than or equal to 1,0 and less than or equal to y is more than or equal to 0.2,0 and less than or equal to z and less than or equal to 0.3, x + y + z + p =1; m is a doping element and is one or more than two of Al, zr, mg, zn, nb, sr, sn, ti, ce, cr, fe, na, K, cu, V, mo, Y, in, ta, ge, bi and Pb; doping elements in the precursor material are circularly distributed in a low-concentration-high-concentration-low-concentration-high-low-concentration mode from inside to outside, and doping areas of the doping elements on the innermost layer and the outermost layer of the precursor material are low-concentration doping areas; cobalt is deposited on the surface of the precursor through a coprecipitation process to form a cobalt coating layer.
Further, in some preferred embodiments of the present invention, the molar ratio of the doping element to the total metal ions in the low-concentration doped region of the doping element is X1,0 < X1 ≦ 0.05; the molar ratio of the doping elements in the high-concentration doping area of the doping elements to the total metal ions in the area is X2, wherein X2 is more than 0 and less than or equal to 0.3; the doping amount of the doping element in the low-concentration doping region of the doping element is smaller than that in the high-concentration doping region.
Further, in some preferred embodiments of the present invention, the cobalt cladding layer has a thickness of less than 3 μm.
Based on the same inventive concept, the invention provides a preparation method of the element-doped and cobalt-in-situ-coated precursor material, which comprises the following steps of:
(1) Feeding a nickel salt solution, a cobalt salt solution, a manganese salt solution, a precipitator solution and a complexing agent solution into a first reaction kettle in a parallel flow manner, and carrying out coprecipitation reaction to form crystal nuclei with the particle size of 0.05-1 mu m;
(2) Introducing the slurry of the first reaction kettle into a second reaction kettle, introducing a nickel salt solution, a cobalt salt solution, a manganese salt solution, a salt solution of a doping element, a precipitator solution and a complexing agent solution in a concurrent flow manner, controlling the flow rate of the salt solution of the doping element to ensure that the doping concentration of the doping element in a precursor follows the cyclic distribution of 'low concentration-high concentration-low concentration', stopping adding the nickel salt solution, the manganese salt solution and the salt solution of the doping element when the granularity of the reaction slurry is 2-15 mu m, and only carrying out the precipitation reaction of cobalt;
(3) And after the reaction is finished, filtering the reaction slurry, and washing, drying, sieving and demagnetizing the solid phase to obtain the element-doped and cobalt-in-situ-coated precursor material.
Further, in some preferred embodiments of the present invention, in the above preparation method, the nickel salt, the cobalt salt, and the manganese salt are at least one of sulfate, nitrate, and chloride; the precipitator is sodium hydroxide; the complexing agent is ammonia water.
In addition, the invention provides a positive electrode material, which is obtained by mixing and sintering the element-doped and cobalt-in-situ-coated precursor material with lithium.
Further, the sintering process is divided into two stages, wherein the sintering temperature in the first stage is 400-500 ℃, and the heat preservation time is 3-5 hours; the sintering temperature in the second stage is 700-1000 ℃, and the temperature is kept for 9-1697 h.
The doping elements in the precursor material provided by the invention are circularly distributed in a 'low concentration-high concentration-low concentration' manner from inside to outside, and the high and low concentrations of the doping elements are circularly distributed to serve as a frame type support, so that the doping elements can obtain higher stability under lower doping amount, and the integrity of a layered structure and the electrochemical activity of the material are ensured; the doping regions of the doping elements of the innermost layer and the outermost layer of the precursor material are low-concentration doping regions, so that the content of the doping elements can be reduced as much as possible while the material performance is ensured.
The cobalt layer is coated outside the precursor material in situ, so that side reaction can be inhibited, the surface stability of the base material is improved, and the transmission of lithium ions is accelerated; the in-situ coating can realize the uniformity and completeness of the coating layer and the controllable thickness, and meanwhile, the coating layer is tightly connected with the matrix material and is not easy to fall off.
