CN114122377A - High-nickel anode material with embedded coating layer and preparation method thereof - Google Patents

High-nickel anode material with embedded coating layer and preparation method thereof Download PDF

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CN114122377A
CN114122377A CN202111367333.4A CN202111367333A CN114122377A CN 114122377 A CN114122377 A CN 114122377A CN 202111367333 A CN202111367333 A CN 202111367333A CN 114122377 A CN114122377 A CN 114122377A
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coating layer
nickel
embedded
cobalt
mixture
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陈志宇
吉长印
吕菲
徐宁
吴孟涛
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Tianjin B&M Science and Technology Co Ltd
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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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a high-nickel anode material with an embedded coating layer and a preparation method thereofxCoyM1‑x‑yO2Wherein M is one or more of Mn, Mg, Al, Ti, Zr, Y, Nb or W, x is more than 0.6 and less than or equal to 0.96, and Y is more than or equal to 0 and less than or equal to 0.4. The high-nickel anode material with the embedded coating layer adopts cobalt boride with excellent mechanical property, inhibits the stress strain of the high-nickel anode material, and leads the unstable and easy separation of interlayer oxygen along with the insertion/separation of lithium ions in the charging and discharging processes and the continuous change of the valence state of nickel, thereby leading the high-nickel material to generate phase change; the cobalt boride can effectively inhibit oxygen after forming boron oxide (a small amount) by oxygen affinityThe stability of the crystal structure is maintained.

Description

High-nickel anode material with embedded coating layer and preparation method thereof
Technical Field
The invention belongs to the field of lithium ion battery materials, and particularly relates to a high-nickel anode material with an embedded coating layer and a preparation method thereof.
Background
With the increase of global energy crisis and environmental pollution problems, new energy electric vehicles become a hot key point, wherein the high-nickel ternary system material is considered as the lithium ion battery anode material with the most potential and application prospect due to the characteristics of high reversible capacity, high working voltage and the like.
The high-nickel ternary material has smooth surface, other impurities are introduced to be attached to the particle surface in the actual process, and the moisture and oxygen atmosphere in the storage environment can accelerate the reaction of the impurities and the electrolyte to generate Li2CO3And LiOH, etc., to form an insulating layer on the surface of the electrode, thereby inhibiting ion diffusion and electron transport. Meanwhile, as the content of nickel increases, the thermal decomposition temperature of the material decreases and the thermal stability becomes poor. During the charge and discharge process, the partial phase transformation to spinel type and NiO type rock salt phase and the formation of pores are accompanied, resulting in irreversible damage of the structure. In addition, the reaction of the electrodes with the electrolyte generates gases, which cause heat to be diffused, thereby causing a series of safety problems.
In view of the above technical problems, researchers often modify the positive electrode material by a coating method. Common coating materials are nonmetallic carbon materials, oxides, fluorides, salts, polymers and the like. In patent CN111313024B, "a nano-lithium magnesium silicate coated high nickel cathode material, and a preparation method and application thereof," the nano-lithium magnesium silicate is mechanically fused and coated on a primary baked semi-finished product to prepare the high nickel cathode material, which improves surface interface stability and cycle performance. Kong et al published in Journal of Power Sources (266, 2014, 433-439) under the title "Ultra in ZnO coating for enhanced electrochemical performance of LiNi0.5Co0.2Mn0.3O2The article by cathode material "on LiNi by methods employing atomic deposition0.5Co0.2Mn0.3O2The ZnO coating is coated on the electrode material, so that the dissolution of metal ions and the corrosion of HF are effectively prevented, and the stability and the discharge capacity of the electrode material are improved.
The modification methods reported above all have certain problems in the practical application process. Firstly, the composite modification methods are limited to the surface of active material particles, and have no modification or improvement on the electron/ion diffusion process in the particles. Secondly, there are very high requirements on the compactness of the coating and the interfacial compatibility of the coating with the active material. Meanwhile, the clad material generally has no activity and poor conductivity, and the mass specific capacity of the material can be reduced after the clad material is compounded with a high-nickel anode material. In addition, the coating process usually involves high temperature sintering, which increases the material preparation cost, and therefore, how to achieve better coating effect becomes a concern in the field.
