CN110120505B - Lithium ion battery positive electrode material, preparation method and lithium ion battery - Google Patents

Lithium ion battery positive electrode material, preparation method and lithium ion battery Download PDF

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CN110120505B
CN110120505B CN201910375283.0A CN201910375283A CN110120505B CN 110120505 B CN110120505 B CN 110120505B CN 201910375283 A CN201910375283 A CN 201910375283A CN 110120505 B CN110120505 B CN 110120505B
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林建雄
张鹏
蒋义淳
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Xiamen Xiaw New Energy Materials Co Ltd
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    • H—ELECTRICITY
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    • 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
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Abstract

The invention provides a lithium ion battery anode material, a preparation method thereof and a lithium ion battery containing the anode material. The core layer comprises a high nickel lithium cathode material with a chemical formula of LiaNibCocMndAleMfO2Wherein a is more than or equal to 0.95 and less than or equal to 1.05, b is more than or equal to 0.8 and less than or equal to 0.95, c is more than or equal to 0.01 and less than or equal to 0.15, d is more than or equal to 0 and less than or equal to 0.1, e is more than or equal to 0 and less than or equal to 0.05, f is more than or equal to 0 and less than or equal to 0.02, b + c + d + e + f is more than or equal to 0 and less than or equal to 1, and M is. The coating layer comprises a boron-containing lithium ion conductor with a chemical formula of LixByM’(1‑y)OzWherein M' is one or more of W, Mo, Se and P, x is more than or equal to 0.1 and less than or equal to 1.5, and y is more than or equal to 0.1 and less than or equal to 1<1，1.5≤z≤2.5。

Description

Lithium ion battery positive electrode material, preparation method and lithium ion battery
Technical Field
The invention relates to the field of lithium ion battery preparation, in particular to a lithium ion battery anode material, a preparation method thereof and a lithium ion battery.
Background
Lithium ion batteries are widely used in the fields of portable mobile devices, new energy vehicles, energy storage, and the like because of their excellent performance. Improving energy density and reducing material cost are the main directions of lithium ion battery development, and the performance of the lithium ion battery is determined by taking the anode material as a key material of the lithium ion battery. From the pursuit of high energy density and low cost, improvement of the performance of the positive electrode material has become a hot spot of research by those skilled in the art.
At present, new metal atoms (such as nickel) are usually introduced into a lithium cobaltate positive electrode material to replace cobalt to form a high-nickel material, so that the material cost is reduced and the energy density is improved. However, the highly reactive nickel ions in the high nickel-based material promote decomposition of the electrolyte, causing loss of the electrolyte and formation of a thick SEI film. Furthermore, in order to prepare ordered high nickel based materials, excess lithium must be introduced, which forms residues on the surface and reacts easily with carbon dioxide and water in the air to form Li2CO3And LiOH. This results in a high pH of the nickelic material, which is easily reacted with NMP during size mixing to form a gel; LiOH and LiPF in electrolyte6The reaction produces HF; li2CO3Which can cause severe ballooning of the battery during high temperature storage. In addition, the nickel-rich material surface side reactions can exacerbate the capacity fading of the material during cycling and high temperature storage, and cause safety problems.
Disclosure of Invention
The invention aims to provide a lithium battery positive electrode material capable of improving performance attenuation and safety problems of a nickel-rich material.
In addition, a preparation method of the lithium ion battery cathode material and a lithium ion battery containing the lithium ion battery cathode material are also needed to be provided.
