CN115490275A - 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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CN115490275A
CN115490275A CN202211150595.XA CN202211150595A CN115490275A CN 115490275 A CN115490275 A CN 115490275A CN 202211150595 A CN202211150595 A CN 202211150595A CN 115490275 A CN115490275 A CN 115490275A
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boron
iron
nickel
positive electrode
doped high
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CN115490275B (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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Hunan Brunp Recycling Technology Co Ltd
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 carrying out primary calcination to obtain a boron-doped high-nickel positive electrode material; dispersing the obtained boron-doped high-nickel anode material into a solution, and adding soluble ferric salt and a precipitator to enable iron to generate precipitate to be attached to the surface of the boron-doped high-nickel anode material; then carrying out secondary calcination to obtain the catalyst. The iron-coated boron-doped high-nickel cathode material provided by the invention has the core and the coating layer, the bonding strength between the coating layer and the core is high, the material structure is stable, and the battery prepared by using the material has excellent cycle performance. The preparation method provided by the invention is simple in 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 cathode material as well as 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 content, have poor cycle stability because Co and Mn are too low in the high nickel positive electrode material. Therefore, it is generally necessary to modify them to improve their electrochemical properties. Doping and cladding are two methods for improving the electrochemical performance of the high-nickel cathode material.
The precipitation method and the solid phase method are common coating methods, but both coating methods have certain defects. The coating layer prepared by the precipitation method is weak in bonding effect because the coating layer is mainly bonded with the internal cathode material through van der waals force. In the process of charging and discharging of the battery, the structure of the anode material is changed after repeated shrinkage and expansion due to repeated insertion and extraction of lithium ions, and the coating layer prepared by a precipitation method is easy to fall off because of weak binding power, so that the inside anode 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 technique of coating the anode material by in-situ generation, for example, patent CN104692352A discloses a method for coating nano-scale iron phosphate on the surface of the anode material of a lithium ion battery, which comprises the following stepsThe preparation method comprises the following steps: preparation of FePO 4 A solution; pulping the positive electrode material; drying the slurry; and sieving the sintered powder to finish the process of coating the nano-scale iron phosphate on the surface of the lithium ion battery anode material. The nano FePO4 can be densely coated on the surface of the anode material in a non-continuous manner by adopting an in-situ generation method, so that the safety performance and the cycle performance of the anode material are improved. The nano FePO4 is used for discontinuously coating the anode material, and the anode material shows good safety performance. However, the coating method has complex process and high cost, and is difficult to realize industrial mass production.
Therefore, it is desirable to provide a method for preparing a high-nickel cathode material, which can improve the bonding strength of the coating layer and the cycling stability of the cathode material; and the process is simple, and industrial mass production can be realized.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides an iron-coated boron-doped high-nickel cathode material and a preparation method and application thereof. The high-nickel anode material provided by the invention has the advantages that the structure is stable, the bonding strength of the coating layer is high, and the cycle performance of a battery prepared by using the high-nickel anode material is excellent; the preparation method is simple and can realize industrial mass production.
The invention provides a preparation method of an iron-coated boron-doped high-nickel cathode material.
Specifically, the preparation method of the iron-coated boron-doped high-nickel cathode material comprises the following steps:
(1) Mixing a high-nickel positive electrode material precursor, a lithium source and a boron source, grinding, drying and then carrying out primary calcination to obtain a boron-doped high-nickel positive electrode material;
(2) Dispersing the boron-doped high-nickel positive electrode material obtained in the step (1) in a solution, and adding a soluble iron salt and a precipitator to enable iron to generate precipitate to be attached to the surface of the boron-doped high-nickel positive electrode material; and then carrying out solid-liquid separation to obtain a solid product, and then carrying out secondary calcination on the solid product to obtain the iron-coated boron-doped high-nickel cathode material.
Preferably, the high-nickel cathode material precursor is Ni x Co y M (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, and M is selected from Mn or Al.
Preferably, a dispersing agent is also added during the grinding in step (1).
Preferably, the dispersant comprises ethanol and/or water.
Preferably, in step (1), the primary calcination process is: calcining at 700-850 deg.C for 8-20 hr in oxygen atmosphere; further preferably, in step (1), the primary calcination process is: calcining at 750-800 deg.C for 10-15 hr in oxygen atmosphere.
Preferably, in the step (1), the molar ratio of lithium in the lithium source to Ni in the high-nickel cathode 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 cathode material precursor is (0.8-1.2): 1.
