CN110518209B - Preparation method of anode material and prepared anode material - Google Patents

Preparation method of anode material and prepared anode material Download PDF

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CN110518209B
CN110518209B CN201910798461.0A CN201910798461A CN110518209B CN 110518209 B CN110518209 B CN 110518209B CN 201910798461 A CN201910798461 A CN 201910798461A CN 110518209 B CN110518209 B CN 110518209B
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lithium
cobalt
oxide
nickel
sintering
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刘玉红
廖钦林
董明月
周源
罗继华
叶浩杰
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Guangdong Fenghua New Energy Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention provides a preparation method of a positive electrode material, which comprises the following steps: A. mixing and sintering a first lithium source and a doped cobalt source to obtain a material A; B. mixing a second lithium source, a nickel-manganese-cobalt ternary precursor and nickel oxide, and sintering to obtain a material B; C. mixing and sintering the material A, the material B and the coating agent; wherein, the doping elements doping the cobalt source comprise Sb and at least one of Mg, Al, Ti and Zr, and the cladding agent comprises nickel oxide and at least one of aluminum oxide, lanthanum oxide and yttrium oxide. The cathode material prepared by the preparation method of the cathode material has the advantages of high specific capacity, good cycle performance, small expansion rate of high-temperature storage thickness, high energy density and the like, and can meet the requirement of the market on the cathode material for the high-capacity and high-performance lithium ion battery.

Description

Preparation method of anode material and prepared anode material
Technical Field
The invention relates to the technical field of preparation of anode materials, in particular to a preparation method of an anode material and the anode material prepared by the same.
Background
Lithium ion batteries have been widely used in small portable electrical appliances such as notebook computers, mobile phones, camcorders and the like, various 3C electronic products are developed in a direction of being lighter and thinner, the 3C products are updated more and more frequently, and the development of lithium ion battery anode materials with higher energy density, better cycle performance and lower cost is a pursued target in the lithium battery industry.
The positive electrode material for the lithium ion battery plays a role in determining the overall performance and the cost performance of the lithium ion battery. The anode material adopted by the current 3C battery product is mainly high-voltage lithium cobaltate anode material, and a mixed anode material adopting a high-voltage ternary material to replace part of the high-voltage lithium cobaltate material is also available. However, as the charge cut-off voltage increases, a large amount of Li is extracted from the positive electrode material during charging+Then, the layered structure of the positive electrode material collapses, thereby deteriorating the cycle performance of the material. In view of the problems of the conventional positive electrode material, such as easy collapse of the layered structure and deterioration of the cycle performance, a high-performance positive electrode material for a lithium ion battery needs to be developed.
Disclosure of Invention
The invention aims to provide a preparation method of a positive electrode material and the prepared positive electrode material, so as to solve the problems that a lithium battery prepared from the conventional positive electrode material is easy to collapse in a laminated structure, worsens in cycle performance and the like.
The technical scheme of the invention is as follows:
the invention provides a preparation method of a positive electrode material, which comprises the following steps:
A. mixing and sintering a first lithium source and a doped cobalt source to obtain a material A;
B. mixing a second lithium source, a nickel-manganese-cobalt ternary precursor and nickel oxide, and sintering to obtain a material B;
C. mixing and sintering the material A, the material B and the coating agent;
wherein, the doping elements doping the cobalt source comprise Sb and at least one of Mg, Al, Ti and Zr, and the cladding agent comprises nickel oxide and at least one of aluminum oxide, lanthanum oxide and yttrium oxide.
The invention also provides the anode material prepared by the preparation method of the anode material.