Compared with the prior art, the invention has the following beneficial effects:
(1) The designed circulating element doping structure can reduce the introduction amount of extra inert cations and ensure the activity of the material. In addition, the cyclic element doping can serve as a frame type support, and plays a role in stabilizing the structure to the maximum extent.
(2) The co-precipitation coating process designed by the invention is different from the traditional coating layer structure, can realize the uniformity and completeness of the coating layer and the controllable thickness, and is tightly connected with the base material and not easy to fall off. The surface layer is of a lithium cobaltate structure after lithium mixing and sintering, so that the lithium cobaltate structure is beneficial to the insertion/extraction of lithium ions, and can effectively inhibit the direct contact of nickel ions and electrolyte and reduce the degree of side reaction.
(3) Gradient doping and in-situ coating are realized in one step in the preparation stage of the precursor, no additional process is needed, the precursor material with excellent quality can be obtained, and the economic benefit is greatly improved.
Drawings
Fig. 1 is an SEM image of the precursor material prepared in example 1.
Fig. 2 is a diagram of the electrochemical performance of the lithium ion button cell assembled in example 1 and comparative examples 1-3.
Fig. 3 is a diagram of the electrochemical performance of the lithium ion button cell assembled in example 2.
Detailed Description
In order to facilitate understanding of the invention, the invention will be described more fully and in detail 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 invention provides a precursor material for element doping and cobalt in-situ coating. The chemical formula of the precursor material is Ni x Co y Mn z M p (OH) 2 @Co(OH) 2 Wherein x is more than or equal to 0.7 and less than or equal to 1,0 and less than or equal to y is more than or equal to 0.2,0 and less than or equal to z is less than or equal to 0.3, and x + y + z =1; m is a doping element. Doping elements in the precursor material are circularly distributed in a mode of 'low concentration-high concentration-low concentration' from inside to outside, and doping areas of the doping elements on the innermost layer and the outermost layer of the precursor material are low-concentration doping areas; cobalt is deposited on the surface of the precursor through a coprecipitation process to form a cobalt coating layer.
The doping element M may be any one of Al, zr, mg, zn, nb, sr, sn, ti, ce, cr, fe, na, K, cu, V, mo, Y, in, ta, ge, bi, and Pb, or a combination of two or more of the above elements, and is not limited to a large number.
The circulating doping structure of the doping element M can reduce the introduction amount of extra inert cations and ensure the activity of the material; can be used as a frame type support, and plays a role in stabilizing the structure to the maximum extent. And the doping areas of the doping elements of the innermost layer and the outermost layer of the precursor material are low-concentration doping areas, so that the content of the doping elements can be reduced as much as possible while the material performance is ensured.
The coprecipitation coating process is different from the traditional coating structure, can realize the uniformity and completeness of the coating layer and the controllable thickness, and is tightly connected with the base material and not easy to fall off. The surface layer is of a lithium cobaltate structure after lithium mixing and sintering, so that the lithium cobaltate structure is beneficial to the insertion/extraction of lithium ions, and can effectively inhibit the direct contact of nickel ions and electrolyte and reduce the degree of side reaction.
The invention also provides a preparation method of the element-doped and cobalt-in-situ-coated precursor material, and the doping elements in the precursor material can be circularly distributed from inside to outside in a low-concentration-high-concentration-low-concentration-high-low-concentration mode by controlling the flow of the salt solution of the doping elements.
Example 1
In this example, the chemical formula of the precursor is Ni 0.694 Co 0.1 Mn 0.2 W 0.006 (OH) 2 The concentration of the doped region of tungsten from inside to outside is 0.1-0.15-0.1 percent of the molar ratio of the total metal ions, and the coating layer is Co (OH) 2 The thickness of the clad layer was 0.1. Mu.m.
The preparation of the precursor material of the above design comprises the following steps:
(1) Respectively preparing a nickel salt solution, a cobalt salt solution, a manganese salt solution, a tungsten salt solution, a sodium hydroxide solution and an ammonia water solution.
