CN113292111A - Cobalt-free single crystal cathode material and preparation method thereof - Google Patents

Cobalt-free single crystal cathode material and preparation method thereof Download PDF

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CN113292111A
CN113292111A CN202110444197.8A CN202110444197A CN113292111A CN 113292111 A CN113292111 A CN 113292111A CN 202110444197 A CN202110444197 A CN 202110444197A CN 113292111 A CN113292111 A CN 113292111A
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oxide
manganese
nickel
cobalt
single crystal
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马娜妮
李崇
方向乾
张彩红
吕明
高峰
杨欣
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Shaanxi Rainbow New Materials Co ltd
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    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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Abstract

The invention discloses a cobalt-free single crystal anode material and a preparation method thereof, wherein metal oxide X, nickel oxide and manganese oxide are uniformly dispersed in a certain mixing mode according to a certain proportion, and are sintered for the first time under a first temperature curve to obtain a metal oxide X-doped nickel manganese X precursor; uniformly dispersing the nickel-manganese X precursor and the lithium source in a certain mixing mode according to a certain proportion, and performing secondary sintering under a second temperature curve to obtain a nickel-manganese X lithium composite material; naturally cooling the lithium nickel manganese oxide X composite material to room temperature, and crushing and sieving to obtain lithium nickel manganese oxide X composite material powder; and uniformly dispersing the lithium nickel manganese X composite material powder and the additive B in a certain mixing mode according to a certain proportion, and sintering for the third time under a third temperature curve to obtain the oxide-coated lithium nickel manganese X composite material. The invention can solve the problems of complex process and long preparation period of the current cobalt-free single crystal anode material preparation process.

Description

Cobalt-free single crystal cathode material and preparation method thereof
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a cobalt-free single crystal cathode material and a preparation method thereof.
Background
The ternary material of the lithium ion battery has been widely noticed due to the advantages of higher specific discharge capacity, better cycle performance, lower production cost and the like. Among them, cobalt-free single crystal materials have become a very necessary research hotspot due to their lower cost and complete positive electrode material structure.
At present, the preparation method of the cobalt-free single crystal material generally comprises the steps of firstly preparing a nickel-manganese-based precursor by using nickel-manganese-based sulfate by adopting a coprecipitation method, and then adding a lithium source to roast the cobalt-free single crystal positive electrode material. The method has the advantages of complex process, high cost and large pollution. For example, in the preparation method disclosed in chinese patent application No. 202011466135.9, "a cobalt-free single crystal positive electrode material, and a preparation method and application thereof," a nickel-manganese-based precursor and a nickel-manganese-aluminum-based precursor are added with a lithium source and a doping element to be calcined during the preparation process.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a cobalt-free single crystal cathode material and a preparation method thereof, which can solve the problems of complex process and long preparation period of the current cobalt-free single crystal cathode material preparation process.
In order to solve the technical problems, the invention is realized by the following technical scheme:
a preparation method of a cobalt-free single crystal cathode material comprises the following steps:
step 1: uniformly dispersing metal oxide X, nickel oxide and manganese oxide in a certain mixing mode according to a certain proportion, and sintering for the first time under a first temperature curve to obtain a nickel-manganese-X precursor doped with the metal oxide X;
step 2: uniformly dispersing the nickel-manganese X precursor and the lithium source in a certain mixing mode according to a certain proportion, and performing secondary sintering under a second temperature curve to obtain a nickel-manganese X lithium composite material;
and step 3: naturally cooling the lithium nickel manganese oxide X composite material to room temperature, and crushing and sieving to obtain lithium nickel manganese oxide X composite material powder;
and 4, step 4: and uniformly dispersing the lithium nickel manganese X composite material powder and the additive B in a certain mixing mode according to a certain proportion, and sintering for the third time under a third temperature curve to obtain an oxide-coated lithium nickel manganese X composite material, namely the cobalt-free single crystal positive electrode material.
Further, in step 1, the metal oxide X comprises one or more of aluminum oxide, magnesium oxide, zirconium oxide, titanium oxide, niobium oxide, tungsten oxide, boron oxide, lanthanum oxide and molybdenum oxide;
the ratio of the metal oxide X to the sum of the weight of the nickel oxide and the manganese oxide is controlled to be between 2 and 5 percent.
Further, in the step 1, the first temperature curve is raised from room temperature to 250-550 ℃ at a temperature raising rate of 0.5-10 ℃/min in an oxygen-containing atmosphere, and the temperature is maintained for 3-13 hours.
Further, in the step 2, the second temperature curve is raised from room temperature to 870-960 ℃ at a temperature raising rate of 0.5-10 ℃/min in an oxygen-containing atmosphere, and the temperature is maintained for 7-19 hours.
Further, in the step 4, the third temperature curve is raised from room temperature to 500-700 ℃ at a temperature raising rate of 0.5-10 ℃/min in an oxygen-containing atmosphere, and the temperature is maintained for 7-15 hours.
Further, in step 4, the additive B comprises one or more of aluminum oxide, yttrium oxide, zirconium oxide, titanium oxide, niobium oxide, tungsten oxide, lanthanum oxide and molybdenum oxide;
the weight ratio of the additive B to the lithium nickel manganese X composite material powder is controlled to be between 0.02 and 1 percent.
Further, the mixing mode in the step 1, the step 2 and the step 4 comprises one of a self-ball mill mixer, a drum mixer, a high-speed mixer, a conical mixer, a spiral belt mixer and a coulter mixer, and is determined according to the mixing weight.
Further, the oxygen-containing atmosphere comprises air atmosphere, pure oxygen and mixed atmosphere of pure oxygen and air, and the oxygen content is controlled to be 20-80%.
The cobalt-free single crystal anode material is prepared by the preparation method of the cobalt-free single crystal anode material.
Compared with the prior art, the invention has at least the following beneficial effects: according to the invention, the nickel oxide, the manganese oxide and the metal oxide X are directly adopted as raw materials, so that a complicated precursor preparation process is omitted, the metal oxide X is directly mixed in at a raw material stage, the uniformity and the structural stability of the anode material can be improved, and the preparation method is simple in process, low in production cost and more environment-friendly.