Preferably, in the step (1), the mass of boron in the boron source is 0.1-1% of the mass of the high-nickel cathode material precursor; further preferably, in the step (1), the mass of boron in the boron source is 0.5% -1% of the mass of the high-nickel cathode 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 the 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 the boron in the boron source is (1-10): 1; further preferably, in step (2), the molar ratio of the soluble iron salt to the boron in the boron source is (1-5): 1.
preferably, in step (2), the soluble ferric salt is selected from at least one of ferric nitrate, ferric sulfate, and ferric chloride.
Preferably, in step (2), the molar ratio of the precipitating agent to the soluble iron salt is 1: (1-2).
Preferably, in step (2), the precipitating agent is a phosphate, a fluoride salt 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 process of the secondary calcination is: calcining for 2-6 hours at 700-850 ℃ under inert gas; further preferably, the process of the secondary calcination is: calcining for 4-5 hours at 750-800 ℃ under the inert gas.
More specifically, the preparation method of the iron-coated boron-doped high-nickel cathode material comprises the following steps:
(1) Mixing and ball-milling a high-nickel positive electrode material precursor, a lithium source, a boron source and a dispersing agent, then drying, sieving and calcining for the first time to obtain a boron-doped high-nickel positive electrode material;
(2) Dispersing the boron-doped high-nickel positive electrode material obtained in the step (1) in a solution, and sequentially adding soluble ferric salt and a precipitator to enable iron to generate precipitate to be attached to the surface of the boron-doped high-nickel positive electrode material; and then carrying out solid-liquid separation to obtain a solid product, drying the solid product, and then carrying out secondary calcination under the condition of inert gas to obtain the iron-coated boron-doped high-nickel cathode material.
In a second aspect, the invention provides an iron-coated boron-doped high-nickel cathode material.
Specifically, an iron-coated boron-doped high-nickel cathode material is prepared by the preparation method; the iron-coated boron-doped high-nickel cathode material comprises 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 and carbon compound, an iron boride and carbon compound, an iron oxide, an iron boride and carbon compound.
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 percentage of the mass of the boron to the mass of the high-nickel positive electrode material precursor.
In a third aspect, the present invention provides a positive electrode sheet.
Specifically, the positive plate comprises the iron-coated boron-doped high-nickel positive electrode material.
In a fourth aspect, the invention provides a lithium ion battery.
Concretely, a 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 cathode material provided by the invention is characterized in that boron is doped in the high-nickel cathode material, and the outer layer is coated with iron. The melting point of boron oxide is low, the boron oxide is uniformly diffused into and on the surface of the anode material in the primary calcining process, and the boron in the anode material can improve the stability and the conductivity of the anode material; the 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 calcining process, so that the bonding strength of the coating layer is improved, and the cycling stability of the battery is improved; the boron on the surface of the positive electrode material can be diffused into the coating layer during secondary calcination to form iron boride, so that the conductivity of the coating layer is improved.
(2) The iron-coated boron-doped high-nickel cathode material provided by the invention has the core and the coating layer, the bonding strength between the coating layer and the core is high, the material structure is stable, and the battery prepared by using the iron-coated boron-doped high-nickel cathode material has excellent cycle performance.
(3) The preparation method provided by the invention is simple in 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 are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
Example 1
A preparation method of an iron-coated boron-doped high-nickel cathode material comprises the following steps:
(1) 10.0g of Ni 0.9 Co 0.05 Mn 0.05 (OH) 2 Putting a precursor, 2.33g of lithium hydroxide (the molar ratio of lithium to Ni is 1;
(2) Dispersing the boron-doped high-nickel positive electrode 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 positive electrode material, carrying out solid-liquid separation on reactants to obtain a solid product, and baking the solid product in an oven at 80 ℃ for 3 hours; and transferring the baked object product into a roller kiln, and calcining for 4 hours at 800 ℃ in a pure oxygen atmosphere to obtain the iron-coated boron-doped high-nickel cathode material.
The iron-coated boron-doped high-nickel cathode material prepared by the method comprises an inner core and a coating layer, wherein the inner core is a boron-doped nickel-cobalt-manganese ternary material, the doping amount of boron is about 0.85%, and the coating layer is iron phosphate. The 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
A preparation method of an iron-coated boron-doped high-nickel cathode material comprises the following steps:
(1) 10.0g of Ni 0.9 Co 0.05 Mn 0.05 (OH) 2 Putting a precursor, 2.33g of lithium hydroxide (the molar ratio of lithium to Ni is 1A positive electrode material;
(2) Dispersing the boron-doped high-nickel positive electrode 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 with sodium phosphate to generate ferric phosphate precipitate, attaching the ferric phosphate precipitate to the surface of the boron-doped high-nickel positive electrode material, carrying out solid-liquid separation on reactants to obtain a solid product, and baking the solid product in an oven at 80 ℃ for 3 hours; and transferring the baked object product into a roller kiln, and calcining for 4 hours at 800 ℃ in a pure oxygen atmosphere to obtain the iron-coated boron-doped high-nickel cathode material.