In order to achieve the above object, the present invention provides a positive electrode material for a lithium ion battery, comprising:
a core layer comprising a high nickel lithium positive electrode material of formula LiaNibCocMndAleMfO2Wherein a is more than or equal to 0.95 and less than or equal to 1.05, b is more than or equal to 0.8 and less than or equal to 0.95, c is more than or equal to 0.01 and less than or equal to 0.15, d is more than or equal to 0 and less than or equal to 0.1, e is more than or equal to 0 and less than or equal to 0.05, f is more than or equal to 0 and less than or equal to 0.02, b + c + d + e + f is more than or equal to 0 and less than or equal to 1, and M is;
a cladding layer formed on the surface of the core layer, the cladding layer including a boron-containing lithium ion conductor of chemical formula LixByM’(1-y)OzWherein M' is one or more of W, Mo, Se and PX is more than or equal to 0.1 and less than or equal to 1.5, and y is more than or equal to 0.1 and less than or equal to 1<1，1.5≤z≤2.5。
The invention also provides a preparation method of the lithium ion battery anode material, which comprises the following steps:
preparing a core layer: mixing a lithium source, a nickel-cobalt-containing composite hydroxide and an oxide of M, stirring, sintering and dispersing to obtain a core layer sintered material, wherein M is one or more of W, Mo, Zr, Nb, Y and Sr; and
surface coating: and washing the sintering material with water, mixing the washed sintering material with boric acid and a compound of M ', wherein M' is one or more of W, Mo, Se and P, stirring, and carrying out a constant-temperature reaction, so as to form the coating layer on the surface of the sintering material, thereby obtaining the lithium ion battery anode material.
The invention also provides a lithium ion battery, which comprises a pole piece prepared from the lithium ion battery anode material, the binder and the conductive agent.
Compared with the prior art, the core layer of the lithium ion battery anode material is a high-nickel lithium anode material, the surface of the lithium ion battery anode material is coated with a boron-containing lithium ion conductor, and the boron-containing lithium ion conductor in the coating layer is in a lithium-deficient state, so that an additional lithium insertion vacancy can be provided, the first efficiency of the lithium ion anode material can be improved, and the first discharge capacity can be improved; moreover, the coating layer has good compactness, can effectively isolate the electrolyte from the core layer, prevent the electrolyte from directly contacting with the core layer, slow down the corrosion of the electrolyte to the core layer and improve the cycle performance of the lithium ion battery anode material; in addition, the coating layer has high chemical stability, and can improve the safety performance of the lithium ion battery cathode material.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of the positive electrode material of the lithium ion battery prepared in example 1 of the present invention.
Fig. 2 is a scanning electron microscope image of the lithium ion battery cathode material prepared in example 2 of the present invention.
Fig. 3 is a Transmission Electron Microscope (TEM) image of the positive electrode material of the lithium ion battery prepared in example 1 of the present invention.
Fig. 4 is a scanning electron micrograph of the positive electrode material for the lithium ion battery prepared in comparative example 1 of the present invention.
Detailed Description
The following describes embodiments of the present invention in detail. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
It should be noted that the terms "first", "second", "third" and "fourth" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, features defined as "first", "second", "third", "fourth" may explicitly or implicitly include one or more of the features. Further, in the description of the present invention, "a plurality" means two or more unless otherwise specified.
One aspect of the present invention provides a lithium ion battery cathode material, which includes a core layer and a cladding layer formed on a surface of the core layer. The core layer comprises a high nickel lithium cathode material with a chemical formula of LiaNibCocMndAleMfO2Wherein a is more than or equal to 0.95 and less than or equal to 1.05, b is more than or equal to 0.8 and less than or equal to 0.95, c is more than or equal to 0.01 and less than or equal to 0.15, d is more than or equal to 0 and less than or equal to 0.1, e is more than or equal to 0 and less than or equal to 0.05, f is more than or equal to 0 and less than or equal to 0.02, b + c + d + e + f is more than or equal to 0 and less than or equal to 1, and M is one. The coating layer comprises a boron-containing lithium ion conductor with a chemical formula of LixByM’(1-y)OzWherein M' is one or more of W, Mo, Se and P, x is more than or equal to 0.1 and less than or equal to 1.5, and y is more than or equal to 0.1 and less than or equal to 1<Z is more than or equal to 1 and 1.5 and less than or equal to 2.5. Preferably, 0.82 ≦ b ≦ 0.90, 0.06 ≦ c ≦ 0.12, 0.02 ≦ d ≦ 0.08, and M' is one or more of W and Mo.
