CN115490275B - Iron-coated boron-doped high-nickel positive electrode material, and preparation method and application thereof - Google Patents

Iron-coated boron-doped high-nickel positive electrode material, and preparation method and application thereof Download PDF

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CN115490275B
CN115490275B CN202211150595.XA CN202211150595A CN115490275B CN 115490275 B CN115490275 B CN 115490275B CN 202211150595 A CN202211150595 A CN 202211150595A CN 115490275 B CN115490275 B CN 115490275B
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boron
positive electrode
nickel
iron
electrode material
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CN115490275A (en
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李爱霞
余海军
谢英豪
李长东
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Guangdong Brunp Recycling Technology Co Ltd
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Abstract

The invention belongs to the technical field of energy storage materials, and discloses an iron-coated boron-doped high-nickel anode material, and a preparation method and application thereof. The preparation method comprises the following steps: mixing a high-nickel positive electrode material precursor, a lithium source and a boron source, grinding, drying, and then performing primary calcination to obtain a boron-doped high-nickel positive electrode material; dispersing the obtained boron-doped high-nickel cathode material in a solution, and adding soluble ferric salt and a precipitant to enable the iron to generate precipitate to be attached to the surface of the boron-doped high-nickel cathode material; and then carrying out secondary calcination to obtain the catalyst. The iron-coated boron-doped high-nickel positive electrode material provided by the invention has the advantages of high bonding strength between the coating layer and the core, stable material structure and excellent cycle performance of a battery prepared by using the iron-coated boron-doped high-nickel positive electrode material. The preparation method provided by the invention has a simple process and can realize industrial mass production.

Description

Iron-coated boron-doped high-nickel positive electrode material, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of energy storage materials, and particularly relates to an iron-coated boron-doped high-nickel positive electrode material, and a preparation method and application thereof.
Background
High nickel positive electrode materials (Ni > 0.6), particularly ultra-high nickel positive electrode materials (Ni > 0.9), although higher initial gram capacity is obtained by increasing the Ni duty ratio, have poor cycling stability because Co and Mn are too low in the high nickel positive electrode materials. Thus, it is generally desirable to modify it to enhance its electrochemical performance. Doping and cladding are two methods for improving the electrochemical performance of high nickel cathode materials.
The precipitation method and the solid phase method are common coating methods, but both coating methods have certain defects. Wherein the coating layer prepared by the precipitation method has weak bonding effect because the coating layer is formed with the internal positive electrode material mainly through van der waals force. In the charge and discharge process of the battery, the structure of the positive electrode material is changed after repeated contraction and expansion due to repeated intercalation and deintercalation of lithium ions, and the coating prepared by the precipitation method is easy to fall off due to weaker binding force, so that internal positive electrode material particles are in direct contact with electrolyte, side reaction occurs, and the service life of the battery is seriously influenced. There is also a technology of coating a positive electrode material by an in-situ generation method, for example, patent CN104692352a discloses a method for coating a surface of a positive electrode material of a lithium ion battery with nanoscale ferric phosphate, which comprises the following preparation steps: preparation of FePO 4 A solution; pulping the anode material; drying the slurry; and sieving the sintered powder to finish the process of coating the surface of the positive electrode material of the lithium ion battery with the nanoscale ferric phosphate. The nano FePO4 can be discontinuously and densely coated on the surface of the positive electrode material by adopting an in-situ generation method, so that the safety performance and the cycle performance of the positive electrode material are improved. The anode material is coated with nano FePO4 in a discontinuous manner, so that the anode material has good safety performance. However, the coating method has complex process and high cost, and is difficult for industrial mass production.
Therefore, it is desirable to provide a method for preparing a high-nickel positive electrode material, which can improve the bonding strength of the coating layer and the cycling stability of the positive electrode material; and the process is simple, and can realize industrialized mass production.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides an iron-coated boron-doped high-nickel positive electrode material, and a preparation method and application thereof. The high-nickel positive electrode material provided by the invention has the advantages of stable structure, high bonding strength of the coating layer and excellent cycle performance of a battery prepared by using the high-nickel positive electrode material; the preparation method is simple, and can realize industrialized mass production.