(2) Pumping nickel salt solution, cobalt salt solution, manganese salt solution, sodium hydroxide solution and ammonia water solution into a reaction kettle 1 by using different peristaltic pumps to perform coprecipitation reaction, and transferring the particles into a reaction kettle 2 when the particles grow to 0.5 mu m.
(3) And (3) continuously introducing a nickel salt solution, a cobalt salt solution, a manganese salt solution, a sodium hydroxide solution and an ammonia water solution into the reaction kettle 2, and controlling the pumping speed of the tungsten salt solution to be slow-fast-slow so as to realize the gradient doping of tungsten. When the particles grow to 10 mu m, the addition of the nickel salt solution, the manganese salt solution and the tungsten salt solution is stopped, and only the cobalt salt solution is pumped. After the particles continue to grow to 10.1 mu m, the feeding is stopped, and precursor slurry is obtained.
(4) Carrying out solid-liquid separation on the precursor slurry obtained in the step (3), collecting solids, washing, drying, sieving and demagnetizing the solids to obtain the ternary precursor Ni-Ni with gradient doping of tungsten and in-situ coating of cobalt 0.694 Co 0.1 Mn 0.2 W 0.006 (OH) 2 @Co(OH) 2 。
FIG. 1 shows a precursor material Ni 0.694 Co 0.1 Mn 0.2 W 0.006 (OH) 2 @Co(OH) 2 SEM image of (d).
(5) And (3) ball-milling and mixing the ternary precursor lithium hydroxide monohydrate obtained in the step (4) according to a molar ratio of 1.06 0.694 Co 0.1 Mn 0.2 W 0.006 O 2 @LiCoO 2 。
And (3) preparing a positive electrode material: conductive agent: the pole piece is coated with a binder in the proportion of 8 -1 The specific capacity of the resin is 157.9 mAh g after 200 cycles of circulation -1 The specific capacity and the capacity retention rate of (2) were 91%.
Comparative example 1
The comparative example 1 is different from the example 1 in that the tungsten doping concentration of the precursor is gradually increased from the inside to the outside.
The chemical formula of the precursor is designed to be Ni 0.694 Co 0.1 Mn 0.2 W 0.006 (OH) 2 The doping concentration of tungsten gradually increases from inside to outside, and the coating layer is Co (OH) 2 The thickness of the clad layer was 0.1. Mu.m.
The preparation of the precursor material of the design comprises the following steps:
(1) Respectively preparing a nickel salt solution, a cobalt salt solution, a manganese salt solution, a tungsten salt solution, a sodium hydroxide solution and an ammonia water solution.
(2) Pumping a nickel salt solution, a cobalt salt solution, a manganese salt solution, a sodium hydroxide solution and an ammonia water solution into a reaction kettle 1 by using different peristaltic pumps to perform coprecipitation reaction, and transferring the nickel salt solution, the cobalt salt solution, the manganese salt solution, the sodium hydroxide solution and the ammonia water solution into a reaction kettle 2 when particles grow to 0.5 mu m.
(3) And (3) continuously introducing a nickel salt solution, a cobalt salt solution, a manganese salt solution, a sodium hydroxide solution and an ammonia water solution into the reaction kettle 2, controlling the nickel salt solution, the cobalt salt solution and the manganese salt solution to be pumped at a constant speed, and controlling the pumping speed of the tungsten salt solution to be gradually increased. When the particles grow to 10 mu m, the addition of the nickel salt solution, the manganese salt solution and the tungsten salt solution is stopped, and only the cobalt salt solution is pumped. After the particles continue to grow to 10.1 mu m, the feeding is stopped, and precursor slurry is obtained.