Disclosure of Invention
In view of the above, the present invention provides a high nickel cathode material with an embedded coating layer and a method for preparing the same, which aims to overcome the defects in the prior art.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a high-nickel anode material with an embedded coating layer is of a pomegranate-shaped structure and comprises a core and the embedded coating layer, wherein the chemical formula of the core is LiNixCoyM1-x-yO2Wherein M is one or more of Mn, Mg, Al, Ti, Zr, Y, Nb or W, x is more than 0.6 and less than or equal to 0.96, and Y is more than or equal to 0 and less than or equal to 0.4.
Furthermore, the inner core is a secondary particle formed by gathering primary particles, and gaps exist among the primary particles; the embedded coating layer is cobalt boride; the coating layer completely covers the surface of the secondary particles and permeates into gaps among the primary particles of the core, a boron oxide passivation layer is formed on the contact surface of the coating layer and the primary particles, and an ion conductor layer is formed between the primary particles and the passivation layer.
Further, the boron oxide passivation layer is at least one of cobalt boride, boron oxide or cobalt oxide.
According to the invention, the embedded coating layer is introduced to coat the high-nickel ternary cathode material, the reaction wettability of the metal boride and the surface of the high-nickel material ensures that the high-nickel ternary cathode material is tightly coated and permeates into crystal gaps of primary particles, and the high-nickel ternary cathode material and the metal boride form a mixed ion/electron conductor, so that the conductivity and the ion conduction rate of the material are improved.
A preparation method of a high-nickel cathode material with an embedded coating layer comprises the following steps:
(1) the ternary precursor NixCoyM1-x-y(OH)2Wherein x is more than 0.6 and less than or equal to 0.96, y is more than or equal to 0 and less than 0.4, and the mixture is mixed with a lithium source and ground to obtain a mixture A;
(2) roasting the mixture A at high temperature, cooling, crushing, washing with water and screening to obtain the LiNi with the chemical formulaxCoyM1-x-yO2The nickel-based positive electrode material B;
(3) adding the high nickel positive electrode material B into an ethanol solution of a cobalt element compound under the protection of inert gas, violently stirring, and uniformly mixing to obtain a mixture C;
(4) and adding the mixture C into an ethanol solution of sodium borohydride, violently stirring under the protection of inert gas, washing the mixture with absolute ethyl alcohol, filtering and drying to obtain the high-nickel cathode material with the embedded coating layer.
Further, the lithium source (calculated as Li) in the step (1) is mixed with NixCoyM1-x-y(OH)2In a molar ratio of (1.02-1.08): 1; the ternary precursor NixCoyM1-x-y(OH)2Wherein M is at least one of Mn, Mg, Al, Ti, Zr, Y, Nb or W; the lithium source is at least one of lithium hydroxide or lithium carbonate.
Further, the temperature of the high-temperature roasting step in the step (2) is 600-1000 ℃, and the roasting time is 4-15 h.
Further, the mass ratio of the high nickel-based positive electrode material B in the step (3) to the cobalt nitrate hexahydrate is 1: (0.1-2); the concentration of the ethanol solution of the cobalt element compound is 0.01-0.1 g/mL; the cobalt element compound is at least one of cobalt nitrate hexahydrate, cobalt chloride hexahydrate or cobalt sulfate heptahydrate.
Further, the concentration of the mixture C in the ethanol solution in the step (4) is 1-3 g/mL; the concentration of the ethanol solution of the sodium borohydride is 0.1-3 g/mL. The sodium borohydride concentration is too low, so that the gap infiltration of the primary particles is incomplete, the surface of the secondary particles is only coated, and the boron source is wasted due to too high concentration.
The application of the high nickel anode material with the embedded coating layer and the application of the high nickel anode material in the preparation of the lithium ion battery are disclosed.
Compared with the prior art, the invention has the following advantages:
the high-nickel anode material with the embedded coating layer adopts cobalt boride with excellent mechanical property, inhibits the stress strain of the high-nickel anode material, and leads the unstable and easy separation of interlayer oxygen along with the insertion/separation of lithium ions in the charging and discharging processes and the continuous change of the valence state of nickel, thereby leading the high-nickel material to generate phase change; the penetration and precipitation of oxygen can be effectively inhibited after the cobalt boride forms boron oxide (a small amount) through oxygen affinity, and the stability of a crystal structure is maintained.