In the step A, at least one of Mg, Al, Ti or Zr and a Sb-doped cobalt source are used, and doping elements can be well distributed in the cobalt source by doping, so that the doping elements can be more uniformly distributed in a lithium cobaltate crystal structure when synthesizing lithium cobaltate, the interlayer spacing of a layered structure of the doped lithium cobaltate material is increased, the intercalation/deintercalation of lithium ions is facilitated, the diffusion coefficient of the lithium ions in the material is improved, and the mass specific capacity of the material is facilitated to be improved; the structural stability of the lithium cobaltate material in the process of lithium ion intercalation/deintercalation is improved, so that the safety performance and the long-term cycle performance of the material are effectively improved; in the step B, nickel oxide is added to enable Ni element to carry out bulk phase doping, so that the specific capacity of the material can be improved, the impedance of the material can be properly improved, Ni enters a Li layer to play a supporting role, Li desorption/insertion is facilitated, and the cycle performance is improved; in the step C, nickel oxide is added for surface coating, the nickel oxide can react with redundant lithium on the surface of the material to reduce the alkalinity of the surface of the material, and the Al, Ga or Y element is added to prevent the structure from collapsing under the condition of high voltage and improve the cycle performance. In the preparation method of the cathode material, the cobalt source is doped in the step A, the nickel oxide is doped in the step B and the coating agent is added in the step C, the three processing methods are mutually matched, the doping substance and the coating agent are mutually promoted to play a role together, the prepared cathode material has the advantages of high specific capacity, good cycle performance, small high-temperature storage thickness expansion rate, high energy density and the like, and the requirement of the market on the cathode material for the high-capacity and high-performance lithium ion battery can be met.
Detailed Description
The invention provides a preparation method of a positive electrode material and a positive electrode material prepared by the preparation method, and the preparation method of the positive electrode material and the positive electrode material prepared by the preparation method are explained in more detail below.
A preparation method of a positive electrode material comprises the following steps:
A. mixing and sintering a first lithium source and a doped cobalt source to obtain a material A;
B. mixing a second lithium source, a nickel-manganese-cobalt ternary precursor and nickel oxide, and sintering to obtain a material B;
C. mixing and sintering the material A, the material B and the coating agent;
wherein, the doping elements of the doped cobalt source comprise Sb and at least one of Mg, Al, Ti and Zr, and the cladding agent comprises nickel oxide and at least one of aluminum oxide, lanthanum oxide and yttrium oxide.
It should be noted that, the step a and the step B are not sequentially divided, the doping of the cobalt source may be mixing a doping element with the cobalt source, sintering at 750-920 ℃ for 1-2h after ball milling, the doping element of the cobalt source may be Mg and Sb, Al and Sb, Ti and Sb, Zr and Sb or Mg, Al, Ti and Sb, the cladding agent may be alumina and nickel oxide, lanthanum oxide and nickel oxide, yttrium oxide and nickel oxide or alumina, lanthanum oxide and nickel oxide, and the proportion of nickel, manganese and cobalt in the nickel, manganese and cobalt ternary precursor may be 424, 333, 523, 701 or 515.
Preferably, the step A also comprises grinding the material A to obtain a powder with the particle size D50 of 10-25 μm; and step B, grinding the material B to obtain the material D50 with the particle size of 3-8 μm. The material A with larger particles and the material B with smaller particles are mixed according to a certain proportion, so that the pole piece compaction density of the anode material can be improved, the advantages of the anode material and the cathode material can be highlighted, and the anode material has higher specific capacity, better cycle performance and lower cost. Specifically, the A material is pulverized to obtain particle sizes D50 of 10 μm, 15 μm and 25 μm, and the B material is pulverized to obtain particle sizes D50 of 3 μm, 4 μm and 8 μm.
Preferably, in step A, the cobalt source includes but is not limited to one or more of cobaltosic oxide, cobalt hydroxide and cobalt hydroxide, the molar ratio of Li to Co is 1.03-1.2, and the sintering temperature is 950-1100 ℃. The cobalt source is preferably one or a mixture of more of tricobalt tetraoxide, cobalt hydroxide and cobalt hydroxide, but the choice of cobalt source is not limited to these materials. Specifically, the molar ratio of Li to Co may be 1.03, 1.07, or 1.2, and the sintering temperature may be 950 ℃, 1000 ℃, or 1100 ℃.
Preferably, in the step A, the doping amount of Sb is 0.02-0.5% of the mole number of Co, and the doping amount of one or more of Mg, Al, Ti and Zr is 0.02-0.5% of the mole number of Co. Specifically, the doping amount of Sb is 0.02%, 0.2%, 0.3%, or 0.5% of the mole number of Co, and the doping amount of one or more of Mg, Al, Ti, and Zr is 0.02%, 0.2%, 0.3%, or 0.5% of the mole number of Co.
Preferably, in the step B, the molar ratio of Li to (Ni + Co + Mn) is 1.03-1.2, and the nickel oxide accounts for 3-7% of the weight of the nickel-cobalt-manganese ternary precursor. The nickel oxide is preferably nano-scale, specifically, the molar ratio of Li to (Ni + Co + Mn) can be 1.03, 1.1 or 1.2, and the nickel oxide accounts for 3%, 4% or 7% of the weight of the nickel-cobalt-manganese ternary precursor.