(3) Carrying out solid-liquid separation on the precursor slurry obtained in the step (2), collecting solids, washing, drying, sieving and demagnetizing the solids to obtain the tungsten-doped cobalt in-situ coated ternary precursor-Ni 0.694 Co 0.1 Mn 0.2 W 0.006 (OH) 2 @Co(OH) 2 。
(4) Ball-milling and mixing the ternary precursor lithium hydroxide monohydrate obtained in the step (3) according to a molar ratio of 1.06 0.694 Co 0.1 Mn 0.2 W 0.006 O 2 @LiCoO 2 。
And (3) preparing a positive electrode material: conductive agent: the pole piece is coated with a binder in a ratio of 8 -1 The specific capacity of the resin is 130.5 mAh g after 200 cycles of circulation -1 The specific capacity and the capacity retention rate of (2) were 78%.
Comparative example 2
The comparative example 2 is different from the example 1 in that the tungsten doping concentration of the precursor is gradually decreased from the inside to the outside.
The chemical formula of the precursor of the comparative example design is Ni 0.694 Co 0.1 Mn 0.2 W 0.006 (OH) 2 The doping concentration of tungsten is gradually reduced from inside to outside, and the coating layer is Co (OH) 2 Thickness of coating layerIs 0.1 μm.
The preparation of the precursor material of the design comprises the following steps:
(1) Respectively preparing a nickel salt solution, a cobalt salt solution, a manganese salt solution, a tungsten salt solution, a sodium hydroxide solution and an ammonia water solution.
(2) Pumping nickel salt solution, cobalt salt solution, manganese salt solution, sodium hydroxide solution and ammonia water solution into a reaction kettle 1 by using different peristaltic pumps to perform coprecipitation reaction, and transferring the particles into a reaction kettle 2 when the particles grow to 0.5 mu m.
(3) And continuously introducing a nickel salt solution, a cobalt salt solution, a manganese salt solution, a sodium hydroxide solution and an ammonia water solution into the reaction kettle 2, controlling the nickel salt solution, the cobalt salt solution and the manganese salt solution to be pumped at a constant speed, and controlling the pumping speed of the tungsten salt solution to be gradually reduced. When the particles grow to 10 mu m, the addition of the nickel salt solution, the manganese salt solution and the tungsten salt solution is stopped, and only the cobalt salt solution is pumped. After the particles continue to grow to 10.1 mu m, the feeding is stopped, and precursor slurry is obtained.
(4) Carrying out solid-liquid separation on the precursor slurry obtained in the step (3), collecting solids, washing, drying, sieving and demagnetizing the solids to obtain the tungsten-doped cobalt in-situ coated ternary precursor-Ni 0.694 Co 0.1 Mn 0.2 W 0.006 (OH) 2 @Co(OH) 2 。
(5) Ball-milling and mixing the ternary precursor lithium hydroxide monohydrate obtained in the step (4) according to a molar ratio of 1.06 0.694 Co 0.1 Mn 0.2 W 0.006 O 2 @LiCoO 2 。
And (3) preparing a positive electrode material: conductive agent: the pole piece is coated by the binder in the proportion of 8 -1 The specific capacity of the resin is 92.1 mAh g after 200 cycles of circulation -1 The capacity retention ratio of (2) was 55%.
Comparative example 3
Comparative example 3 differs from example 1 in that the precursor is not in-situ coated with a cobalt layer.
The chemical formula of the precursor of the design of the comparative example is Ni 0.694 Co 0.1 Mn 0.2 W 0.006 (OH) 2 The concentration of the tungsten doped region from inside to outside is 0.1-0.15-0.1 percent of the molar ratio of the total metal ions, and no coating layer is formed.
The preparation of the precursor material of the design comprises the following steps:
(1) Respectively preparing a nickel salt solution, a cobalt salt solution, a manganese salt solution, a tungsten salt solution, a sodium hydroxide solution and an ammonia water solution.
(2) Pumping a nickel salt solution, a cobalt salt solution, a manganese salt solution, a sodium hydroxide solution and an ammonia water solution into a reaction kettle 1 by using different peristaltic pumps to perform coprecipitation reaction, and transferring the nickel salt solution, the cobalt salt solution, the manganese salt solution, the sodium hydroxide solution and the ammonia water solution into a reaction kettle 2 when particles grow to 0.5 mu m.