The high-nickel anode material with the embedded coating layer adopts the cobalt boride to perform thermodynamic reaction with oxygen on the surface of particles of the high-nickel material to form a complex boron oxide stable compound, so that a passivation layer is effectively formed to inhibit oxygen penetration, and the stability of the material is improved.
The high-nickel anode material with the embedded coating layer adopts the reaction wettability between cobalt boride and high-nickel material particles, and the coating layer can not only completely cover the surfaces of secondary particles, but also can infiltrate into primary particles, so that the embedded coating ensures the close combination and complete coverage of the coating layer and the infiltration of the coating layer into crystal gaps of the primary particles.
According to the high-nickel positive electrode material with the embedded coating layer, part of cobalt is combined with oxygen to form cobalt oxide, movable borate ions can be combined with lithium on the surface of high-nickel to form interface polyanionic borate, and the interface polyanionic borate is combined with lithium metal on the surface of high-nickel to form a mixed ion/electron conductor, so that the electron conduction and the ion transmission of the positive electrode material of the lithium battery are improved.
The preparation method of the high-nickel anode material with the embedded coating layer adopts a sol-gel method for coating, the whole process is carried out in a solvent, and the liquid flow characteristic enables the anode material to be completely soaked, so that the embedded coating is realized, the embedded coating can be carried out at room temperature, the high-temperature complex treatment is eliminated, and the energy loss and the preparation cost of the traditional high-temperature sintering are reduced; the cobalt boride and the surface oxygen of the high-nickel cathode material have strong reactivity, the reaction wettability ensures the close and penetration embedding of the coating layer, but the reaction product boron oxide and the like can form a close passivation layer, so the reaction kinetics is self-limiting, and the oxygen penetration can be further inhibited.
Drawings
Fig. 1 is a structural diagram of a high nickel cathode material with an embedded cladding layer according to an embodiment of the invention;
fig. 2 is an SEM image of the high nickel cathode material with embedded cladding layer according to example 1 of the present invention;
fig. 3 is an XRD pattern of the high nickel cathode material with embedded cladding layer according to example 1 of the present invention;
fig. 4 is a graph of electrochemical cycling performance of the high nickel cathode materials with embedded cladding layers described in example 1 and comparative example 1 of the present invention.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
A high-nickel anode material with an embedded coating layer is of a core-shell structure and comprises a core and a coating layer, wherein the chemical formula of the core is LiNixCoyM1-x-yO2Wherein M is one or more of Mn, Mg, Al, Ti, Zr, Y, Nb or W, x is more than 0.6 and less than or equal to 0.96, and Y is more than or equal to 0 and less than or equal to 0.4. The inner core is secondary particles formed by gathering primary particles, and gaps exist among the primary particles; the coating layer is cobalt boride; the coating layer completely covers the surface of the inner coreAnd the boron oxide passivation layer is formed on the contact surface of the coating layer and the core, and an ion conductor layer is formed between the core and the passivation layer.
A preparation method of a high-nickel cathode material with an embedded coating layer comprises the following steps:
(1) the ternary precursor NixCoyM1-x-y(OH)2Wherein x is more than 0.6 and less than or equal to 0.96, y is more than or equal to 0 and less than 0.4, and the mixture is mixed with a lithium source and ground to obtain a mixture A;
(2) roasting the mixture A at high temperature, cooling, crushing, washing with water and screening to obtain the LiNi with the chemical formulaxCoyM1-x-yO2The nickel-based positive electrode material B;
(3) adding the high-nickel positive electrode material B into an ethanol solution of cobalt nitrate hexahydrate under the protection of inert gas, violently stirring, and uniformly mixing to obtain a mixture C;
(4) and adding the mixture C into an ethanol solution of sodium borohydride, violently stirring under the protection of inert gas, washing the mixture with absolute ethyl alcohol, filtering and drying to obtain the high-nickel cathode material with the embedded coating layer.
The present invention will be described in detail with reference to examples.