In order to make the aforementioned and other objects, features and advantages of the present invention comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
FIG. 1 is a schematic diagram of a preparation method of a cobalt-free single crystal cathode material of the present invention.
FIG. 2 is the electron microscope topography of the cobalt-free single crystal cathode material obtained in example III.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the present invention are described clearly and completely below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention relates to a preparation method of a cobalt-free single crystal anode material, which comprises the following steps:
step 1: uniformly dispersing metal oxide X, nickel oxide and manganese oxide in a certain mixing mode according to a certain proportion, and sintering for the first time under a first temperature curve to obtain a nickel-manganese-X precursor doped with the metal oxide X;
specifically, the metal oxide X includes one or more of alumina, magnesia, zirconia, titania, niobium oxide, tungsten oxide, boron oxide, lanthanum oxide, and molybdenum oxide;
the ratio of the metal oxide X to the sum of the weight of the nickel oxide and the manganese oxide is controlled to be between 2 and 5 percent;
the mixing mode comprises one of a self-ball-milling mixer, a drum mixer, a high-speed mixer, a conical mixer, a spiral belt mixer and a coulter mixer, and is determined according to the mixing weight;
the first temperature curve is that the temperature is raised from room temperature to 250-550 ℃ at the temperature raising rate of 0.5-10 ℃/min in the oxygen-containing atmosphere, the temperature is kept for 3-13 hours, the oxygen-containing atmosphere comprises air atmosphere, pure oxygen and the mixed atmosphere of the pure oxygen and the air, and the oxygen content is controlled to be 20-80%.
Step 2: uniformly dispersing the nickel-manganese X precursor and the lithium source in a certain mixing mode according to a certain proportion, and performing secondary sintering under a second temperature curve to obtain a nickel-manganese X lithium composite material;
specifically, the mixing mode comprises one of a self-ball-milling mixer, a drum mixer, a high-speed mixer, a conical mixer, a spiral mixer and a coulter mixer, and is determined according to the mixing weight;
the second temperature curve is that the temperature is raised from room temperature to 870-960 ℃ at the temperature raising rate of 0.5-10 ℃/min in the oxygen-containing atmosphere, the temperature is kept for 7-19 hours, the oxygen-containing atmosphere comprises air atmosphere, pure oxygen and the mixed atmosphere of the pure oxygen and the air, and the oxygen content is controlled to be 20-80%.
S3: naturally cooling the lithium nickel manganese oxide X composite material to room temperature, and crushing and sieving to obtain lithium nickel manganese oxide X composite material powder;
s4: uniformly dispersing the lithium nickel manganese X composite material powder and the additive B in a certain mixing mode according to a certain proportion, and sintering for the third time under a third temperature curve to obtain an oxide-coated lithium nickel manganese X composite material, namely the cobalt-free single crystal positive electrodeThe chemical expression of the cathode material and the cobalt-free single crystal cathode material is as follows: li1+xNiaMnbXcO2Wherein a is more than or equal to 0.50 and less than or equal to 0.90, b is more than or equal to 0 and less than or equal to 0.70, c is more than or equal to 0.02 and less than or equal to 0.05, and x is more than or equal to 0 and less than or equal to 1;
specifically, the additive B comprises one or more of aluminum oxide, yttrium oxide, zirconium oxide, titanium oxide, niobium oxide, tungsten oxide, lanthanum oxide and molybdenum oxide;
the weight ratio of the additive B to the lithium nickel manganese oxide X composite material powder is controlled to be between 0.02 and 1 percent;
the mixing mode comprises one of a self-ball-milling mixer, a drum mixer, a high-speed mixer, a conical mixer, a spiral belt mixer and a coulter mixer, and is determined according to the mixing weight;
the third temperature curve is that the temperature is raised from room temperature to 500-700 ℃ at the temperature raising rate of 0.5-10 ℃/min in the oxygen-containing atmosphere, the temperature is kept for 7-15 hours, the oxygen-containing atmosphere comprises air atmosphere, pure oxygen and the mixed atmosphere of the pure oxygen and the air, and the oxygen content is controlled to be 20-80%.
Example one
A preparation method of a cobalt-free single crystal cathode material comprises the following steps:
step 1: adding metal aluminum oxide, nickel oxide and manganese oxide into a high-speed mixer, uniformly mixing and dispersing, sintering the mixed material for the first time under the air atmosphere condition, heating from room temperature to 250 ℃ at the heating rate of 0.5 ℃/min, and preserving heat for 10 hours to obtain a nickel-manganese-aluminum precursor doped with metal oxide X;
the ratio of metallic alumina to the sum of the weight of nickel oxide and manganese oxide was 2%.
Step 2: adding the nickel-manganese-aluminum precursor and the lithium source into a high-speed mixer, uniformly mixing and dispersing, carrying out secondary sintering on the mixed material under the air atmosphere condition, heating to 960 ℃ from room temperature at the heating rate of 7 ℃/min, and carrying out heat preservation for 7 hours to obtain the nickel-manganese-aluminum lithium composite material.
And step 3: naturally cooling the lithium nickel manganese aluminate composite material to room temperature, and crushing and sieving to obtain lithium nickel manganese aluminate composite material powder;
and 4, step 4: adding the lithium nickel manganese aluminate composite material powder and titanium oxide into a high-speed mixer, uniformly mixing and dispersing, sintering the mixed material for the third time under the air atmosphere condition, heating the mixed material from room temperature to 500 ℃ at the heating rate of 4 ℃/min, and preserving the heat for 7 hours to obtain an oxide-coated lithium nickel manganese aluminate composite material, namely the cobalt-free single crystal anode material;
the weight ratio of the titanium oxide to the lithium nickel manganese aluminate composite powder was 1%.