(3) And (3) continuously introducing a nickel salt solution, a cobalt salt solution, a manganese salt solution, a sodium hydroxide solution and an ammonia water solution into the reaction kettle 2, and stopping feeding after the particles grow to 10 mu m to obtain precursor slurry.
(4) Carrying out solid-liquid separation on the precursor slurry obtained in the step (3), collecting solids, washing, drying, sieving and demagnetizing the solids to obtain the tungsten gradient doped ternary precursor-Ni 0.694 Co 0.1 Mn 0.2 W 0.006 (OH) 2 。
(4) Ball-milling and mixing the ternary precursor lithium hydroxide monohydrate obtained in the step (3) according to a molar ratio of 1.06 0.694 Co 0.1 Mn 0.2 W 0.006 O 2 。
And (3) preparing a positive electrode material: conductive agent: the pole piece is coated with a binder in the proportion of 8 -1 The specific capacity of the resin is 81.9 mAh g after 200 cycles of circulation -1 The specific capacity and the capacity retention rate of (2) were 50%.
Fig. 2 is a diagram of the electrochemical performance of the lithium ion button cell assembled in example 1 and comparative examples 1-3.
Example 2
In this example, the chemical formula of the precursor is Ni 0.694 Co 0.1 Mn 0.2 Zr 0.006 (OH) 2 The concentration of the doped region of zirconium from inside to outside is 0.1-0.15-0.1% of the molar ratio of the total metal ions, and the coating layer is Co (OH) 2 The thickness of the clad layer was 0.1. Mu.m.
The preparation of the precursor material of the above design comprises the following steps:
(1) Respectively preparing a nickel salt solution, a cobalt salt solution, a manganese salt solution, a zirconium salt solution, a sodium hydroxide solution and an ammonia water complexing agent solution.
(2) Pumping nickel salt solution, cobalt salt solution, manganese salt solution, sodium hydroxide solution and ammonia water solution into a reaction kettle 1 by using different peristaltic pumps to perform coprecipitation reaction, and transferring the particles into a reaction kettle 2 when the particles grow to 0.5 mu m.
(3) And continuously introducing a nickel salt solution, a cobalt salt solution, a manganese salt solution, sodium hydroxide and an ammonia water solution into the reaction kettle, introducing a zirconium salt solution, and controlling the pumping speed of the zirconium salt solution to be slow-fast-slow so as to realize gradient doping of zirconium. When the particles grow to 10 mu m, the addition of the nickel, manganese and zirconium salt solution is stopped, and only the cobalt salt solution is pumped. After the particles continue to grow to 10.1 mu m, the feeding is stopped, and precursor slurry is obtained.
(3) Carrying out solid-liquid separation on the precursor slurry obtained in the step (2), collecting solids, washing, drying, sieving and demagnetizing the solids to obtain the zirconium gradient doped and cobalt in-situ coated ternary precursor-Ni 0.694 Co 0.1 Mn 0.2 Zr 0.006 (OH) 2 @Co(OH) 2 。
(4) Ball-milling and mixing the ternary precursor lithium hydroxide monohydrate obtained in the step (3) according to a molar ratio of 1.06 0.694 Co 0.1 Mn 0.2 Zr 0.006 O 2 @LiCoO 2 。
And (3) preparing a positive electrode material: conductive agent: the pole piece is coated by the binder in the proportion of 8 -1 The specific capacity of the resin is 154.1 mAh g after 200 cycles of circulation -1 The specific capacity and the capacity retention ratio of (2) were 90%.
Fig. 3 is a graph of the electrochemical performance of the lithium ion coin cell of example 2.
Example 3
In this example, the chemical formula of the precursor is Ni 0.694 Co 0.1 Mn 0.2 Ti 0.006 (OH) 2 The concentration of the doped region of titanium from inside to outside is 0.1-0.15-0.1 percent of the molar ratio of the total metal ions, and the coating layer is Co (OH) 2 The thickness of the clad layer was 0.1. Mu.m.