In some embodiments of the present invention, the ratio of the number of moles of boron-containing lithium ion conductor in the cladding layer to the number of moles of high nickel lithium positive electrode material in the core layer is defined as 0<Less than or equal to 0.03. Namely, the lithium ion battery positive electrode materialCan be represented by LiaNibCocMndAleMfO2·LixByM’(1-y)Oz. By limiting the range of the value, the situation that the complete coating cannot be formed due to too small amount of the boron-containing lithium ion conductor in the coating layer is avoided, and the situation that the migration speed of lithium ions in the coating layer is reduced due to too thick coating layer due to too much amount of the boron-containing lithium ion conductor is avoided.
In some embodiments of the present invention, the boron-containing lithium ion conductor in the cladding layer is a glassy lithium ion conductor, and a glass film with lithium ion selective passing capacity is formed on the surface of the core layer. Wherein, M' is selected from W, Mo, Se or P, and the four elements can form lithium metal glass, and the doping of the elements can improve the thermal stability of the material. Further, W, Mo element has a high lithium ion conductivity, and P element is advantageous for penetrating into crystal lattice and blocking electrolyte components (such as LiF)6) Decomposition and good Se element stability.
The core layer of the lithium ion battery anode material provided by the invention is a high nickel lithium anode material (Ni is more than or equal to 80%), and the surface of the lithium ion battery anode material is coated with a boron-containing lithium ion conductor (coated lithium ion battery anode material). Due to Ni2+And Li+Are relatively close in radius, Ni2+And Li+Therefore, the stability of the core layer material structure is improved by introducing Mn, Al, M and other elements, and capacity loss and structural damage to a certain degree caused by cation mixed discharge are avoided.
Moreover, the boron-containing lithium ion conductor in the coating layer is in a lithium-deficient state, so that additional lithium insertion vacancies can be provided, the first efficiency of the lithium ion cathode material can be improved, and the first discharge capacity can be improved. And secondly, the coating layer has good compactness, can effectively isolate the electrolyte from the core layer, prevents the electrolyte from directly contacting with the core layer, slows down the corrosion of the electrolyte to the core layer, and improves the cycle performance of the lithium ion battery anode material. In addition, the coating layer has high chemical stability, and can improve the safety performance of the lithium ion battery cathode material.
The invention also provides a preparation method of the lithium ion battery anode material, which comprises the following steps:
step one, preparing a core layer: and (3) mixing a lithium source, a nickel-cobalt-containing composite hydroxide and an oxide of M, stirring, sintering and dispersing to obtain the core layer sintering material. M is one or more of W, Mo, Zr, Nb, Y, Sr and the like.
Wherein the lithium source, the nickel-cobalt-containing composite hydroxide and the M oxide are proportioned according to the molar ratio of each metal element of the high-nickel-lithium cathode material in the core layer, and the lithium element is excessive. The chemical formula of the high nickel-lithium cathode material is LiaNibCocMndAleMfO2Wherein a is more than or equal to 0.95 and less than or equal to 1.05, b is more than or equal to 0.8 and less than or equal to 0.95, c is more than or equal to 0.01 and less than or equal to 0.15, d is more than or equal to 0 and less than or equal to 0.1, e is more than or equal to 0 and less than or equal to 0.05, f is more than or equal to 0 and less than or equal to 0.02, and b + c + d +. Preferably, 0.82 < b < 0.90, 0.06 < c < 0.12 and 0.02 < d < 0.08.
In some embodiments of the invention, the lithium source is lithium hydroxide, preferably lithium hydroxide monohydrate (LiOH. H)2O)。
In some embodiments of the invention, the stirring is performed in a high-speed mixing device, the stirring speed is 500rpm to 800rpm, and the stirring time is 10 min to 30 min.