Example two
A preparation method of a cobalt-free single crystal cathode material comprises the following steps:
step 1: adding metal magnesium oxide, nickel oxide and manganese oxide into a high-speed mixer, uniformly mixing and dispersing, sintering the mixed material for the first time under the air atmosphere condition, heating from room temperature to 550 ℃ at the heating rate of 10 ℃/min, and preserving heat for 13 hours to obtain a metal magnesium oxide doped nickel manganese magnesium precursor;
the ratio of metallic magnesium oxide to the sum of the weight of nickel oxide and manganese oxide was 4%.
Step 2: adding the nickel-manganese-magnesium precursor and a lithium source into a high-speed mixer, uniformly mixing and dispersing, carrying out secondary sintering on the mixed material under the air atmosphere condition, heating to 870 ℃ from room temperature at the heating rate of 4 ℃/min, and carrying out heat preservation for 19 hours to obtain the nickel-manganese-magnesium-lithium carbonate composite material.
And step 3: naturally cooling the lithium nickel manganese magnesium acid composite material to room temperature, crushing and sieving to obtain lithium nickel manganese magnesium acid composite material powder;
and 4, step 4: adding the lithium nickel manganese magnesium oxide composite material powder and titanium oxide into a high-speed mixer, uniformly mixing and dispersing, sintering the mixed material for the third time under the air atmosphere condition, heating from room temperature to 500 ℃ at the heating rate of 7 ℃/min, and preserving heat for 7 hours to obtain an oxide-coated lithium nickel manganese magnesium oxide composite material, namely obtaining a cobalt-free single crystal positive electrode material;
the weight ratio of the titanium oxide to the lithium nickel manganese magnesium oxide composite powder was 1%.
EXAMPLE III
A preparation method of a cobalt-free single crystal cathode material comprises the following steps:
step 1: adding metal zirconia, nickel oxide and manganese oxide into a high-speed mixer, uniformly mixing and dispersing, sintering the mixed material for the first time under the air atmosphere condition, heating the mixed material from room temperature to 380 ℃ at the heating rate of 5 ℃/min, and preserving the heat for 3 hours to obtain a nickel-manganese-zirconium precursor doped with the metal zirconia;
the ratio of metallic zirconia to the sum of the weight of nickel oxide and manganese oxide was 5%.
Step 2: adding the nickel-manganese-zirconium precursor and a lithium source into a high-speed mixer, uniformly mixing and dispersing, carrying out secondary sintering on the mixed material under the air atmosphere condition, heating from room temperature to 870 ℃ at the heating rate of 0.5 ℃/min, and carrying out heat preservation for 13 hours to obtain the nickel-manganese-lithium zirconate composite material.
And step 3: naturally cooling the nickel-manganese-lithium zirconate composite material to room temperature, crushing and sieving to obtain nickel-manganese-lithium zirconate composite material powder;
and 4, step 4: adding the nickel-manganese-lithium zirconate composite material powder and titanium oxide into a high-speed mixer, uniformly mixing and dispersing, sintering the mixed material for the third time under the air atmosphere condition, heating from room temperature to 600 ℃ at the heating rate of 10 ℃/min, and preserving the heat for 10 hours to obtain an oxide-coated nickel-manganese-lithium zirconate composite material, namely obtaining a cobalt-free single crystal positive electrode material, wherein the appearance picture of an electron microscope of the cobalt-free single crystal positive electrode material is shown in figure 2;
the weight ratio of the titanium oxide to the nickel manganese zirconate composite powder was 0.02%.
Example four
A preparation method of a cobalt-free single crystal cathode material comprises the following steps:
step 1: adding metal titanium oxide, nickel oxide and manganese oxide into a high-speed mixer, uniformly mixing and dispersing, sintering the mixed material for the first time under the air atmosphere condition, heating from room temperature to 400 ℃ at the heating rate of 5 ℃/min, and preserving heat for 8 hours to obtain a nickel-manganese-titanium precursor doped with the metal titanium oxide;
the ratio of the metal titanium oxide to the sum of the weight of the nickel oxide and the manganese oxide was 3%.
Step 2: adding the nickel-manganese-titanium precursor and a lithium source into a high-speed mixer, uniformly mixing and dispersing, carrying out secondary sintering on the mixed material under the air atmosphere condition, heating to 960 ℃ from room temperature at the heating rate of 10 ℃/min, and carrying out heat preservation for 13 hours to obtain the nickel-manganese-lithium titanate composite material.
And step 3: naturally cooling the nickel-manganese-lithium titanate composite material to room temperature, and crushing and sieving to obtain nickel-manganese-lithium titanate composite material powder;
and 4, step 4: adding the nickel-manganese-lithium titanate composite material powder and titanium oxide into a high-speed mixer, uniformly mixing and dispersing, carrying out third sintering on the mixed material under the air atmosphere condition, heating from room temperature to 550 ℃ at the heating rate of 0.5 ℃/min, and carrying out heat preservation for 15 hours to obtain an oxide-coated nickel-manganese-lithium titanate composite material, namely obtaining a cobalt-free single crystal positive electrode material;
the weight ratio of the titanium oxide to the nickel-manganese-lithium titanate composite material powder is 0.06%.
EXAMPLE five
A preparation method of a cobalt-free single crystal cathode material comprises the following steps:
step 1: adding metal niobium oxide, nickel oxide and manganese oxide into a high-speed mixer, uniformly mixing and dispersing, sintering the mixed material for the first time under the air atmosphere condition, heating the mixed material from room temperature to 250 ℃ at the heating rate of 5 ℃/min, and preserving the heat for 6 hours to obtain a nickel manganese niobium precursor doped with the metal niobium oxide;
the ratio of niobium metal oxide to the sum of the weight of nickel oxide and manganese oxide was 2%.
Step 2: adding the nickel-manganese-niobium precursor and the lithium source into a high-speed mixer, uniformly mixing and dispersing, carrying out secondary sintering on the mixed material under the air atmosphere condition, heating to 900 ℃ from room temperature at the heating rate of 6 ℃/min, and carrying out heat preservation for 19 hours to obtain the nickel-manganese-niobium lithium composite material.