The iron-coated boron-doped high-nickel cathode 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 doping amount of boron is about 0.85%, and the coating layer is iron phosphate.
Example 3
A preparation method of an iron-coated boron-doped high-nickel cathode material comprises the following steps:
(1) 10.0g of 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;
(2) Dispersing the boron-doped high-nickel anode 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 anode material, carrying out solid-liquid separation on reactants to obtain a solid product, and baking the solid product in an oven at 80 ℃ for 3 hours; and transferring the baked object product into a roller kiln, and calcining for 4 hours at 800 ℃ in a pure oxygen atmosphere to obtain the iron-coated boron-doped high-nickel cathode material.
The iron-coated boron-doped high-nickel cathode material prepared by the method comprises an inner core and a coating layer, wherein the inner core is a boron-doped nickel-cobalt-manganese ternary material, the doping amount of boron is about 0.85%, and the coating layer is iron oxide.
Example 4
A preparation method of an iron-coated boron-doped high-nickel cathode material comprises the following steps:
(1) 10.0g of 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;
(2) Dispersing the boron-doped high-nickel positive electrode 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 positive electrode material, carrying out solid-liquid separation on reactants to obtain a solid product, and baking the solid product in an oven at 80 ℃ for 3 hours; and transferring the baked object product into a roller kiln, and calcining 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 cathode 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 doping amount of boron is about 0.85%, and the coating layer is iron phosphate.
Example 5
A preparation method of an iron-coated boron-doped high-nickel cathode material comprises the following steps:
(1) 10.0g of Ni 0.9 Co 0.05 Mn 0.05 (OH) 2 The precursor, 2.33g of lithium hydroxide (molar ratio of lithium to Ni is 1Finally, transferring the mixture into a roller kiln, calcining the mixture for 12 hours at 800 ℃ in a pure oxygen atmosphere, and cooling the mixture to obtain a boron-doped high-nickel cathode material;
(2) Dispersing the boron-doped high-nickel positive electrode 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 and sodium phosphate to generate iron phosphate precipitate, attaching the iron phosphate precipitate to the surface of the boron-doped high-nickel positive electrode material, carrying out solid-liquid separation on reactants to obtain a solid product, and baking the solid product in an oven at 80 ℃ for 3 hours; and transferring the baked object product into a roller kiln, and calcining for 4 hours at 800 ℃ in a pure oxygen atmosphere to obtain the iron-coated boron-doped high-nickel cathode material.
The iron-coated boron-doped high-nickel cathode material prepared by the method comprises an inner core and a coating layer, wherein the inner core is a boron-doped nickel-cobalt-manganese ternary material, the doping amount of boron is about 0.1%, and the coating layer is iron phosphate.
Comparative example 1
A preparation method of an iron-coated high-nickel cathode material comprises the following steps:
(1) 10.0g of 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);
(2) Dispersing the high-nickel anode 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 iron phosphate precipitate, attaching the iron phosphate precipitate to the surface of the boron-doped high-nickel anode 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 calcining for 4 hours at 800 ℃ in a pure oxygen atmosphere to obtain the iron-coated high-nickel cathode material.
The iron-coated high-nickel positive electrode material prepared by the method comprises an inner core and a coating layer, wherein the inner core is a nickel-cobalt-manganese ternary material, and the coating layer is iron phosphate.
Comparative example 2
A preparation method of an iron-coated fluorine-doped high-nickel cathode material comprises the following steps:
(1) 10.0g of Ni 0.9 Co 0.05 Mn 0.05 (OH) 2 Putting a precursor, 2.33g of lithium hydroxide (the molar ratio of lithium to Ni is 1;
(2) Dispersing the fluorine-doped high-nickel positive electrode material obtained in the step (1) in 50mL of water, adding 40mL of 2mol/L ferric sulfate solution, 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 positive electrode material, carrying out solid-liquid separation on reactants to obtain a solid product, and baking the solid product in an oven at 80 ℃ for 3 hours; and transferring the baked object product into a roller kiln, and calcining for 4 hours at 800 ℃ in a pure oxygen atmosphere to obtain the iron-coated fluorine-doped high-nickel cathode material.
The iron-coated fluorine-doped high-nickel cathode 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 iron phosphate.