Preferably, in the step C, the weight ratio of the material A to the material B is (60-90): (40-10), and the sintering temperature is 800-950 ℃. Specifically, the weight ratio of the material A to the material B can be 60:40, 90:10, 90:40 or 60:10, and the like, and the sintering temperature can be 800 ℃, 880 ℃ or 950 DEG C
Preferably, in the step C, the weight ratio of the coating agent to the material A is 0.05-1%, and the sintering temperature is 850-. Specifically, the weight ratio of the coating agent to the material A can be 0.05%, 0.8% or 1%, and the sintering temperature can be 850 ℃, 900 ℃ or 950 ℃.
Preferably, the first lithium source is selected from one or more of lithium carbonate, lithium fluoride, lithium hydroxide and lithium acetate, and the second lithium source is selected from one or more of lithium carbonate, lithium fluoride, lithium hydroxide and lithium acetate. The first lithium source and the second lithium source may be selected to be the same or different, and the selection of the first lithium source and the second lithium source is not limited to these materials.
Preferably, the step C treatment further comprises a crushing and screening treatment.
The cathode material prepared by the preparation method of the cathode material.
In order to make the objects, technical solutions and effects of the present invention clearer and clearer, the present invention is described in further detail below with reference to examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A preparation method of a positive electrode material comprises the following steps:
A. doping Sb and Zr with cobaltosic oxide, mixing the Sb and Zr with lithium carbonate, and sintering to obtain a material A;
B. mixing and sintering lithium carbonate, a nickel-manganese-cobalt ternary precursor and nickel oxide to obtain a material B;
C. mixing the material A, the material B, yttrium oxide and nickel oxide, and sintering.
Example 2
A preparation method of a positive electrode material comprises the following steps:
A. doping Sb and Mg with cobaltosic oxide, uniformly mixing the Sb and Mg with lithium carbonate, sintering the mixture at 1030 ℃ for 2 hours, cooling the mixture, and performing ball milling on the mixture to obtain a material A with the particle size D50 of 25 mu m;
B. uniformly mixing a ternary precursor of lithium carbonate, nickel manganese cobalt (523) and nano nickel oxide, sintering at 900 ℃ for 10 hours, cooling, and ball-milling to obtain a material B with the particle size D50 of 8 mu m;
C. uniformly mixing the material A, the material B, nickel oxide and aluminum oxide, preserving heat for 8 hours at the temperature of 900 ℃, cooling, crushing and screening;
in the step A, the doping amounts of Sb and Mg are respectively 0.1 percent and 0.15 percent of the mole number of Co, and the cobaltosic oxide raw material is mixed according to the molar ratio of Li to Co of 1.05; in the step B, lithium carbonate, a nickel-cobalt-manganese (523) ternary precursor and a nano nickel oxide raw material are mixed according to the molar ratio of Li to (Ni + Co + Mn) of 1.05, wherein the weight of the nickel oxide accounts for 5% of that of the nickel-cobalt-manganese (523) ternary precursor; in the step C, the weight ratio of the material A to the material B is 80:20, and the weight ratio of the coating agent to the material A is 1%.
Example 3
A preparation method of a positive electrode material comprises the following steps:
A. doping Sb, Al and Mg with hydroxyl cobalt, uniformly mixing with lithium hydroxide, sintering at 950 ℃ for 2.5h, cooling, and ball-milling into a material A with the particle size D50 of 20 mu m;
B. uniformly mixing a ternary precursor of lithium hydroxide, nickel manganese cobalt (523) and nano nickel oxide, sintering at 900 ℃ for 10 hours, cooling, and ball-milling to obtain a material B with the particle size D50 of 5 mu m;
C. uniformly mixing the material A, the material B, nickel oxide and aluminum oxide, preserving heat for 6 hours at 950 ℃, cooling, crushing and screening;
in the step A, the doping amount of Sb is 0.5 percent of the mole number of Co, the doping amounts of Al and Mg are 0.5 percent of the mole number of Co, and the hydroxy cobalt raw material is prepared according to the molar ratio of Li to Co of 1.2; in the step B, the lithium hydroxide, the nickel-cobalt-manganese (523) ternary precursor and the nano nickel oxide raw material are mixed according to the molar ratio of Li to (Ni + Co + Mn) of 1.2, wherein the weight of the nickel oxide accounts for 7 percent of that of the nickel-cobalt-manganese (523) ternary precursor; in the step C, the weight ratio of the material A to the material B is 90:10, and the weight ratio of the coating agent to the material A is 0.05%.