And step 3: naturally cooling the lithium nickel manganese niobate composite material to room temperature, and crushing and sieving to obtain lithium nickel manganese niobate composite material powder;
and 4, step 4: adding the lithium nickel manganese niobate composite material powder and titanium oxide into a high-speed mixer, uniformly mixing and dispersing, carrying out third sintering on the mixed material under the air atmosphere condition, heating the mixed material from room temperature to 700 ℃ at the heating rate of 6 ℃/min, and carrying out heat preservation for 13 hours to obtain an oxide-coated lithium nickel manganese niobate composite material, namely obtaining a cobalt-free single crystal anode material;
the weight ratio of the titanium oxide to the lithium nickel manganese niobate composite powder was 0.05%.
EXAMPLE six
A preparation method of a cobalt-free single crystal cathode material comprises the following steps:
step 1: adding metal tungsten oxide, nickel oxide and manganese oxide into a high-speed mixer, uniformly mixing and dispersing, sintering the mixed material for the first time under the air atmosphere condition, heating from room temperature to 340 ℃ at the heating rate of 5 ℃/min, and preserving heat for 6 hours to obtain a nickel-manganese-tungsten precursor doped with the metal tungsten oxide;
the ratio of metallic tungsten oxide to the sum of the weight of nickel oxide and manganese oxide was 2%.
Step 2: adding the nickel-manganese-tungsten precursor and a lithium source into a high-speed mixer, uniformly mixing and dispersing, carrying out secondary sintering on the mixed material under the air atmosphere condition, heating to 910 ℃ from room temperature at the heating rate of 10 ℃/min, and carrying out heat preservation for 10 hours to obtain the nickel-manganese-tungsten composite material.
And step 3: naturally cooling the nickel-manganese-lithium tungstate composite material to room temperature, and crushing and sieving to obtain nickel-manganese-lithium tungstate composite material powder;
and 4, step 4: adding the nickel-manganese-lithium tungstate composite material powder and titanium oxide into a high-speed mixer, uniformly mixing and dispersing, sintering the mixed material for the third time under the air atmosphere condition, heating from room temperature to 690 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 14 hours to obtain an oxide-coated nickel-manganese-lithium tungstate composite material, namely the cobalt-free single crystal anode material;
the weight ratio of the titanium oxide to the nickel manganese lithium tungstate composite material powder is 0.07%.
EXAMPLE seven
A preparation method of a cobalt-free single crystal cathode material comprises the following steps:
step 1: adding metal boron oxide, nickel oxide and manganese oxide into a high-speed mixer, uniformly mixing and dispersing, sintering the mixed material for the first time under the air atmosphere condition, heating the mixed material from room temperature to 260 ℃ at the heating rate of 5 ℃/min, and preserving the heat for 7 hours to obtain a nickel manganese boron precursor doped with the metal boron oxide;
the ratio of metallic boron oxide to the sum of the weight of nickel oxide and manganese oxide was 3%.
Step 2: adding the nickel-manganese-boron precursor and the lithium source into a high-speed mixer, uniformly mixing and dispersing, carrying out secondary sintering on the mixed material under the air atmosphere condition, heating to 880 ℃ from room temperature at the heating rate of 1 ℃/min, and carrying out heat preservation for 10 hours to obtain the nickel-manganese-boron lithium composite material.
And step 3: naturally cooling the lithium nickel manganese borate composite material to room temperature, and crushing and sieving to obtain lithium nickel manganese borate composite material powder;
and 4, step 4: adding the lithium nickel manganese borate composite material powder and titanium oxide into a high-speed mixer, uniformly mixing and dispersing, sintering the mixed material for the third time under the air atmosphere condition, heating the mixed material from room temperature to 680 ℃ at the heating rate of 10 ℃/min, and preserving the heat for 10 hours to obtain an oxide-coated lithium nickel manganese borate composite material, namely the cobalt-free single crystal anode material;
the weight ratio of the titanium oxide to the lithium nickel manganese borate composite powder was 0.09%.
Example eight
A preparation method of a cobalt-free single crystal cathode material comprises the following steps:
step 1: adding metal lanthanum oxide, nickel oxide and manganese oxide into a high-speed mixer, uniformly mixing and dispersing, sintering the mixed material for the first time under the air atmosphere condition, heating from room temperature to 550 ℃ at the heating rate of 5 ℃/min, and preserving heat for 8 hours to obtain a metal lanthanum oxide doped nickel manganese lanthanum precursor;
the ratio of the metal lanthanum oxide to the sum of the weight of the nickel oxide and the manganese oxide was 4%.
Step 2: adding the nickel manganese lanthanum precursor and the lithium source into a high-speed mixer, uniformly mixing and dispersing, carrying out secondary sintering on the mixed material under the air atmosphere condition, heating from room temperature to 870 ℃ at the heating rate of 2 ℃/min, and carrying out heat preservation for 11 hours to obtain the lithium nickel manganese lanthanum composite material.
And step 3: naturally cooling the lithium nickel manganese lanthanum oxide composite material to room temperature, and crushing and sieving to obtain lithium nickel manganese lanthanum oxide composite material powder;
and 4, step 4: adding the lithium nickel manganese lanthanum oxide composite material powder and titanium oxide into a high-speed mixer, uniformly mixing and dispersing, carrying out third sintering on the mixed material under the air atmosphere condition, heating from room temperature to 530 ℃ at the heating rate of 4 ℃/min, and preserving heat for 11 hours to obtain an oxide-coated lithium nickel manganese lanthanum oxide composite material, namely obtaining a cobalt-free single crystal positive electrode material;
the weight ratio of the titanium oxide to the lithium nickel manganese lanthanum oxide composite powder was 1%.
Example nine
A preparation method of a cobalt-free single crystal cathode material comprises the following steps:
step 1: adding metal molybdenum oxide, nickel oxide and manganese oxide into a high-speed mixer, uniformly mixing and dispersing, sintering the mixed material for the first time under the air atmosphere condition, heating from room temperature to 370 ℃ at the heating rate of 5 ℃/min, and preserving heat for 7 hours to obtain a nickel-manganese-molybdenum precursor doped with metal molybdenum oxide;
the ratio of metallic molybdenum oxide to the sum of the weight of nickel oxide and manganese oxide was 4%.