The invention provides a preparation method of an iron-coated boron-doped high-nickel positive electrode material.
Specifically, the preparation method of the iron-coated boron-doped high-nickel positive electrode material comprises the following steps of:
(1) Mixing a high-nickel positive electrode material precursor, a lithium source and a boron source, grinding, drying, and then performing primary calcination to obtain a boron-doped high-nickel positive electrode material;
(2) Dispersing the boron-doped high-nickel anode material obtained in the step (1) in a solution, and adding soluble ferric salt and a precipitant to enable iron to generate precipitate and adhere to the surface of the boron-doped high-nickel anode material; and then solid-liquid separation is carried out to obtain a solid product, and the solid product is subjected to secondary calcination to obtain the iron-coated boron-doped high-nickel anode material.
Preferably, the high nickel positive electrode material precursor is Ni x Co y M (1-x-y) (OH) 2 Wherein 0.95 is greater than or equal to x is greater than or equal to 0.8,0.2 is greater than or equal to y is greater than or equal to 0.05, and M is selected from Mn or Al.
Preferably, a dispersing agent is also added during the milling of step (1).
Preferably, the dispersant comprises ethanol and/or water.
Preferably, in step (1), the process of the primary calcination is: calcining for 8-20 hours at 700-850 ℃ in oxygen atmosphere; further preferably, in step (1), the process of the primary calcination is: calcining at 750-800 deg.C for 10-15 hr under oxygen atmosphere.
Preferably, in step (1), the molar ratio of lithium in the lithium source to Ni in the high nickel positive electrode material precursor is (0.8-1.5): 1; further preferably, the molar ratio of lithium in the lithium source to Ni in the high nickel positive electrode material precursor is (0.8-1.2): 1.
Preferably, in step (1), the mass of boron in the boron source is 0.1% -1% of the mass of the high nickel positive electrode material precursor; further preferably, in step (1), the mass of boron in the boron source is 0.5% -1% of the mass of the high nickel positive electrode material precursor.
Preferably, in step (1), the boron source is at least one of boric acid, a borate, and an oxide of boron.
Preferably, in step (2), the solvent is selected from at least one of water and ethanol.
Preferably, in step (2), the molar ratio of the soluble iron salt to boron in the boron source is (1-10): 1, a step of; further preferably, in step (2), the molar ratio of the soluble iron salt to boron in the boron source is (1-5): 1.
preferably, in step (2), the soluble iron salt is selected from at least one of ferric nitrate, ferric sulfate, ferric chloride.
Preferably, in step (2), the molar ratio of the precipitant to the soluble iron salt is 1: (1-2).
Preferably, in step (2), the precipitant is a phosphate, a fluoride or a base. The phosphate comprises sodium phosphate, potassium phosphate or ammonium phosphate; the fluoride salt comprises ammonium fluoride or magnesium fluoride; the alkali comprises sodium hydroxide, potassium hydroxide or ammonia water.
Preferably, in step (2), the secondary calcination is performed by: calcining for 2-6 hours under the condition of 700-850 ℃ under inert gas; further preferably, the secondary calcination is performed by: calcining under inert gas at 750-800 deg.C for 4-5 hr.
More specifically, the preparation method of the iron-coated boron-doped high-nickel positive electrode material comprises the following steps of:
(1) Mixing and ball milling a high nickel anode material precursor, a lithium source, a boron source and a dispersing agent, drying, sieving and calcining for one time to obtain a boron doped high nickel anode material;
(2) Dispersing the boron-doped high-nickel cathode material obtained in the step (1) in a solution, and sequentially adding a soluble ferric salt and a precipitant to enable iron to generate precipitate and adhere to the surface of the boron-doped high-nickel cathode material; and then solid-liquid separation is carried out to obtain a solid product, and the solid product is dried and then subjected to secondary calcination under the condition of inert gas, thus obtaining the iron-coated boron-doped high-nickel anode material.