Example 4
A preparation method of a positive electrode material comprises the following steps:
A. doping Sb and Zr with cobaltosic oxide, uniformly mixing the Sb and Zr with lithium carbonate, sintering the mixture at 1000 ℃ for 2 hours, cooling the mixture, and performing ball milling on the cooled mixture to obtain a material A with the particle size D50 of 20 mu m;
B. uniformly mixing a ternary precursor of lithium carbonate, nickel manganese cobalt (523) and nano nickel oxide, sintering at 900 ℃ for 10 hours, cooling, and ball-milling to obtain a material B with the particle size D50 of 5 mu m;
C. uniformly mixing the material A, the material B, nickel oxide and lanthanum oxide, preserving heat for 6 hours at the temperature of 900 ℃, cooling, crushing and screening;
in the step A, the doping amount of Sb is 0.3 percent of the mole number of Co, the doping amount of Zr is 0.4 percent of the mole number of Co, and the cobaltosic oxide raw material is mixed according to the mole ratio of Li to Co of 1.08; in the step B, lithium carbonate, a nickel-cobalt-manganese (523) ternary precursor and a nano nickel oxide raw material are mixed according to the molar ratio of Li to (Ni + Co + Mn) of 1.15, wherein the weight of the nickel oxide accounts for 6% of that of the nickel-cobalt-manganese (523) ternary precursor; in the step C, the weight ratio of the material A to the material B is 90:20, and the weight ratio of the coating agent to the material A is 0.08%.
Example 5
A preparation method of a positive electrode material comprises the following steps:
A. doping Sb and Ti with cobalt hydroxide, mixing the mixture with lithium fluoride uniformly, sintering the mixture at 1100 ℃ for 2 hours, cooling the mixture, and performing ball milling on the cooled mixture to obtain a material A with the particle size D50 of 10 mu m;
B. uniformly mixing a ternary precursor of lithium carbonate, nickel manganese cobalt (523) and nano nickel oxide, sintering at 800 ℃ for 11 hours, cooling, and ball-milling to obtain a material B with the particle size D50 of 3 mu m;
C. uniformly mixing the material A, the material B, nickel oxide and yttrium oxide, preserving the heat for 8 hours at the temperature of 800 ℃, cooling, crushing and screening;
in the step A, the doping amount of Sb is 0.02 percent of the mole number of Co, the doping amount of Ti is 0.02 percent of the mole number of Co, and cobalt hydroxide raw materials are mixed according to the mole ratio of Li to Co of 1.03; in the step B, lithium carbonate, a nickel-cobalt-manganese (523) ternary precursor and a nano nickel oxide raw material are mixed according to the molar ratio of Li to (Ni + Co + Mn) of 1.03, wherein the weight of the nickel oxide accounts for 3% of that of the nickel-cobalt-manganese (523) ternary precursor; in the step C, the weight ratio of the material A to the material B is 60:40, and the weight ratio of the coating agent to the material A is 1%.
Example 6
A preparation method of a positive electrode material comprises the following steps:
A. doping Sb, Mg, Al, Ti and Zr with cobaltosic oxide, uniformly mixing with lithium acetate, sintering at 950 ℃ for 3h, cooling, and ball-milling into a material A with the particle size D50 of 15 mu m;
B. uniformly mixing a ternary precursor of lithium carbonate, nickel manganese cobalt (523) and nano nickel oxide, sintering at 850 ℃ for 10h, cooling, and ball-milling to obtain a material B with the particle size D50 of 7 mu m;
C. uniformly mixing the material A, the material B, nickel oxide, aluminum oxide, lanthanum oxide and yttrium oxide, preserving heat for 6 hours at 950 ℃, cooling, crushing and screening;
in the step A, the doping amount of Sb is 0.2 percent of the mole number of Co, the doping amounts of Mg, Al, Ti and Zr are 0.3 percent of the mole number of Co, and the cobaltosic oxide raw material is prepared according to the mole ratio of Li to Co of 1.1; in the step B, lithium carbonate, a nickel-cobalt-manganese (523) ternary precursor and a nano nickel oxide raw material are mixed according to the molar ratio of Li to (Ni + Co + Mn) of 1.1, wherein the weight of the nickel oxide accounts for 5% of that of the nickel-cobalt-manganese (523) ternary precursor; in the step C, the weight ratio of the material A to the material B is 70:40, and the weight ratio of the coating agent to the material A is 1%.