Step 2: adding the nickel-manganese-molybdenum precursor and the lithium source into a high-speed mixer, uniformly mixing and dispersing, carrying out secondary sintering on the mixed material under the air atmosphere condition, and heating from room temperature to 870 ℃ at the heating rate of 4 ℃/min, and carrying out heat preservation for 14 hours to obtain the nickel-manganese-molybdenum lithium composite material.
And step 3: naturally cooling the lithium nickel manganese molybdate composite material to room temperature, and crushing and sieving to obtain lithium nickel manganese molybdate composite material powder;
and 4, step 4: adding the lithium nickel manganese molybdate composite material powder and titanium oxide into a high-speed mixer, uniformly mixing and dispersing, sintering the mixed material for the third time under the air atmosphere condition, heating the mixed material from room temperature to 500 ℃ at the heating rate of 3 ℃/min, and preserving the heat for 8 hours to obtain an oxide-coated lithium nickel manganese molybdate composite material, namely the cobalt-free single crystal anode material;
the weight ratio of the titanium oxide to the lithium nickel manganese molybdate composite powder was 0.02%.
Example ten
A preparation method of a cobalt-free single crystal cathode material comprises the following steps:
step 1: adding metal aluminum oxide, nickel oxide and manganese oxide into a high-speed mixer, uniformly mixing and dispersing, sintering the mixed materials for the first time under the air atmosphere condition, heating the mixed materials from room temperature to 300 ℃ at the heating rate of 0.5 ℃/min, and preserving heat for 13 hours to obtain a nickel-manganese-aluminum precursor doped with metal oxide X;
the ratio of metallic alumina to the sum of the weight of nickel oxide and manganese oxide was 5%.
Step 2: adding the nickel-manganese-aluminum precursor and the lithium source into a high-speed mixer, uniformly mixing and dispersing, carrying out secondary sintering on the mixed material under the air atmosphere condition, heating to 960 ℃ from room temperature at the heating rate of 3 ℃/min, and carrying out heat preservation for 13 hours to obtain the nickel-manganese-aluminum lithium composite material.
And step 3: naturally cooling the lithium nickel manganese aluminate composite material to room temperature, and crushing and sieving to obtain lithium nickel manganese aluminate composite material powder;
and 4, step 4: adding the lithium nickel manganese aluminate composite material powder and alumina into a high-speed mixer, uniformly mixing and dispersing, sintering the mixed material for the third time under the air atmosphere condition, heating the mixed material from room temperature to 700 ℃ at the heating rate of 6 ℃/min, and keeping the temperature for 13 hours to obtain an oxide-coated lithium nickel manganese aluminate composite material, namely the cobalt-free single crystal anode material;
the weight ratio of the alumina to the lithium nickel manganese aluminate composite powder was 0.02%.
EXAMPLE eleven
A preparation method of a cobalt-free single crystal cathode material comprises the following steps:
step 1: adding metal aluminum oxide, nickel oxide and manganese oxide into a high-speed mixer, uniformly mixing and dispersing, sintering the mixed material for the first time under the air atmosphere condition, heating from room temperature to 250 ℃ at the heating rate of 0.5 ℃/min, and preserving heat for 4 hours to obtain a nickel-manganese-aluminum precursor doped with metal oxide X;
the ratio of metallic alumina to the sum of the weight of nickel oxide and manganese oxide was 3%.
Step 2: adding the nickel-manganese-aluminum precursor and the lithium source into a high-speed mixer, uniformly mixing and dispersing, carrying out secondary sintering on the mixed material under the air atmosphere condition, heating to 900 ℃ from room temperature at the heating rate of 6 ℃/min, and carrying out heat preservation for 17 hours to obtain the nickel-manganese-aluminum lithium composite material.
And step 3: naturally cooling the lithium nickel manganese aluminate composite material to room temperature, and crushing and sieving to obtain lithium nickel manganese aluminate composite material powder;
and 4, step 4: adding the lithium nickel manganese aluminate composite material powder and yttrium oxide into a high-speed mixer, uniformly mixing and dispersing, sintering the mixed material for the third time under the air atmosphere condition, heating the mixed material from room temperature to 700 ℃ at the heating rate of 4.5 ℃/min, and preserving the heat for 9 hours to obtain an oxide-coated lithium nickel manganese aluminate composite material, namely the cobalt-free single crystal positive electrode material;
the weight ratio of the yttrium oxide to the lithium nickel manganese aluminate composite powder was 1%.
Example twelve
A preparation method of a cobalt-free single crystal cathode material comprises the following steps:
step 1: adding metal aluminum oxide, nickel oxide and manganese oxide into a high-speed mixer, uniformly mixing and dispersing, sintering the mixed materials for the first time under the air atmosphere condition, heating from room temperature to 500 ℃ at the heating rate of 0.5 ℃/min, and preserving heat for 3 hours to obtain a nickel-manganese-aluminum precursor doped with metal oxide X;
the ratio of metallic alumina to the sum of the weight of nickel oxide and manganese oxide was 2%.
Step 2: adding the nickel-manganese-aluminum precursor and the lithium source into a high-speed mixer, uniformly mixing and dispersing, carrying out secondary sintering on the mixed material under the air atmosphere condition, heating to 900 ℃ from room temperature at the heating rate of 4.5 ℃/min, and carrying out heat preservation for 16 hours to obtain the nickel-manganese-aluminum lithium composite material.
And step 3: naturally cooling the lithium nickel manganese aluminate composite material to room temperature, and crushing and sieving to obtain lithium nickel manganese aluminate composite material powder;
and 4, step 4: adding the lithium nickel manganese aluminate composite material powder and zirconia into a high-speed mixer, uniformly mixing and dispersing, sintering the mixed material for the third time under the air atmosphere condition, heating the mixed material from room temperature to 610 ℃ at the heating rate of 7 ℃/min, and preserving the heat for 7 hours to obtain an oxide-coated lithium nickel manganese aluminate composite material, namely obtaining a cobalt-free single crystal anode material;
the weight ratio of the zirconia to the lithium nickel manganese aluminate composite powder was 0.07%.