In some embodiments of the present invention, the sintering temperature is 750-800 ℃ and the sintering time is 10-25 h.
Step two, surface coating: washing the sintering material with water, and mixing the washed sintering material with boric acid (H)3BO3) And mixing the compounds of M', stirring, and carrying out constant temperature reaction to form the coating layer on the surface of the sintering material, thereby obtaining the lithium ion battery anode material.
Wherein the sintering material, the boric acid and the compound of M' are mixed in a proportion that Li in the lithium ion battery cathode materialaNibCocMndAleMfO2·LixByM’(1-y)OzX is more than or equal to 0.1 and less than or equal to 1.5, and y is more than or equal to 0.1 and less than or equal to 1<1，1.5≤z≤2.5，0<≤0.03。
The chemical formula of the coating layer is LixByM’(1-y)OzWherein M' is one or more of W, Mo, Se and P, x is more than or equal to 0.1 and less than or equal to 1.5, and y is more than or equal to 0.1 and less than or equal to 1<1，1.5≤z≤2.5。
In some embodiments of the invention, M ' is one or more of W and Mo, and when M ' is W, the compound of M ' corresponds to ammonium metatungstate (H)28N6O41W12) When M 'is Mo, the compound of M' corresponds to ammonium molybdate (H)8MoN2O4). The weight ratio of the sintering material to the boric acid to the ammonium metatungstate/ammonium molybdate is 100 (0.4-0.5) to (0.3-0.4).
In some embodiments of the invention, the stirring is performed in a high-speed mixing device, the stirring speed is 600-800 rpm, and the stirring time is 15 min.
In some embodiments of the present invention, the isothermal reaction is performed in an atmosphere sintering furnace, the atmosphere of the isothermal reaction is an oxygen atmosphere, the time of the isothermal reaction is 5 to 12 hours, and the temperature of the isothermal reaction is above 250 ℃, preferably 250 ℃ to 350 ℃.
In some embodiments of the invention, the cladding comprises a glassy lithium ion conductor, of the type Li2O-B2O3-LiM' O phase structure. Because the core layer is a high-nickel lithium anode material and more lithium is remained on the surface, the coating material capable of reacting with lithium is added, the temperature is heated to more than 250 ℃ by utilizing the characteristic that the coating layer is in a glass state, the coating material can be converted into a molten state and uniformly covered on the surface of the core layer and fully reacts with the lithium remained on the surface, and the Li content is reduced2O、LiOH、Li2CO3Etc. form of residual lithium. Moreover, the coating method has the following advantages: 1) the coating is in a glass state and is uniformly coated; 2) the core layer and the electrolyte are effectively isolated, and the cycle performance of the lithium ion battery anode material is improved; 3) the coating layer provides additional lithium insertion vacant sites, and the lithium ion battery anode material can be improvedThe first efficiency of the material; 4) the coating layer has high chemical stability, and can improve the safety performance of the lithium ion battery anode material.
The invention also provides a lithium ion battery, which comprises a pole piece, a lithium piece and electrolyte, wherein the pole piece is prepared from the lithium ion battery anode material, the binder and the conductive agent, and the capacity retention rate of the lithium ion battery can reach more than 94% after 50 cycles at 0.5 ℃.