Comparative example 1
A preparation method of a positive electrode material comprises the following steps:
A. uniformly mixing cobaltosic oxide with lithium carbonate, sintering at 1030 ℃ for 2h, cooling, and ball-milling to obtain a material A with the particle size D50 of 25 mu m;
B. uniformly mixing a ternary precursor of lithium carbonate, nickel manganese cobalt (523) and nano nickel oxide, sintering at 900 ℃ for 10 hours, cooling, and ball-milling to obtain a material B with the particle size D50 of 8 mu m;
C. uniformly mixing the material A, the material B, nickel oxide and aluminum oxide, preserving heat for 8 hours at the temperature of 900 ℃, cooling, crushing and screening;
wherein, in the step A, the cobaltosic oxide raw material is mixed according to the molar ratio of Li to Co of 1.05; in the step B, lithium carbonate, a nickel-cobalt-manganese (523) ternary precursor and a nano nickel oxide raw material are mixed according to the molar ratio of Li to (Ni + Co + Mn) of 1.05, wherein the weight of the nickel oxide accounts for 5% of that of the nickel-cobalt-manganese (523) ternary precursor; in the step C, the weight ratio of the material A to the material B is 80:20, and the weight ratio of the coating agent to the material A is 1%.
Comparative example 2
A preparation method of a positive electrode material comprises the following steps:
A. doping Sb and Mg with cobaltosic oxide, uniformly mixing the Sb and Mg with lithium carbonate, sintering the mixture at 1030 ℃ for 2 hours, cooling the mixture, and performing ball milling on the mixture to obtain a material A with the particle size D50 of 25 mu m;
B. uniformly mixing lithium carbonate and a ternary nickel manganese cobalt (523) precursor, sintering at 900 ℃ for 10 hours, cooling, and ball-milling to obtain a material B with the particle size D50 of 8 mu m;
C. uniformly mixing the material A, the material B, nickel oxide and aluminum oxide, preserving heat for 8 hours at the temperature of 900 ℃, cooling, crushing and screening;
in the step A, the doping amounts of Sb and Mg are respectively 0.1 percent and 0.15 percent of the mole number of Co, and the cobaltosic oxide raw material is mixed according to the molar ratio of Li to Co of 1.05; in the step B, lithium carbonate and nickel cobalt manganese (523) ternary precursor raw materials are mixed according to the molar ratio of Li to (Ni + Co + Mn) of 1.05; in the step C, the weight ratio of the material A to the material B is 80:20, and the weight ratio of the coating agent to the material A is 1%.
Comparative example 3
A preparation method of a positive electrode material comprises the following steps:
A. doping Sb and Mg with cobaltosic oxide, uniformly mixing the Sb and Mg with lithium carbonate, sintering the mixture at 1030 ℃ for 2 hours, cooling the mixture, and performing ball milling on the mixture to obtain a material A with the particle size D50 of 25 mu m;
B. uniformly mixing a ternary precursor of lithium carbonate, nickel manganese cobalt (523) and nano nickel oxide, sintering at 900 ℃ for 10 hours, cooling, and ball-milling to obtain a material B with the particle size D50 of 8 mu m;
C. uniformly mixing the material A and the material B, preserving heat for 8 hours at the temperature of 900 ℃, cooling, crushing and screening;
in the step A, the doping amounts of Sb and Mg are respectively 0.1 percent and 0.15 percent of the mole number of Co, and the cobaltosic oxide raw material is mixed according to the molar ratio of Li to Co of 1.05; in the step B, lithium carbonate, a nickel-cobalt-manganese (523) ternary precursor and a nano nickel oxide raw material are mixed according to the molar ratio of Li to (Ni + Co + Mn) of 1.05, wherein the weight of the nickel oxide accounts for 5% of that of the nickel-cobalt-manganese (523) ternary precursor; in the step C, the weight ratio of the material A to the material B is 80: 20.