The preparation of the precursor material of the design comprises the following steps:
(1) Respectively preparing a nickel salt solution, a cobalt salt solution, a manganese salt solution, a titanium salt solution, a sodium hydroxide solution and an ammonia water complexing agent solution.
(2) Pumping nickel salt solution, cobalt salt solution, manganese salt solution, sodium hydroxide solution and ammonia water solution into a reaction kettle 1 by using different peristaltic pumps to perform coprecipitation reaction, and transferring the particles into a reaction kettle 2 when the particles grow to 0.5 mu m.
(3) And continuously introducing a nickel salt solution, a cobalt salt solution, a manganese salt solution, sodium hydroxide and an ammonia water solution into the reaction kettle, introducing a titanium salt solution, and controlling the pumping speed of the titanium salt solution to be slow-fast-slow so as to realize the gradient doping of the titanium. When the particles grow to 10 mu m, the addition of the nickel, manganese and titanium salt solution is stopped, and only the cobalt salt solution is pumped. After the particles continue to grow to 10.1 mu m, the feeding is stopped, and precursor slurry is obtained.
(3) Carrying out solid-liquid separation on the precursor slurry obtained in the step (2), collecting solids, washing, drying, sieving and demagnetizing the solids to obtain the ternary precursor Ni-Ni with gradient doped titanium and in-situ coated cobalt 0.694 Co 0.1 Mn 0.2 Ti 0.006 (OH) 2 @Co(OH) 2 。
(4) Ball-milling and mixing the ternary precursor lithium hydroxide monohydrate obtained in the step (3) according to a molar ratio of 1.06 0.694 Co 0.1 Mn 0.2 Ti 0.006 O 2 @LiCoO 2 。
And (3) preparing a positive electrode material: conductive agent: the adhesive is 8 -1 The specific capacity of the resin is 155.6 mAh g after 200 cycles of circulation -1 The specific capacity and the capacity retention rate of (2) are 90%.
Example 4
In this example, the chemical formula of the precursor is Ni 0.694 Co 0.1 Mn 0.2 In 0.006 (OH) 2 The concentration of the indium doped region from inside to outside is 0.1-0.15-0.1 percent of the total metal ion molar ratio, and the coating layer is Co (OH) 2 The thickness of the clad layer was 0.1. Mu.m.
The preparation of the precursor material of the design comprises the following steps:
(1) Respectively preparing a nickel salt solution, a cobalt salt solution, a manganese salt solution, an indium salt solution, a sodium hydroxide solution and an ammonia water complexing agent solution.
(2) Pumping a nickel salt solution, a cobalt salt solution, a manganese salt solution, a sodium hydroxide solution and an ammonia water solution into a reaction kettle 1 by using different peristaltic pumps to perform coprecipitation reaction, and transferring the nickel salt solution, the cobalt salt solution, the manganese salt solution, the sodium hydroxide solution and the ammonia water solution into a reaction kettle 2 when particles grow to 0.5 mu m.
(3) And continuously introducing a nickel salt solution, a cobalt salt solution, a manganese salt solution, sodium hydroxide and an ammonia water solution into the reaction kettle, introducing an indium salt solution, and controlling the pumping speed of the indium salt solution to be slow-fast-slow so as to realize the gradient doping of indium. When the particles grow to 10 μm, the addition of the nickel, manganese and indium salt solution is stopped, and only the cobalt salt solution is pumped in. After the particles continue to grow to 10.1 mu m, the feeding is stopped, and precursor slurry is obtained.