Example 1
A preparation method of a high-nickel cathode material with an embedded coating layer comprises the following steps:
(1) weighing ternary precursor Ni0.96Co0.02Mn0.01W0.01(OH)2And LiOH, in terms of molar ratios, LiOH: ni0.96Co0.02Mn0.01W0.01(OH)21.02: 1, fully mixing and ball-milling to obtain a mixture A;
(2) roasting the mixture A at 800 ℃ for 10h in an oxygen atmosphere, cooling, crushing and screening to obtain the LiNi with the chemical formula0.96Co0.02Mn0.01W0.01O2The nickel-based positive electrode material B;
(3) weighing 50g of the prepared nickelic anode material B, and adding the nickelic anode material B into 1000mL of 0.0291g/mL of ethanol solution of cobalt nitrate hexahydrate under the conditions of vigorous stirring and argon protection to obtain a mixture C;
(4) and adding 20mL of 1.5g/mL sodium borohydride ethanol solution into the mixture C, vigorously stirring for 3h under the protection of argon, washing the mixture for 3 times by using absolute ethyl alcohol, filtering, and drying in vacuum at 120 ℃ for 12h to obtain the high-nickel cathode material with the embedded coating.
Comparative example 1
A preparation method of a high-nickel cathode material comprises the following steps: weighing ternary precursor Ni0.96Co0.02Mn0.01W0.01(OH)2And LiOH, in terms of molar ratios, LiOH: ni0.96Co0.02 Mn0.01W0.01(OH)21.02: 1, fully mixing, ball-milling, roasting at 800 ℃ for 10 hours in an oxygen atmosphere, cooling, crushing and screening to obtain uncoated LiNi0.96Co0.02Mn0.01W0.01O2A high nickel-based positive electrode material; in comparison with example 1, no cobalt boride coating was performed.
Comparative example 2
A preparation method of a high-nickel cathode material comprises the following steps: weighing ternary precursor Ni0.96Co0.02Mn0.02(OH)2And LiOH, in terms of molar ratios, LiOH: ni0.96Co0.02Mn0.02(OH)21.02: 1, fully mixing, ball-milling, roasting at 800 ℃ for 10 hours in an oxygen atmosphere, cooling, crushing and screening to obtain uncoated Li Ni0.96Co0.02Mn0.02O2Weighing 50g of the prepared high-nickel positive electrode material, adding 1000mL of 0.0291g/mL of ethanol solution of cobalt nitrate hexahydrate under the conditions of vigorous stirring and argon protection, then adding 20mL of 1.5g/mL of ethanol solution of sodium borohydride into the mixture, vigorously stirring for 3 hours under the condition of argon protection, washing the mixture for 3 times by using absolute ethyl alcohol, filtering, and drying in vacuum for 12 hours at 120 ℃ to obtain the nickel-doped lithium iron phosphate with the embedded ionsLi Ni of formula (II) coating layer0.96Co0.02Mn0.02O2。
Example 2
A preparation method of a high-nickel cathode material with an embedded coating layer comprises the following steps:
(1) weighing ternary precursor Ni0.8Co0.1Mn0.1(OH)2And LiOH, in terms of molar ratios, LiOH: ni0.8Co0.1Mn0.1(OH)21.02: 1, fully mixing and ball-milling to obtain a mixture A;
(2) roasting the mixture A at 800 ℃ for 10h in an oxygen atmosphere, cooling, crushing and screening to obtain the compound with the chemical formula of Li Ni0.8Co0.1Mn0.1A nickel-based positive electrode material B of O2;
(3) weighing 50g of the prepared nickelic anode material B, and adding the nickelic anode material B into 1000mL of 0.0291g/mL of ethanol solution of cobalt nitrate hexahydrate under the conditions of vigorous stirring and argon protection to obtain a mixture C;
(4) and adding 20mL of 1.5g/mL sodium borohydride ethanol solution into the mixture C, vigorously stirring for 3h under the protection of argon, washing the mixture for 3 times by using absolute ethyl alcohol, filtering, and drying in vacuum at 120 ℃ for 12h to obtain the high-nickel cathode material with the embedded coating.