The scheme of the invention will be explained with reference to the examples. It will be appreciated by persons skilled in the art that the following examples are illustrative only and are not to be construed as limiting the invention. Reagents, software and equipment not specifically submitted to the following examples are conventional commercial products or open sources unless otherwise submitted.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Example 1
Lithium hydroxide monohydrate, precursor (Ni)0.82Co0.12Mn0.06)(OH)2And the zirconium oxide is prepared according to the element molar ratio Li (Ni + Co + Mn) and Zr (1.03: 1: 0.004), placed in high-speed mixing equipment, stirred for 15min at 500rpm and uniformly discharged. And placing the mixed materials in an atmosphere sintering furnace, heating to 800 ℃ in an oxygen atmosphere, sintering for 20 hours, and dispersing to obtain the core layer sintering material. The chemical formula of the sintering material is Li (Ni) due to partial lithium volatilization0.82Co0.12Mn0.06)Zr0.004O2。
Washing the sintering material with water, and then mixing with boric acid and ammonium metatungstateProportioning according to the weight ratio of 100:0.5:0.4, placing the mixture into high-speed mixing equipment, stirring the mixture for 15min at 600rpm, placing the mixed material into an atmosphere sintering furnace, heating the mixed material to 350 ℃ under the oxygen atmosphere, and preserving the heat for 6 hours. The final product formed has the formula Li (Ni)0.82Co0.12Mn0.06)0.996Zr0.004O2·0.010Li0.4B0.80W0.20O2. That is, example 1 is a sample coated with Li-B-W-O on the surface.
Example 2
Lithium hydroxide monohydrate, precursor (Ni)0.82Co0.12Mn0.06)(OH)2And the zirconium oxide is prepared according to the element molar ratio Li (Ni + Co + Mn) and Zr (1.03: 1: 0.004), placed in high-speed mixing equipment, stirred for 15min at 500rpm and uniformly discharged. And placing the mixed materials in an atmosphere sintering furnace, heating to 800 ℃ in an oxygen atmosphere, sintering for 20 hours, and dispersing to obtain the core layer sintering material. The chemical formula of the sintering material is Li (Ni)0.82Co0.12Mn0.06)Zr0.004O2。
Washing the sintering material with water, then mixing the sintering material with boric acid and ammonium molybdate according to the weight ratio of 100:0.5:0.4, placing the mixture in high-speed mixing equipment, stirring the mixture for 15min at 600rpm, placing the mixed material in an atmosphere sintering furnace, heating the mixed material to 350 ℃ in an oxygen atmosphere, and preserving the temperature for 6 hours. The final product formed has the formula Li (Ni)0.82Co0.12Mn0.06)0.996Zr0.004O2·0.010Li0.4B0.80Mo0.20O2. That is, example 2 is a sample coated with Li-B-Mo-O on the surface.
Example 3
Lithium hydroxide monohydrate, precursor (Ni)0.88Co0.08Mn0.02Al0.02)(OH)2The materials are mixed according to the element molar ratio Li (Ni + Co + Mn + Al) of 1.04:1, placed in high-speed mixing equipment, stirred at 700rpm for 15min, and uniformly discharged. Placing the mixed materials in an atmosphere sintering furnace, heating to 800 ℃ in an oxygen atmosphere, sintering for 20 hours, and then dispersing to obtain nucleiAnd (4) sintering the core layer. The chemical formula of the sintering material is Li (Ni)0.88Co0.08Mn0.02Al0.02)O2。
Washing the sintering material with water, then mixing the sintering material with boric acid and ammonium metatungstate according to the weight ratio of 100:0.4:0.3, placing the mixture into high-speed mixing equipment, stirring the mixture for 15min at 800rpm, placing the mixed material into an atmosphere sintering furnace, heating the mixed material to 400 ℃ in an oxygen atmosphere, preserving the temperature for 6 hours, and finally obtaining a product with the chemical formula of LiNi0.88Co0.08Mn0.02Al0.02O2·0.008Li0.52B0.84W0.16O2. That is, example 3 is a sample coated with Li-B-W-O on the surface.
Example 4
A sintered material was prepared according to the same procedure as in example 3.