The second aspect of the invention provides an iron-coated boron-doped high nickel positive electrode material.
Specifically, the iron-coated boron-doped high-nickel positive electrode material is prepared by the preparation method; the iron-coated boron-doped high-nickel positive electrode material consists of an inner core and a coating layer, wherein the inner core is a boron-doped nickel-cobalt-manganese ternary material, and the coating layer is an iron oxide, an iron fluoride, an iron phosphate, an iron boride, an iron oxide-carbon composite, an iron boride-carbon composite, an iron oxide-iron boride-carbon composite and an iron boride-carbon composite.
Preferably, the doping amount of the boron is 0.1% -1%; further preferably, the doping amount of boron is 0.5% -1%. The doping amount of the boron refers to the mass of the boron accounting for the mass of the high-nickel positive electrode material precursor.
In a third aspect of the invention, a positive electrode sheet is provided.
Specifically, the positive plate comprises the iron-coated boron-doped high-nickel positive electrode material.
In a fourth aspect, the present invention provides a lithium ion battery.
Concretely, the lithium ion battery comprises the positive plate.
Compared with the prior art, the invention has the following beneficial effects:
(1) The iron-coated boron-doped high-nickel positive electrode material provided by the invention is characterized in that boron is doped in the high-nickel positive electrode material, and the iron is coated on the outer layer. The melting point of the boron oxide is low, the boron oxide is uniformly diffused into the interior and the surface of the positive electrode material in the primary calcination process, and the stability and the conductivity of the positive electrode material can be improved by the boron in the positive electrode material; boron on the surface of the anode material can further react with iron in the coating layer to form a chemical bond in the secondary calcination process, so that the bonding strength of the coating layer is improved, and the cycling stability of the battery is improved; boron on the surface of the positive electrode material can also diffuse into the coating layer during secondary calcination to form iron boride, thereby improving the conductivity of the coating layer.
(2) The iron-coated boron-doped high-nickel positive electrode material provided by the invention has the advantages of high bonding strength between the coating layer and the core, stable material structure and excellent cycle performance of a battery prepared by using the iron-coated boron-doped high-nickel positive electrode material.
(3) The preparation method provided by the invention has a simple process and can realize industrial mass production.
Drawings
Fig. 1 is an SEM image of the iron-coated boron-doped high nickel cathode material prepared in example 1.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples will be presented. It should be noted that the following examples do not limit the scope of the invention.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
Example 1
The preparation method of the iron-coated boron-doped high-nickel positive electrode material comprises the following steps of:
(1) 10.0g Ni 0.9 Co 0.05 Mn 0.05 (OH) 2 Adding precursor, 2.33g of lithium hydroxide (the molar ratio of lithium to Ni is 1:1), 0.28g of boron oxide and 2mL of ethanol into a ball mill for ball milling for 8 hours, uniformly mixing, drying in an oven at 80 ℃ for 3 hours, sieving with a 300-mesh sieve, transferring the obtained powder into a roller kiln, calcining at 800 ℃ for 12 hours under pure oxygen atmosphere, and cooling to obtain a boron-doped high-nickel anode material;
(2) Dispersing the boron-doped high-nickel cathode material obtained in the step (1) in 50mL of water, adding 40mL of 2mol/L ferric sulfate solution, then adding 10mL of 2mol/L sodium phosphate as a precipitator, reacting ferric sulfate with sodium phosphate to generate ferric phosphate precipitate, attaching the ferric phosphate precipitate to the surface of the boron-doped high-nickel cathode material, carrying out solid-liquid separation on reactants to obtain a solid product, and placing the solid product in an oven to be baked for 3 hours at 80 ℃; and transferring the baked object product into a roller kiln, and performing secondary calcination for 4 hours at 800 ℃ in a pure oxygen atmosphere to obtain the iron-coated boron-doped high-nickel anode material.
The iron-coated boron-doped high-nickel anode material prepared by the method comprises a core and a coating layer, wherein the core is a boron-doped nickel-cobalt-manganese ternary material, the boron doping amount is about 0.85%, and the coating layer is ferric phosphate. An SEM image of the iron-coated boron-doped high nickel cathode material is shown in fig. 1, and it can be seen from fig. 1 that a coating layer is formed on the surface of the material.