(3) The step (A) is2) Carrying out solid-liquid separation on the obtained precursor slurry, collecting solids, washing, drying, sieving and demagnetizing the solids to obtain the indium gradient doped cobalt in-situ coated ternary precursor-Ni 0.694 Co 0.1 Mn 0.2 In 0.006 (OH) 2 @Co(OH) 2 。
(4) Ball-milling and mixing the ternary precursor lithium hydroxide monohydrate obtained in the step (3) according to a molar ratio of 1.06 0.694 Co 0.1 Mn 0.2 In 0.006 O 2 @LiCoO 2 。
And (3) preparing a positive electrode material: conductive agent: the pole piece is coated by the binder in the proportion of 8 -1 The specific capacity of the resin is 152.4 mAh g after 200 cycles of circulation -1 The capacity retention ratio of (2) was 88%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (7)

1. The precursor material is characterized in that the chemical formula of the precursor material is Ni x Co y Mn z M p (OH) 2 @Co(OH) 2 Wherein x is more than or equal to 0.7 and less than or equal to 1,0 and less than or equal to y is more than or equal to 0.2,0 and less than or equal to z and less than or equal to 0.3, x + y + z + p =1; m is a doping element and is one or more than two of Al, zr, mg, zn, nb, sr, sn, ti, ce, cr, fe, na, K, cu, V, mo, Y, in, ta, ge, bi and Pb; doping elements in the precursor material are circularly distributed in a low-concentration-high-concentration-low-concentration-high-low-concentration mode from inside to outside, and doping areas of the doping elements on the innermost layer and the outermost layer of the precursor material are low-concentration doping areas; cobalt is deposited on the surface of the precursor through a coprecipitation process to form cobaltAnd (4) coating.
2. The element-doped and cobalt-in-situ coated precursor material of claim 1, wherein the molar ratio of the doping element in the low-concentration doped region of the doping element to the total metal ions in the region is X1, X1 is greater than 0 and less than or equal to 0.05; the molar ratio of the doping elements in the high-concentration doping area of the doping elements to the total metal ions in the area is X2, wherein X2 is more than 0 and less than or equal to 0.3; the doping amount of the doping element in the low-concentration doping region of the doping element is less than that in the high-concentration doping region.
3. The element-doped and cobalt-in-situ coated precursor material of claim 1, wherein the cobalt coating layer has a thickness of less than 3 μ ι η.
4. A preparation method of element-doped and cobalt in-situ-coated precursor material is characterized by comprising the following steps:
(1) Feeding a nickel salt solution, a cobalt salt solution, a manganese salt solution, a precipitator solution and a complexing agent solution into a first reaction kettle in a parallel flow manner, and carrying out coprecipitation reaction to form crystal nuclei with the particle size of 0.05-1 mu m;
(2) Introducing the slurry of the first reaction kettle into a second reaction kettle, and introducing a nickel salt solution, a cobalt salt solution, a manganese salt solution, a doping element salt solution, a precipitator solution and a complexing agent solution in a concurrent flow manner, controlling the flow rate of the doping element salt solution to ensure that the doping concentration of the doping element in a precursor follows the cyclic distribution of 'low concentration-high concentration-low concentration', stopping adding the nickel salt solution, the manganese salt solution and the doping element salt solution when the granularity of the reaction slurry is 2-15 mu m, and only carrying out the precipitation reaction of cobalt;
(3) And after the reaction is finished, filtering the reaction slurry, and washing, drying, sieving and demagnetizing the solid phase to obtain the element-doped and cobalt-in-situ-coated precursor material.
5. The method according to claim 4, wherein the nickel salt, cobalt salt, and manganese salt are at least one of sulfate, nitrate, and chloride; the precipitant is sodium hydroxide; the complexing agent is ammonia water.
6. A positive electrode material, which is obtained by lithium-mixed sintering of the element-doped and cobalt-in-situ-coated precursor material according to any one of claims 1 to 3.