Example 3
A preparation method of a high-nickel cathode material with an embedded coating layer comprises the following steps:
(1) weighing ternary precursor Ni0.8Co0.1Al0.1(OH)2And LiOH, in terms of molar ratios, LiOH: ni0.8Co0.1Al0.1(OH)21.02: 1, fully mixing and ball-milling to obtain a mixture A;
(2) roasting the mixture A at 800 ℃ for 10h in an oxygen atmosphere, cooling, crushing and screening to obtain the compound with the chemical formula of Li Ni0.8Co0.1Al0.1O2The nickel-based positive electrode material B;
(3) weighing 50g of the prepared nickelic anode material B, and adding the nickelic anode material B into 1000mL of 0.0291g/mL of ethanol solution of cobalt nitrate hexahydrate under the conditions of vigorous stirring and argon protection to obtain a mixture C;
(4) and adding 20mL of 1.5g/mL sodium borohydride ethanol solution into the mixture C, vigorously stirring for 3h under the protection of argon, washing the mixture for 3 times by using absolute ethyl alcohol, filtering, and drying in vacuum at 120 ℃ for 12h to obtain the high-nickel cathode material with the embedded coating.
The ion conductivity of the high nickel cathode materials prepared in examples 1 to 3 and comparative examples 1 to 3 was measured by a four-probe method, and the conductivity of the final material was as shown in table 1.
TABLE 1 sample Ionic conductivities
Sample (I) Conductivity (S.cm)-1)
Example 1 9.83*10-4
Comparative example 1 1.22*10-5
Comparative example 2 6.57*10-5
Comparative example 3 3.19*10-4
Example 2 2.46*10-4
Example 3 1.35*10-4
As can be seen from the data in table 1, the high nickel cathode material with an embedded coating layer prepared in examples 1 to 3 has higher ionic conductivity, and meets the application requirements of a lithium ion battery. Comparative example 1 was not coated with an embedded layer of cobalt boride, and the conductivity was significantly reduced compared to example 1; the comparative example 2 is a nickel-cobalt-manganese ternary material, and compared with the example 1, the conductivity is correspondingly reduced without doping tungsten; comparative example 3 the raw material of the coating layer is reduced, and the inventor speculates that the formed coating layer is thinner, and the density of the coating layer is reduced and the conductivity is reduced compared with that of the coating layer of example 1.
Fig. 2 and 3 are an XRD chart and an SEM photograph of the high nickel based positive electrode material prepared in example 1, respectively, from which it can be seen that a compact coating layer is present on the surface and pores of the high nickel secondary particles, and the XRD result shows a sharp diffraction peak, indicating that the crystal structure is good and the crystallinity is high.
Table 2 lists the first specific capacity, first coulombic efficiency, and capacity retention after 500 cycles of the button cell assembled using the high nickel materials of example 1, comparative examples 1-3, and examples 2-3. The test conditions of the button cell are LR 2032, 0.1C, 2.5-4.25V, vs. Li+and/Li. The positive pole piece of the battery is as follows: conductive agent: PVDF-90: 3:7 mass ratio batch, and conventional sample: conductive agent: compared with the positive pole piece proportioning of 85:10:5, the positive pole piece has the advantages that the conductivity of the positive pole material is improved, the consumption of the conductive agent is obviously reduced, and the energy density of the battery is effectively improved.
TABLE 2 comparison table of first charge and discharge performance of sample
Figure BDA0003361056210000111
Figure BDA0003361056210000121
The data in the table show that the high-nickel positive electrode material for power prepared in the embodiments 1 to 3 of the invention has higher specific capacity and good cycle performance, and has good application prospect in the field of lithium ion batteries, compared with the uncoated comparative example 1, the embodiment 1 of the invention has obviously improved capacity and cycle performance, and the comparative example 3 has slightly poor cycle performance because the coating layer of the positive electrode material is thinner and lower in conductivity.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (9)

1. A high nickel anode material with an embedded coating layer is characterized in that: the high-nickel anode material is of a pomegranate-shaped structure and comprises a core and an embedded coating layer, wherein the chemical formula of the core is LiNixCoyM1-x-yO2Wherein M is one or more of Mn, Mg, Al, Ti, Zr, Y, Nb or W, x is more than 0.6 and less than or equal to 0.96, and Y is more than or equal to 0 and less than or equal to 0.4.