EXAMPLE thirteen
A preparation method of a cobalt-free single crystal cathode material comprises the following steps:
step 1: adding metal aluminum oxide, nickel oxide and manganese oxide into a high-speed mixer, uniformly mixing and dispersing, sintering the mixed material for the first time under the air atmosphere condition, heating from room temperature to 490 ℃ at the heating rate of 0.5 ℃/min, and preserving heat for 10 hours to obtain a metal oxide X-doped nickel-manganese-aluminum precursor;
the ratio of metallic alumina to the sum of the weight of nickel oxide and manganese oxide was 2%.
Step 2: adding the nickel-manganese-aluminum precursor and the lithium source into a high-speed mixer, uniformly mixing and dispersing, carrying out secondary sintering on the mixed material under the air atmosphere condition, heating to 900 ℃ from room temperature at the heating rate of 7 ℃/min, and carrying out heat preservation for 18 hours to obtain the nickel-manganese-aluminum lithium composite material.
And step 3: naturally cooling the lithium nickel manganese aluminate composite material to room temperature, and crushing and sieving to obtain lithium nickel manganese aluminate composite material powder;
and 4, step 4: adding the lithium nickel manganese aluminate composite material powder and niobium oxide into a high-speed mixer, uniformly mixing and dispersing, sintering the mixed material for the third time under the air atmosphere condition, heating the mixed material from room temperature to 660 ℃ at the heating rate of 5 ℃/min, and preserving the temperature for 15 hours to obtain an oxide-coated lithium nickel manganese aluminate composite material, namely the cobalt-free single crystal anode material;
the weight ratio of niobium oxide to lithium nickel manganese aluminate composite powder was 0.06%.
Example fourteen
A preparation method of a cobalt-free single crystal cathode material comprises the following steps:
step 1: adding metal aluminum oxide, nickel oxide and manganese oxide into a high-speed mixer, uniformly mixing and dispersing, sintering the mixed material for the first time under the air atmosphere condition, heating from room temperature to 390 ℃ at the heating rate of 0.5 ℃/min, and preserving heat for 11 hours to obtain a nickel-manganese-aluminum precursor doped with metal oxide X;
the ratio of metallic alumina to the sum of the weight of nickel oxide and manganese oxide was 3%.
Step 2: adding the nickel-manganese-aluminum precursor and the lithium source into a high-speed mixer, uniformly mixing and dispersing, carrying out secondary sintering on the mixed material under the air atmosphere condition, heating to 890 ℃ from room temperature at the heating rate of 6 ℃/min, and carrying out heat preservation for 17 hours to obtain the nickel-manganese-aluminum lithium composite material.
And step 3: naturally cooling the lithium nickel manganese aluminate composite material to room temperature, and crushing and sieving to obtain lithium nickel manganese aluminate composite material powder;
and 4, step 4: adding the lithium nickel manganese aluminate composite material powder and tungsten oxide into a high-speed mixer, uniformly mixing and dispersing, sintering the mixed material for the third time under the air atmosphere condition, heating the mixed material from room temperature to 600 ℃ at the heating rate of 4 ℃/min, and preserving the heat for 7 hours to obtain an oxide-coated lithium nickel manganese aluminate composite material, namely the cobalt-free single crystal anode material;
the weight ratio of the tungsten oxide to the lithium nickel manganese aluminate composite powder was 1%.
Example fifteen
A preparation method of a cobalt-free single crystal cathode material comprises the following steps:
step 1: adding metal aluminum oxide, nickel oxide and manganese oxide into a high-speed mixer, uniformly mixing and dispersing, sintering the mixed material for the first time under the air atmosphere condition, heating from room temperature to 270 ℃ at the heating rate of 0.5 ℃/min, and preserving heat for 12 hours to obtain a metal oxide X-doped nickel-manganese-aluminum precursor;
the ratio of metallic alumina to the sum of the weight of nickel oxide and manganese oxide was 5%.
Step 2: adding the nickel-manganese-aluminum precursor and the lithium source into a high-speed mixer, uniformly mixing and dispersing, carrying out secondary sintering on the mixed material under the air atmosphere condition, heating to 920 ℃ from room temperature at the heating rate of 5 ℃/min, and carrying out heat preservation for 19 hours to obtain the lithium nickel-manganese-aluminum composite material.
And step 3: naturally cooling the lithium nickel manganese aluminate composite material to room temperature, and crushing and sieving to obtain lithium nickel manganese aluminate composite material powder;
and 4, step 4: adding the lithium nickel manganese aluminate composite material powder and lanthanum oxide into a high-speed mixer, uniformly mixing and dispersing, sintering the mixed material for the third time under the air atmosphere condition, heating the mixed material from room temperature to 530 ℃ at the heating rate of 6 ℃/min, and preserving the heat for 15 hours to obtain an oxide-coated lithium nickel manganese aluminate composite material, namely the cobalt-free single crystal anode material;
the weight ratio of lanthanum oxide to lithium nickel manganese aluminate composite powder was 0.02%.
Example sixteen
A preparation method of a cobalt-free single crystal cathode material comprises the following steps:
step 1: adding metal aluminum oxide, nickel oxide and manganese oxide into a high-speed mixer, uniformly mixing and dispersing, sintering the mixed materials for the first time under the air atmosphere condition, heating from room temperature to 510 ℃ at the heating rate of 0.5 ℃/min, and preserving heat for 13 hours to obtain a metal oxide X-doped nickel-manganese-aluminum precursor;
the ratio of metallic alumina to the sum of the weight of nickel oxide and manganese oxide was 5%.
Step 2: adding the nickel-manganese-aluminum precursor and the lithium source into a high-speed mixer, uniformly mixing and dispersing, carrying out secondary sintering on the mixed material under the air atmosphere condition, heating to 910 ℃ from room temperature at the heating rate of 4 ℃/min, and carrying out heat preservation for 7 hours to obtain the lithium nickel-manganese-aluminum composite material.