Example 2
The preparation method of the iron-coated boron-doped high-nickel positive electrode material comprises the following steps of:
(1) 10.0g Ni 0.9 Co 0.05 Mn 0.05 (OH) 2 Adding precursor, 2.33g of lithium hydroxide (the molar ratio of lithium to Ni is 1:1), 0.28g of boron oxide and 2mL of ethanol into a ball mill for ball milling for 8 hours, uniformly mixing, drying in an oven at 80 ℃ for 3 hours, sieving with a 300-mesh sieve, transferring the obtained powder into a roller kiln, calcining at 800 ℃ for 12 hours under pure oxygen atmosphere, and cooling to obtain a boron-doped high-nickel anode material;
(2) Dispersing the boron-doped high-nickel cathode material obtained in the step (1) in 50mL of water, adding 40mL of 2mol/L ferric nitrate solution, then adding 10mL of 2mol/L sodium phosphate as a precipitator, reacting ferric nitrate and sodium phosphate to generate ferric phosphate precipitate, attaching the ferric phosphate precipitate to the surface of the boron-doped high-nickel cathode material, carrying out solid-liquid separation on reactants to obtain a solid product, and placing the solid product in an oven to be baked for 3 hours at 80 ℃; and transferring the baked object product into a roller kiln, and performing secondary calcination for 4 hours at 800 ℃ in a pure oxygen atmosphere to obtain the iron-coated boron-doped high-nickel anode material.
The iron-coated boron-doped high-nickel anode material prepared by the method comprises a core and a coating layer, wherein the core is a boron-doped nickel-cobalt-manganese ternary material, the boron doping amount is about 0.85%, and the coating layer is ferric phosphate.
Example 3
The preparation method of the iron-coated boron-doped high-nickel positive electrode material comprises the following steps of:
(1) 10.0g Ni 0.9 Co 0.05 Mn 0.05 (OH) 2 Adding precursor, 2.33g of lithium hydroxide (the molar ratio of lithium to Ni is 1:1), 0.28g of boron oxide and 2mL of ethanol into a ball mill for ball milling for 8 hours, uniformly mixing, drying in an oven at 80 ℃ for 3 hours, sieving with a 300-mesh sieve, transferring the obtained powder into a roller kiln, calcining at 800 ℃ for 12 hours under pure oxygen atmosphere, and cooling to obtain a boron-doped high-nickel anode material;
(2) Dispersing the boron-doped high-nickel cathode material obtained in the step (1) in 50mL of water, adding 40mL of 2mol/L ferric nitrate solution, then adding 10mL of 4mol/L sodium hydroxide as a precipitator, reacting ferric nitrate and sodium hydroxide to generate ferric hydroxide precipitate, attaching the ferric hydroxide precipitate to the surface of the boron-doped high-nickel cathode material, separating solid and liquid of reactants to obtain a solid product, and placing the solid product in an oven to bake for 3 hours at 80 ℃; and transferring the baked object product into a roller kiln, and performing secondary calcination for 4 hours at 800 ℃ in a pure oxygen atmosphere to obtain the iron-coated boron-doped high-nickel anode material.
The iron-coated boron-doped high-nickel anode material prepared by the method comprises a core and a coating layer, wherein the core is a boron-doped nickel-cobalt-manganese ternary material, the boron doping amount is about 0.85%, and the coating layer is ferric oxide.