Washing the sintering material with water, then mixing the sintering material with boric acid and ammonium molybdate according to the weight ratio of 100:0.4:0.25, placing the mixture in high-speed mixing equipment, stirring the mixture for 15min at 800rpm, placing the mixed material in an atmosphere sintering furnace, heating the mixed material to 400 ℃ in an oxygen atmosphere, and preserving the temperature for 6 hours. Formation of the product LiNi0.88Co0.08Mn0.02Al0.02O2·0.008Li0.52B0.84Mo0.16O2. That is, example 4 is a sample coated with Li-B-Mo-O on the surface.
Comparative example 1
A sintered material was prepared according to the same procedure as in example 1.
Treating the sintered material in 30-DEG C salt-free water for 30min to remove residual lithium on the surface, drying, placing in an atmosphere sintering furnace, heating to 350℃ in oxygen atmosphere, and keeping the temperature for 6 h to finally form a product with the chemical formula of Li (Ni)0.82Co0.12Mn0.06)0.996Zr0.004O2. That is, comparative example 1 is a sample whose surface is not coated.
Comparative example 2
A sintered material was prepared according to the same procedure as in example 3.
Treating the sintered material in 15-degree salt-free water for 15min to remove the surface residuesDrying lithium, placing the dried lithium in an atmosphere sintering furnace, heating the lithium to 400 ℃ in an oxygen atmosphere, and preserving the temperature for 6 hours to finally form a product with a chemical formula of LiNi0.88Co0.08Mn0.02Al0.02O2. That is, comparative example 2 is a sample whose surface is not coated.
Comparative example 3
A sintered material was prepared according to the same procedure as in example 3.
Washing the sintering material with water, then mixing the sintering material with boric acid according to the weight ratio of 100:0.5, placing the mixture into high-speed mixing equipment, stirring the mixture for 15min at 800rpm, placing the mixed material into an atmosphere sintering furnace, heating the mixed material to 400 ℃ in an oxygen atmosphere, and preserving the heat for 6 hours. The final product formed is of the formula LiNi0.88Co0.08Mn0.02Al0.02O2·0.008Li0.5BO1.75. That is, comparative example 3 is a sample whose surface is coated with Li-B-O.
Scanning electron microscope tests are performed on the lithium ion battery positive electrode materials prepared in the embodiment 1, the embodiment 2 and the comparative example 1, and as shown in fig. 1, fig. 2 and fig. 4, the lithium ion battery positive electrode material is granular in shape and has a particle size of approximately 10 micrometers. The lithium ion battery cathode material prepared in example 1 was subjected to a transmission electron microscope test, and as shown in fig. 3, a uniform and distinct coating layer was formed on the surface of the lithium ion battery cathode material, and the interplanar spacing of the coating layer was 13.75 nm.
The lithium ion battery positive electrode materials prepared in examples 1-4 and comparative examples 1-3, the binder and the conductive agent are respectively prepared into a pole piece, and then the pole piece is assembled with the diaphragm paper, the lithium piece and the electrolyte into the button cell in an argon cycle glove box. The charge and discharge capacity and the charge and discharge cycle performance were measured on the novice battery tester, and the results are shown in table 1.
Table 1 electrical property test results
Figure BDA0002051435790000101
The data in table 1 show that the first efficiency of the lithium ion battery cathode materials of examples 1 to 4 is higher than that of comparative examples 1 to 3, and the capacity retention rate of the lithium ion battery cathode materials of examples 1 to 4 after 50 cycles is higher than that of comparative examples 1 to 3, which indicates that the coating layer on the surface of the lithium ion battery cathode material can improve the first efficiency and the charge-discharge cycle performance. The lithium ion battery positive electrode materials of examples 3 to 4 have high charge and discharge capacities. From the DSC 1 st exothermic peak temperature, the DSC first exothermic peak temperature of comparative example 3 (sample coated with Li-B-O) is the same as that of comparative example 2 (sample uncoated on the surface), while the DSC first exothermic peak temperature of example 3 (sample coated with Li-B-W-O) is relatively high, representing better safety performance.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention.