And step 3: naturally cooling the lithium nickel manganese aluminate composite material to room temperature, and crushing and sieving to obtain lithium nickel manganese aluminate composite material powder;
and 4, step 4: adding the lithium nickel manganese aluminate composite material powder and molybdenum oxide into a high-speed mixer, uniformly mixing and dispersing, sintering the mixed material for the third time under the air atmosphere condition, heating the mixed material from room temperature to 580 ℃ at the heating rate of 3 ℃/min, and preserving heat for 9 hours to obtain an oxide-coated lithium nickel manganese aluminate composite material, namely obtaining a cobalt-free single crystal anode material;
the weight ratio of the molybdenum oxide to the lithium nickel manganese aluminate composite powder was 1%.
Comparative example 1
Step 1: weighing ternary precursor (Ni) according to calculated amount0.5Co0.2Mn0.3(OH)2) Lithium carbonate, wherein Li is Ni0.5Co0.2Mn0.3(OH)2Is 1.07: 1.
Step 2: adding the mixture into a high-speed mixer for mixing, wherein the mixing frequency is 45Hz, and the mixing time is 20 min.
And step 3: sintering the uniformly mixed materials under the air atmosphere condition, heating the materials from room temperature to 900 ℃ at the heating rate of 6 ℃/min, and preserving the heat for 13 hours.
And 4, step 4: and finally, naturally cooling the sintered material obtained in the step 3 to room temperature, taking out the powder, crushing the powder, and sieving the crushed powder with a 400-mesh sieve to obtain the comparative example sample 1.
Comparative example No. two
Step 1: weighing oxides of nickel, cobalt and manganese and lithium carbonate according to calculated amount, wherein Li: ni: co: the molar ratio of Mn is 1.07: 0.5: 0.2: 0.3.
step 2: NiO, Mn2O3And Co2O3Proportionally adding the materials into a high-speed mixer for mixing, wherein the mixing frequency is 45Hz, and the mixing time is 20 min.
And step 3: and (3) sintering the uniformly mixed materials for the first time under the air atmosphere condition, heating the materials from room temperature to 450 ℃ at the heating rate of 6 ℃/min, and preserving the heat for 10 hours.
And 4, step 4: and adding the uniformly dispersed materials and a lithium source into a high-speed mixer in proportion for mixing, wherein the mixing frequency is 45Hz, and the mixing time is 30 min.
And 5: and (3) sintering the uniformly mixed materials for the first time under the air atmosphere condition, heating the materials from room temperature to 900 ℃ at the heating rate of 6 ℃/min, and preserving the heat for 13 hours.
Step 6: and finally, naturally cooling the material sintered in the step 5 to room temperature, taking out the powder, crushing the powder, and sieving the powder with a 400-mesh sieve to obtain the comparative example 2.
2025 type power-on manufacturing tests are respectively carried out on the samples of the embodiment and the samples of the comparative example, and multiplying power charge and discharge tests are carried out in a voltage range of 3.0V-4.3V, wherein the multiplying power performance test conditions are as follows: 0.2C, 0.5C, 1C, 2C.
Table 1 shows the electrochemical properties of the samples of examples and of comparative examples
Figure BDA0003036132690000171
Finally, it should be noted that: the above-mentioned embodiments are only specific embodiments of the present invention, which are used for illustrating the technical solutions of the present invention and not for limiting the same, and the protection scope of the present invention is not limited thereto, although the present invention is described in detail with reference to the foregoing embodiments, those skilled in the art should understand that: any person skilled in the art can modify or easily conceive the technical solutions described in the foregoing embodiments or equivalent substitutes for some technical features within the technical scope of the present disclosure; such modifications, changes or substitutions do not depart from the spirit and scope of the embodiments of the present invention, and they should be construed as being included therein. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (9)

1. The preparation method of the cobalt-free single crystal cathode material is characterized by comprising the following steps of:
step 1: uniformly dispersing metal oxide X, nickel oxide and manganese oxide in a certain mixing mode according to a certain proportion, and sintering for the first time under a first temperature curve to obtain a nickel-manganese-X precursor doped with the metal oxide X;
step 2: uniformly dispersing the nickel-manganese X precursor and the lithium source in a certain mixing mode according to a certain proportion, and performing secondary sintering under a second temperature curve to obtain a nickel-manganese X lithium composite material;
and step 3: naturally cooling the lithium nickel manganese oxide X composite material to room temperature, and crushing and sieving to obtain lithium nickel manganese oxide X composite material powder;
and 4, step 4: and uniformly dispersing the lithium nickel manganese X composite material powder and the additive B in a certain mixing mode according to a certain proportion, and sintering for the third time under a third temperature curve to obtain an oxide-coated lithium nickel manganese X composite material, namely the cobalt-free single crystal positive electrode material.
2. The method for preparing a cobalt-free single crystal cathode material according to claim 1, wherein in the step 1, the metal oxide X comprises one or more of aluminum oxide, magnesium oxide, zirconium oxide, titanium oxide, niobium oxide, tungsten oxide, boron oxide, lanthanum oxide, and molybdenum oxide;
the ratio of the metal oxide X to the sum of the weight of the nickel oxide and the manganese oxide is controlled to be between 2 and 5 percent.
3. The method for preparing a cobalt-free single crystal cathode material according to claim 1, wherein in the step 1, the first temperature curve is raised from room temperature to 250-550 ℃ at a temperature rise rate of 0.5-10 ℃/min in an oxygen-containing atmosphere, and the temperature is maintained for 3-13 hours.
4. The method for preparing a cobalt-free single crystal cathode material according to claim 1, wherein in the step 2, the second temperature curve is raised from room temperature to 870-960 ℃ at a temperature raising rate of 0.5-10 ℃/min in an oxygen-containing atmosphere, and the temperature is maintained for 7-19 hours.