Example 4
The preparation method of the iron-coated boron-doped high-nickel positive electrode material comprises the following steps of:
(1) 10.0g Ni 0.9 Co 0.05 Mn 0.05 (OH) 2 Putting the precursor, 2.33g of lithium hydroxide (the molar ratio of lithium to Ni is 1:1), 0.28g of boron oxide and 10mL of ethanol into a ball mill for ball milling for 8 hours, uniformly mixing, drying in an oven at 80 ℃ for 3 hours, sieving with a 300-mesh sieve, transferring the obtained powder into a roller kiln, and carrying out pure oxygen atmosphereCalcining at 800 ℃ for 12 hours, and cooling to obtain the boron-doped high-nickel anode material;
(2) Dispersing the boron-doped high-nickel cathode material obtained in the step (1) in 50mL of water, adding 40mL of 2mol/L ferric sulfate solution, then adding 10mL of 2mol/L sodium phosphate as a precipitator, reacting ferric sulfate with sodium phosphate to generate ferric phosphate precipitate, attaching the ferric phosphate precipitate to the surface of the boron-doped high-nickel cathode material, carrying out solid-liquid separation on reactants to obtain a solid product, and placing the solid product in an oven to be baked for 3 hours at 80 ℃; and transferring the baked object product into a roller kiln, and performing secondary calcination for 4 hours at 400 ℃ in a pure oxygen atmosphere to obtain the iron-coated boron-doped high-nickel anode material.
The iron-coated boron-doped high-nickel anode material prepared by the method comprises a core and a coating layer, wherein the core is a boron-doped nickel-cobalt-manganese ternary material, the boron doping amount is about 0.85%, and the coating layer is ferric phosphate.
Example 5
The preparation method of the iron-coated boron-doped high-nickel positive electrode material comprises the following steps of:
(1) 10.0g Ni 0.9 Co 0.05 Mn 0.05 (OH) 2 Adding precursor, 2.33g of lithium hydroxide (the molar ratio of lithium to Ni is 1:1), 0.033g of boron oxide and 2mL of ethanol into a ball mill for ball milling for 8 hours, uniformly mixing, drying in an oven at 80 ℃ for 3 hours, sieving with a 300-mesh sieve, transferring the obtained powder into a roller kiln, calcining at 800 ℃ for 12 hours under pure oxygen atmosphere, and cooling to obtain a boron-doped high-nickel anode material;
(2) Dispersing the boron-doped high-nickel cathode material obtained in the step (1) in 50mL of water, adding 60mL of 2mol/L ferric sulfate solution, then adding 10mL of 2mol/L sodium phosphate as a precipitator, reacting ferric sulfate with sodium phosphate to generate ferric phosphate precipitate, attaching the ferric phosphate precipitate to the surface of the boron-doped high-nickel cathode material, carrying out solid-liquid separation on reactants to obtain a solid product, and placing the solid product in an oven to be baked for 3 hours at 80 ℃; and transferring the baked object product into a roller kiln, and performing secondary calcination for 4 hours at 800 ℃ in a pure oxygen atmosphere to obtain the iron-coated boron-doped high-nickel anode material.
The iron-coated boron-doped high-nickel anode material prepared by the method comprises a core and a coating layer, wherein the core is a boron-doped nickel-cobalt-manganese ternary material, the boron doping amount is about 0.1%, and the coating layer is ferric phosphate.
Comparative example 1
The preparation method of the iron-coated high-nickel positive electrode material comprises the following steps:
(1) 10.0g Ni 0.9 Co 0.05 Mn 0.05 (OH) 2 Putting the precursor, 2.33g of lithium hydroxide (the molar ratio of lithium to Ni is 1:1) and 2mL of ethanol into a ball mill for ball milling for 8 hours, uniformly mixing, drying in an oven at 80 ℃ for 3 hours, sieving with a 300-mesh sieve, transferring the obtained powder into a roller kiln, calcining for 12 hours at 800 ℃ in a pure oxygen atmosphere, and cooling to obtain a high-nickel anode material;
(2) Dispersing the high-nickel cathode material obtained in the step (1) in 50mL of water, adding 40mL of 2mol/L ferric sulfate solution, then adding 10mL of 2mol/L sodium phosphate as a precipitator, reacting ferric sulfate and sodium phosphate to generate ferric phosphate precipitate, attaching the ferric phosphate precipitate to the surface of the boron-doped high-nickel cathode material, separating solid and liquid of reactants to obtain a solid product, and placing the solid product in an oven to bake for 3 hours at 80 ℃; and transferring the baked object product into a roller kiln, and secondarily calcining for 4 hours at 800 ℃ in a pure oxygen atmosphere to obtain the iron-coated high-nickel anode material.