The positive electrode materials prepared according to the positive electrode material preparation methods of examples 1 to 6 and comparative examples 1 to 3 were used as full cells and examined, and the examination results are shown in tables 1 to 2:
table 1 examples 1-5 battery performance
Figure BDA0002181624780000091
Figure BDA0002181624780000101
Table 2 example 6 and comparative examples 1-3 cell performance
Figure BDA0002181624780000102
As can be seen from tables 1-2, the full cells prepared in examples 1-6 were much better than comparative examples 1-3 in terms of 1C specific volume, 1C cycle capacity retention rate of 400 weeks, thickness expansion rate measured after storage at 85 ℃ for 4 hours in full electric state and 3C5V overcharge, etc., the examples 1-6 and comparative examples 1-2 were not much different in 135 ℃ heat abuse, and examples 1-6 were much better than comparative example 3 in 135 ℃ heat abuse.
This is because: in examples 1 to 6, a cobalt source is used in step a, nickel oxide is doped in step B, and a coating agent is added in step C, the cobalt source is doped in step a, nickel oxide is doped in step B, and the coating agent is added in step C, these three processing methods are mutually matched, the doping substance and the coating agent are mutually promoted and act together, and the prepared positive electrode material has the advantages of high specific capacity, good cycle performance, small high-temperature storage thickness expansion rate, high energy density, and the like. In the step A in the comparative example 1, a doped cobalt source is not used, only nickel oxide and a coating agent play a role, in the step B in the comparative example 2, nickel oxide is not doped, only the doped cobalt source and the coating agent play a role, in the comparative example 3, the coating agent is added in the step C, only the doped cobalt source and the doped nickel oxide play a role, and in the comparative examples 1-3, the combined action of the three treatment methods is lacked, so that the comprehensive performances of the prepared anode material, such as specific capacity, cycle performance, high-temperature storage performance, energy density and the like, can not reach the optimal state.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.

Claims (10)

1. The preparation method of the cathode material is characterized by comprising the following steps of:
A. mixing and sintering a first lithium source and a doped cobalt source to obtain a material A;
B. mixing a second lithium source, a nickel-manganese-cobalt ternary precursor and nickel oxide, and sintering to obtain a material B;
C. mixing and sintering the material A, the material B and the coating agent;
wherein, the doping element doping the cobalt source comprises Sb and at least one of Mg, Al, Ti and Zr, and the cladding agent comprises nickel oxide and at least one of aluminum oxide, lanthanum oxide and yttrium oxide.
2. The method for preparing the cathode material according to claim 1, wherein the step a further comprises grinding the material a to obtain a powder with a particle size D50 of 10 to 25 μm; and step B, grinding the material B to obtain the material D50 with the particle size of 3-8 μm.
3. The method for preparing a positive electrode material according to claim 1, wherein in the step A, the cobalt source is one or more of cobaltosic oxide, hydroxycobalt and cobalt hydroxide, the molar ratio of Li to Co is 1.03-1.2, and the sintering temperature is 950-1100 ℃.
4. The method for producing a positive electrode material according to claim 1, wherein in the step A, the doping amount of Sb is 0.02 to 0.5% by mole of Co, and the doping amount of one or more of Mg, Al, Ti and Zr is 0.02 to 0.5% by mole of Co.
5. The method for preparing the cathode material according to claim 1, wherein in the step B, the molar ratio of Li to (Ni + Co + Mn) is 1.03-1.2, and the nickel oxide accounts for 3-7% of the weight of the nickel-manganese-cobalt ternary precursor.
6. The method for preparing a positive electrode material according to claim 1, wherein in the step C, the weight ratio of the material A to the material B is (60-90) to (40-10).
7. The method for preparing a cathode material as claimed in claim 1, wherein in the step C, the weight ratio of the coating agent to the material A is 0.05-1%, and the sintering temperature is 850-.
8. The method for preparing a positive electrode material according to claim 1, wherein the first lithium source is one or more selected from lithium carbonate, lithium fluoride, lithium hydroxide and lithium acetate, and the second lithium source is one or more selected from lithium carbonate, lithium fluoride, lithium hydroxide and lithium acetate.
9. The method for producing a positive electrode material according to claim 1, wherein step C further comprises a pulverization screening treatment.
10. A positive electrode material, characterized by being produced according to the method for producing a positive electrode material as claimed in any one of claims 1 to 9.
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