7. The positive electrode material as claimed in claim 6, wherein the sintering process is divided into two stages, the sintering temperature in the first stage is 400-500 ℃, and the heat preservation time is 3-5h; the sintering temperature in the second stage is 700-1000 ℃, and the temperature is kept for 9-1697 h.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115286051A (en) * 2022-08-09 2022-11-04 荆门市格林美新材料有限公司 Quaternary positive electrode precursor and preparation method and application thereof
CN117239103A (en) * 2023-11-10 2023-12-15 浙江帕瓦新能源股份有限公司 High-nickel ternary positive electrode material, preparation method thereof and lithium ion battery

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109336193A (en) * 2018-10-21 2019-02-15 圣戈莱（北京）科技有限公司 Multielement original position codope ternary material precursor and its preparation method and application
CN110364711A (en) * 2019-07-08 2019-10-22 光鼎铷业(广州)集团有限公司 A kind of nickel cobalt manganese anode material and preparation method thereof of gradient rubidium doping
CN111628149A (en) * 2020-06-02 2020-09-04 格林美股份有限公司 Gradient-doped high-nickel ternary positive electrode material and preparation method thereof
CN113258072A (en) * 2021-06-16 2021-08-13 浙江帕瓦新能源股份有限公司 Nickel-cobalt-manganese positive electrode material and preparation method thereof
CN113299907A (en) * 2021-07-26 2021-08-24 浙江帕瓦新能源股份有限公司 Multi-element regionally-doped cobalt-free cathode material and preparation method thereof
CN113387401A (en) * 2021-06-25 2021-09-14 浙江帕瓦新能源股份有限公司 Preparation method of scandium-tungsten doped anode material precursor
CN113620354A (en) * 2021-08-06 2021-11-09 湖南杉杉能源科技有限公司 Surface-coated lithium ion battery anode material precursor and preparation method thereof
CN113666436A (en) * 2021-08-31 2021-11-19 中南大学 Nickel-rich ternary precursor and preparation method and application thereof
CN114551863A (en) * 2022-04-21 2022-05-27 浙江帕瓦新能源股份有限公司 Precursor material with element concentration gradient distribution, preparation method thereof and positive electrode material

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109336193A (en) * 2018-10-21 2019-02-15 圣戈莱（北京）科技有限公司 Multielement original position codope ternary material precursor and its preparation method and application
CN110364711A (en) * 2019-07-08 2019-10-22 光鼎铷业(广州)集团有限公司 A kind of nickel cobalt manganese anode material and preparation method thereof of gradient rubidium doping
CN111628149A (en) * 2020-06-02 2020-09-04 格林美股份有限公司 Gradient-doped high-nickel ternary positive electrode material and preparation method thereof
CN113258072A (en) * 2021-06-16 2021-08-13 浙江帕瓦新能源股份有限公司 Nickel-cobalt-manganese positive electrode material and preparation method thereof
CN113387401A (en) * 2021-06-25 2021-09-14 浙江帕瓦新能源股份有限公司 Preparation method of scandium-tungsten doped anode material precursor
CN113299907A (en) * 2021-07-26 2021-08-24 浙江帕瓦新能源股份有限公司 Multi-element regionally-doped cobalt-free cathode material and preparation method thereof
CN113620354A (en) * 2021-08-06 2021-11-09 湖南杉杉能源科技有限公司 Surface-coated lithium ion battery anode material precursor and preparation method thereof
CN113666436A (en) * 2021-08-31 2021-11-19 中南大学 Nickel-rich ternary precursor and preparation method and application thereof
CN114551863A (en) * 2022-04-21 2022-05-27 浙江帕瓦新能源股份有限公司 Precursor material with element concentration gradient distribution, preparation method thereof and positive electrode material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李永光等: "在三元前驱体Ni0.82Co0.12Mn0.06(OH)2表面包覆氢氧化钴的研究" *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115286051A (en) * 2022-08-09 2022-11-04 荆门市格林美新材料有限公司 Quaternary positive electrode precursor and preparation method and application thereof
CN117239103A (en) * 2023-11-10 2023-12-15 浙江帕瓦新能源股份有限公司 High-nickel ternary positive electrode material, preparation method thereof and lithium ion battery
CN117239103B (en) * 2023-11-10 2024-02-23 浙江帕瓦新能源股份有限公司 High-nickel ternary positive electrode material, preparation method thereof and lithium ion battery

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