Claims (10)

1. A lithium ion battery positive electrode material comprising:
a core layer comprising a high nickel lithium positive electrode material of formula LiaNibCocMndAleMfO2Wherein a is more than or equal to 0.95 and less than or equal to 1.05, b is more than or equal to 0.8 and less than or equal to 0.95, c is more than or equal to 0.01 and less than or equal to 0.15, d is more than or equal to 0 and less than or equal to 0.1, e is more than or equal to 0 and less than or equal to 0.05, f is more than or equal to 0 and less than or equal to 0.02, b + c + d + e + f is more than or equal to 0 and less than or equal to 1, and M;
a cladding layer formed on the surface of the core layer, the cladding layer including a boron-containing lithium ion conductor of chemical formula LixByM’(1-y)OzWherein M' is one or more of W, Mo, Se and P, x is more than or equal to 0.1 and less than or equal to 1.5, and y is more than or equal to 0.1 and less than or equal to 1<Z is more than or equal to 1, 1.5 and less than or equal to 2.5, and the boron-containing lithium ion conductor in the coating layer is a glassy state lithium ion conductor.
2. The positive electrode material for a lithium ion battery according to claim 1, wherein the ratio of the number of moles of the boron-containing lithium ion conductor in the clad layer to the number of moles of the high nickel lithium positive electrode material in the core layer is defined as 0< ≦ 0.03.
3. The positive electrode material for a lithium ion battery according to claim 1, wherein b is 0.82. ltoreq. b.ltoreq.0.90, c is 0.06. ltoreq. c.ltoreq.0.12, and d is 0.02. ltoreq. d.ltoreq.0.08.
4. The positive electrode material for a lithium ion battery according to claim 1, wherein M' is one or more of W and Mo.
5. The method for preparing the positive electrode material of the lithium ion battery according to claim 1, comprising the steps of:
preparing a core layer: mixing a lithium source, a composite hydroxide and an oxide of M, stirring, sintering and dispersing to obtain a core layer sintering material, wherein the composite hydroxide comprises multiple of nickel, cobalt, manganese and aluminum, at least two of the multiple are nickel and cobalt, and M is one or more of W, Mo, Zr, Nb, Y and Sr; and
surface coating: and washing the sintering material with water, mixing the washed sintering material with boric acid and a compound of M ', wherein M' is one or more of W, Mo, Se and P, stirring, and carrying out a constant-temperature reaction, so as to form the coating layer on the surface of the sintering material, thereby obtaining the lithium ion battery anode material.
6. The method for preparing the positive electrode material of the lithium ion battery according to claim 5, wherein in the step of preparing the core layer, the stirring is performed in a high-speed mixing device, the stirring speed is 500rpm to 800rpm, and the time is 10 min to 30 min; in the surface coating step, the stirring is carried out in high-speed mixing equipment, the stirring speed is 600-800 rpm, and the stirring time is 15 min.
7. The method for preparing the positive electrode material of the lithium ion battery as claimed in claim 5, wherein the sintering temperature is 750-800 ℃ and the time is 10-25 h.
8. The method for preparing the positive electrode material of the lithium ion battery according to claim 5, wherein M ' is one or more of W and Mo, when M ' is W, the compound of M ' is ammonium metatungstate, when M ' is Mo, the compound of M ' is ammonium molybdate, and the weight ratio of the sintering material, the boric acid and the ammonium metatungstate/ammonium molybdate is 100 (0.4-0.5) to (0.3-0.4).
9. The method for preparing the positive electrode material of the lithium ion battery according to claim 5, wherein the isothermal reaction is performed in an atmosphere sintering furnace, the atmosphere of the isothermal reaction is an oxygen atmosphere, the time of the isothermal reaction is 5 to 12 hours, and the temperature of the isothermal reaction is 250 ℃ or higher.
10. A lithium ion battery, characterized by comprising a pole piece made of the lithium ion battery positive electrode material of any one of claims 1 to 4, a binder and a conductive agent.
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