The iron-coated high-nickel anode material prepared by the method comprises an inner core and a coating layer, wherein the inner core is made of a nickel-cobalt-manganese ternary material, and the coating layer is made of ferric phosphate.
Comparative example 2
The preparation method of the iron-coated fluorine-doped high-nickel positive electrode material comprises the following steps of:
(1) 10.0g Ni 0.9 Co 0.05 Mn 0.05 (OH) 2 Putting the precursor, 2.33g of lithium hydroxide (the molar ratio of lithium to Ni is 1:1), 0.171g of ammonium fluoride and 2mL of ethanol into a ball mill for ball milling for 8 hours, uniformly mixing, drying for 3 hours at 80 ℃ in an oven, sieving with a 300-mesh sieve, transferring the obtained powder into a roller kiln, calcining for 12 hours at 800 ℃ in a pure oxygen atmosphere,cooling to obtain a fluorine-doped high-nickel anode material;
(2) Dispersing the fluorine-doped high-nickel cathode material obtained in the step (1) in 50mL of water, adding 40mL of 2mol/L ferric sulfate solution, then adding sodium phosphate as a precipitator, reacting ferric sulfate and sodium phosphate to generate ferric phosphate precipitate, attaching the ferric phosphate precipitate to the surface of the fluorine-doped high-nickel cathode material, carrying out solid-liquid separation on reactants to obtain a solid product, and placing the solid product in an oven to bake for 3 hours at 80 ℃; and transferring the baked object product into a roller kiln, and performing secondary calcination for 4 hours at 800 ℃ in a pure oxygen atmosphere to obtain the iron-coated fluorine-doped high-nickel anode material.
The iron-coated fluorine-doped high-nickel anode material prepared by the method comprises an inner core and a coating layer, wherein the inner core is a fluorine-doped nickel-cobalt-manganese ternary material, the fluorine doping amount is about 0.87%, and the coating layer is ferric phosphate.
Comparative example 3
A preparation method of a boron-doped high-nickel positive electrode material comprises the following steps:
(1) 10.0g Ni 0.9 Co 0.05 Mn 0.05 (OH) 2 The precursor, 2.33g of lithium hydroxide (the molar ratio of lithium to Ni is 1:1), 0.28g of boron oxide and 2mL of ethanol are put into a ball mill for ball milling for 8 hours, after being uniformly mixed, the mixture is dried in an oven at 80 ℃ for 3 hours, then the mixture is sieved by a 300-mesh sieve, the obtained powder is transferred into a roller kiln, and is calcined for 12 hours at 800 ℃ under pure oxygen atmosphere, and then the boron-doped high-nickel anode material is obtained after cooling.
The boron-doped high-nickel positive electrode material prepared by the method does not contain a coating layer, and the doping amount of boron is about 0.85%.
Product effect test
The iron-coated boron-doped high-nickel cathode materials prepared in examples 1 to 5, the iron-coated high-nickel cathode material prepared in comparative example 1, the iron-coated fluorine-doped high-nickel cathode material prepared in comparative example 2, and the boron-doped high-nickel cathode material prepared in comparative example 3 were prepared into button cells, and electrochemical performance tests of lithium ion batteries were performed thereon. The method comprises the following specific steps: n-methyl pyrrolidone is used as a solvent, the high-nickel anode material, acetylene black and PVDF are uniformly mixed according to the mass ratio of 9.2:0.5:0.3, the mixture is coated on an aluminum foil, and the mixture is dried for 8 hours by blowing at 80 ℃ and then is dried for 12 hours in vacuum at 120 ℃. The battery is assembled in an argon-protected glove box, the negative electrode is a metal lithium sheet, the diaphragm is a polypropylene film, the electrolyte is 1M LiPF6-EC/DMC (1:1, V/V), a 2032 button battery shell is adopted to assemble the button battery in the argon-protected glove box, and then electrochemical performance test is carried out at 25 ℃ at 3.0-4.5V. The results are shown in Table 1.