2. The high nickel positive electrode material with an embedded cladding layer according to claim 1, characterized in that: the inner core is secondary particles formed by gathering primary particles, and gaps exist among the primary particles; the embedded coating layer is cobalt boride; the coating layer completely covers the surface of the secondary particles and permeates into gaps among the primary particles of the core, a boron oxide passivation layer is formed on the contact surface of the coating layer and the primary particles, and an ion conductor layer is formed between the primary particles and the passivation layer.
3. The high nickel positive electrode material with an embedded cladding layer according to claim 2, characterized in that: the boron oxide passivation layer is at least one of cobalt boride, boron oxide or cobalt oxide.
4. The method of preparing a high nickel positive electrode material with an embedded coating layer according to any one of claims 1 to 3, wherein: the method comprises the following steps:
(1) the ternary precursor NixCoyM1-x-y(OH)2Wherein x is more than 0.6 and less than or equal to 0.96, y is more than or equal to 0 and less than 0.4, and the mixture is mixed with a lithium source and ground to obtain a mixture A;
(2) roasting the mixture A at high temperature, cooling, crushing, washing with water and screening to obtain the LiNi with the chemical formulaxCoyM1-x-yO2The nickel-based positive electrode material B;
(3) adding the high nickel positive electrode material B into an ethanol solution of a cobalt element compound under the protection of inert gas, violently stirring, and uniformly mixing to obtain a mixture C;
(4) and adding the mixture C into an ethanol solution of sodium borohydride, violently stirring under the protection of inert gas, washing the mixture with absolute ethyl alcohol, filtering and drying to obtain the high-nickel cathode material with the embedded coating layer.
5. The method for preparing a high-nickel cathode material with an embedded coating layer according to claim 4, wherein the method comprises the following steps: the lithium source and Ni in the step (1)xCoyM1-x-y(OH)2In a molar ratio of (1.02-1.08): 1; the ternary precursor NixCoyM1-x-y(OH)2Wherein M is at least one of Mn, Mg, Al, Ti, Zr, Y, Nb or W; the lithium source is at least one of lithium hydroxide or lithium carbonate.
6. The method for preparing a high nickel cathode material with an embedded coating layer according to claim 1, wherein the method comprises the following steps: the temperature of the high-temperature roasting step in the step (2) is 600-1000 ℃, and the roasting time is 4-15 h.
7. The method for preparing a high nickel cathode material with an embedded coating layer according to claim 1, wherein the method comprises the following steps: the mass ratio of the nickelic positive electrode material B in the step (3) to the cobalt nitrate hexahydrate is 1: (0.1-2); the concentration of the ethanol solution of the cobalt element compound is 0.01-0.1 g/mL; the cobalt element compound is at least one of cobalt nitrate hexahydrate, cobalt chloride hexahydrate or cobalt sulfate heptahydrate.
8. The method for preparing a high nickel cathode material with an embedded coating layer according to claim 1, wherein the method comprises the following steps: the concentration of the mixture C in the step (4) in the ethanol solution is 1-3 g/mL; the concentration of the ethanol solution of the sodium borohydride is 0.1-3 g/mL.
9. Use of a high nickel positive electrode material with an embedded cladding layer according to any of claims 1 to 3, characterized in that: the high nickel anode material is applied to the preparation of lithium ion batteries.
CN202111367333.4A 2022-01-07 2022-01-07 High-nickel anode material with embedded coating layer and preparation method thereof Pending CN114122377A (en)

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Cited By (3)

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CN114709377A (en) * 2022-03-29 2022-07-05 东莞理工学院 High-nickel positive electrode material and preparation method and application thereof
CN115064678A (en) * 2022-06-28 2022-09-16 天津巴莫科技有限责任公司 High-nickel low-cobalt positive electrode material, and preparation method and application thereof
WO2023173403A1 (en) * 2022-03-18 2023-09-21 宁德时代新能源科技股份有限公司 High-nickel ternary positive electrode material and preparation method therefor, secondary battery, battery module, battery pack, and electrical device

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