Comparative example 3
A preparation method of a boron-doped high-nickel cathode material comprises the following steps:
(1) 10.0g of 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 1And (4) burning for 12 hours, and cooling to obtain the boron-doped high-nickel cathode material.
The boron-doped high-nickel cathode material prepared by the method does not contain a coating layer, and the doping amount of boron is about 0.85%.
Product effectiveness testing
The iron-coated boron-doped high-nickel positive electrode material prepared in examples 1 to 5, the iron-coated high-nickel positive electrode material prepared in comparative example 1, the iron-coated fluorine-doped high-nickel positive electrode material prepared in comparative example 2, and the boron-doped high-nickel positive electrode material prepared in comparative example 3 were formulated into a button cell, and the electrochemical performance of the lithium ion battery was tested. The method comprises the following specific steps: the method comprises the steps of taking N-methylpyrrolidone as a solvent, uniformly mixing a high-nickel positive electrode material, acetylene black and PVDF according to the mass ratio of 9.2: 0.5: 0.3, coating on an aluminum foil, carrying out forced air drying at 80 ℃ for 8 hours, and carrying out vacuum drying at 120 ℃ for 12 hours. 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, V/V), a 2032 type button battery case 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
Figure BDA0003856956330000081
As can be seen from table 1, the iron-coated boron-doped high-nickel cathode material prepared in examples 1 and 2 has a coating layer made of iron phosphate, the bonding strength between the coating layer and the core component is high, excellent cycle stability is shown in the charge-discharge process, the specific discharge capacity is still greater than 190mAh/g after 100 cycles, and the cycle retention rate is greater than 90%. Analysis of examples 1 and 2-5 reveals that when alkali (sodium hydroxide) is used as a precipitant, the final coating layer is iron oxide, which has stability and conductivity slightly lower than those of high nickel cathode materials having iron phosphate coating layers. When the secondary calcination temperature is reduced to 400 ℃, the temperature is lower than the melting point of boron oxide, 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, the boron is easy to fall off in circulation, and the circulation stability of the battery is influenced. When the amount of boron added is reduced, the conductivity is reduced, the actual gram-volume (0.1C discharge capacity) is reduced, and the cycle stability is reduced. Analysis of example 1 and comparative examples 1 to 3 shows that the problems of poor cycle stability and poor conductivity of the high nickel positive electrode material can not be improved well when boron is not doped and only iron is used for coating; when fluorine is doped and iron is coated, the conductivity of the material is improved to a certain extent, the actual gram capacity (0.1C discharge capacity) is improved to a certain extent, but the 0.1C discharge capacity and the cycle stability of the material are far inferior to those of the iron-coated boron-doped high-nickel cathode material prepared in the example 1; when boron is doped, the conductive performance of the battery is obviously improved without coating iron, 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 (10)

1. A preparation method of an iron-coated boron-doped high-nickel cathode material is characterized by comprising the following steps of:
(1) Mixing a high-nickel positive electrode material precursor, a lithium source and a boron source, grinding, drying and then carrying out primary calcination to obtain a boron-doped high-nickel positive electrode material;
(2) Dispersing the boron-doped high-nickel positive electrode material obtained in the step (1) in a solution, and adding a soluble iron salt and a precipitator to enable iron to generate precipitate to be attached to the surface of the boron-doped high-nickel positive electrode material; and then carrying out solid-liquid separation to obtain a solid product, and then carrying out secondary calcination on the solid product to obtain the iron-coated boron-doped high-nickel cathode material.
2. The preparation method according to claim 1, wherein in the step (1), the primary calcination is carried out by: calcining at 700-850 deg.C for 8-20 hr in oxygen atmosphere.
3. The method according to claim 1, wherein 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.
4. The method according to claim 1, wherein in the step (1), the boron source is at least one of boric acid, a borate, and an oxide of boron.
5. The method according to claim 4, wherein, in the step (2), the molar ratio of the soluble iron salt to boron in the boron source is (1-10): 1.
6. the production method according to claim 1 or 2, characterized in that, in step (2), the secondary calcination is carried out by: calcining for 2-6 hours at 700-850 ℃ under inert gas.
7. An iron-coated boron-doped high-nickel cathode material, characterized by being produced by the production method according to any one of claims 1 to 6; the high-nickel anode material is composed 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 or a composite of the iron oxide and carbon.
8. The iron-clad boron-doped high-nickel cathode material according to claim 7, wherein the doping amount of boron is 0.1 to 1%.
9. A positive electrode sheet comprising the iron-clad boron-doped high-nickel positive electrode material according to claim 7 or 8.
10. A lithium ion battery comprising the positive electrode sheet according to claim 9.
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