TABLE 1
As can be seen from table 1, the iron-coated boron-doped high-nickel positive electrode materials prepared in examples 1 and 2 have a coating layer of iron phosphate, a coating layer and a core component of the high-nickel positive electrode material have high bonding strength, excellent cycling stability in the charge and discharge processes, a specific discharge capacity of more than 190mAh/g after 100 cycles, and a cycle retention rate of more than 90%. Analysis of examples 1 and 2-5 shows that when alkali (sodium hydroxide) is used as the precipitant, the final coating is iron oxide, which has stability and conductivity slightly lower than the high nickel positive electrode material having an iron phosphate coating. When the secondary calcination temperature is reduced to 400 ℃, the temperature is lower than the melting point of boron oxide, and boron cannot diffuse into the coating layer, so that the conductivity is reduced, and the actual gram capacity (0.1C discharge capacity) is reduced; in addition, boron cannot diffuse into the coating layer, so that the bonding strength between the coating layer and the core material is reduced, and the boron is easy to fall off in circulation, thereby influencing the circulation stability of the battery. When the amount of boron added is reduced, the conductivity is reduced, the actual gram capacity (0.1C discharge capacity) is reduced, and the cycle stability is lowered. Analysis of example 1 and comparative examples 1-3 revealed that when boron is not doped and only iron is used for coating, the problems of poor cycling stability and poor conductivity of the high-nickel positive electrode material still cannot be well improved; when fluorine is doped and iron is coated, the conductivity is improved to a certain extent, the practical gram capacity (0.1C discharge capacity) is improved to a certain extent, but the 0.1C discharge capacity and the cycle stability of the iron-coated boron-doped high-nickel anode material prepared in the embodiment 1 are far lower; when boron is doped, the conductive performance is obviously improved, the battery has high charge-discharge capacity at 0.1 ℃, but the bonding strength of the coating layer and the core component is low, and the cycling stability of the battery is poor.

Claims (6)

1. The preparation method of the iron-coated boron-doped high-nickel positive electrode material is characterized by comprising the following steps of:
(1) Mixing a high-nickel positive electrode material precursor, a lithium source and a boron oxide source, grinding, drying, and then performing primary calcination to obtain a boron-doped high-nickel positive electrode material;
the precursor of the high nickel positive electrode material is Ni x Co y Mn (1-x-y) (OH) 2 Wherein x is more than or equal to 0.95 and more than or equal to 0.8, y is more than or equal to 0.2 and more than or equal to 0.05;
(2) Dispersing the boron-doped high-nickel anode material obtained in the step (1) in a solution, and adding soluble ferric salt and phosphate to enable iron to generate precipitate and adhere to the surface of the boron-doped high-nickel anode material; then solid-liquid separation is carried out to obtain a solid product, and the solid product is subjected to secondary calcination to obtain the iron-coated boron-doped high-nickel anode material;
the secondary calcination process is as follows: calcining for 2-6 hours under the condition of 700-850 ℃ under inert gas;
the molar ratio of the soluble iron salt to boron in the boron oxide is further defined as (1-5): 1.
2. the method according to claim 1, wherein in the step (1), the primary calcination is performed by: calcining at 700-850 deg.C for 8-20 hr under oxygen atmosphere.
3. The method according to claim 1, wherein in the step (1), a molar ratio of lithium in the lithium source to Ni in the high nickel positive electrode material precursor is (0.8-1.5): 1.
4. An iron-coated boron-doped high nickel positive electrode material, characterized by being produced by the production method according to any one of claims 1 to 3; the high-nickel anode material consists of an inner core and a coating layer, wherein the inner core is a boron-doped nickel-cobalt-manganese ternary material, and the coating layer is ferric phosphate; the doping amount of the boron is 0.5% -1%.
5. A positive electrode sheet comprising the iron-coated boron-doped high nickel positive electrode material according to claim 4.
6. A lithium ion battery comprising the positive electrode sheet according to claim 5.
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