5. The method for preparing a cobalt-free single crystal cathode material according to claim 1, wherein in the step 4, the third temperature curve is raised from room temperature to 500 ℃ to 700 ℃ at a temperature rise rate of 0.5 ℃/min to 10 ℃/min in an oxygen-containing atmosphere, and the temperature is maintained for 7 to 15 hours.
6. The method for preparing a cobalt-free single crystal cathode material according to claim 1, wherein in the step 4, the additive B comprises one or more of aluminum oxide, yttrium oxide, zirconium oxide, titanium oxide, niobium oxide, tungsten oxide, lanthanum oxide and molybdenum oxide;
the weight ratio of the additive B to the lithium nickel manganese X composite material powder is controlled to be between 0.02 and 1 percent.
7. The method of claim 1, wherein the mixing in step 1, step 2 and step 4 comprises one of a ball mill mixer, a drum mixer, a high speed mixer, a conical mixer, a ribbon mixer and a coulter mixer, based on the weight of the mixture.
8. The method for preparing the cobalt-free single crystal cathode material according to any one of claims 3 to 5, wherein the oxygen-containing atmosphere comprises an air atmosphere, pure oxygen and a mixed atmosphere of pure oxygen and air, and the oxygen content is controlled to be 20-80%.
9. A cobalt-free single crystal positive electrode material, characterized in that the cobalt-free single crystal positive electrode material is produced by the method for producing a cobalt-free single crystal positive electrode material according to any one of claims 1 to 8.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114420907A (en) * 2022-01-08 2022-04-29 陕西彩虹新材料有限公司 Semiconductor-doped and oxidant-coated single crystal ternary positive electrode material and preparation method thereof
CN114551862A (en) * 2022-02-28 2022-05-27 宜宾锂宝新材料有限公司 Cobalt-free binary single crystal material and preparation method thereof
CN115057487A (en) * 2022-06-30 2022-09-16 蜂巢能源科技股份有限公司 Single-crystal cobalt-free cathode material, preparation method thereof and lithium ion battery

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104733725A (en) * 2015-04-09 2015-06-24 奇瑞汽车股份有限公司 Application and modified preparation method of manganese and lithium rich solid solution material
US20150194662A1 (en) * 2014-01-06 2015-07-09 Shenzhen Btr New Energy Materials Inc. Cathode material of lithium-nickel-cobalt-aluminum composite oxide, a method of fabricating the same and a lithium ion battery including the same
CN105206811A (en) * 2015-09-23 2015-12-30 中信国安盟固利电源技术有限公司 Wrapped and modified anode material doped with metallic oxide and preparation method of anode material
CN105355905A (en) * 2015-11-26 2016-02-24 中信大锰矿业有限责任公司大新锰矿分公司 Method for preparing high-voltage modified lithium ion cell cathode material lithium nickel manganese oxide
CN107785561A (en) * 2017-11-22 2018-03-09 江门市科恒实业股份有限公司 A kind of preparation method of high voltage monocrystalline lithium ion tertiary cathode material
CN109273710A (en) * 2018-08-22 2019-01-25 中伟新材料有限公司 One kind being mixed with type monocrystalline tertiary cathode material preparation method
CN110698189A (en) * 2019-11-15 2020-01-17 中国科学院新疆理化技术研究所 Lanthanum ion doped deep low temperature thermistor material and preparation method thereof
CN111599999A (en) * 2020-05-25 2020-08-28 蜂巢能源科技有限公司 Cobalt-free cathode material, preparation method thereof and lithium ion battery
CN112582597A (en) * 2020-11-20 2021-03-30 昆明理工大学 Preparation method and modification method of ternary cobalt-free cathode material
CN112626606A (en) * 2020-11-23 2021-04-09 陕西彩虹新材料有限公司 Method for preparing high-nickel quaternary monocrystal cathode material by pure solid phase method
WO2021068448A1 (en) * 2019-10-10 2021-04-15 蜂巢能源科技有限公司 Quaternary positive electrode material for lithium ion battery and preparation method therefor, and lithium ion battery

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150194662A1 (en) * 2014-01-06 2015-07-09 Shenzhen Btr New Energy Materials Inc. Cathode material of lithium-nickel-cobalt-aluminum composite oxide, a method of fabricating the same and a lithium ion battery including the same
CN104733725A (en) * 2015-04-09 2015-06-24 奇瑞汽车股份有限公司 Application and modified preparation method of manganese and lithium rich solid solution material
CN105206811A (en) * 2015-09-23 2015-12-30 中信国安盟固利电源技术有限公司 Wrapped and modified anode material doped with metallic oxide and preparation method of anode material
CN105355905A (en) * 2015-11-26 2016-02-24 中信大锰矿业有限责任公司大新锰矿分公司 Method for preparing high-voltage modified lithium ion cell cathode material lithium nickel manganese oxide
CN107785561A (en) * 2017-11-22 2018-03-09 江门市科恒实业股份有限公司 A kind of preparation method of high voltage monocrystalline lithium ion tertiary cathode material
CN109273710A (en) * 2018-08-22 2019-01-25 中伟新材料有限公司 One kind being mixed with type monocrystalline tertiary cathode material preparation method
WO2021068448A1 (en) * 2019-10-10 2021-04-15 蜂巢能源科技有限公司 Quaternary positive electrode material for lithium ion battery and preparation method therefor, and lithium ion battery
CN110698189A (en) * 2019-11-15 2020-01-17 中国科学院新疆理化技术研究所 Lanthanum ion doped deep low temperature thermistor material and preparation method thereof
CN111599999A (en) * 2020-05-25 2020-08-28 蜂巢能源科技有限公司 Cobalt-free cathode material, preparation method thereof and lithium ion battery
CN112582597A (en) * 2020-11-20 2021-03-30 昆明理工大学 Preparation method and modification method of ternary cobalt-free cathode material
CN112626606A (en) * 2020-11-23 2021-04-09 陕西彩虹新材料有限公司 Method for preparing high-nickel quaternary monocrystal cathode material by pure solid phase method

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
NUTTHAPHON PHATTHARASUPAKUN ET AL: ""Impact of Al Doping and Surface Coating on the Electrochemical Performances of Li-Rich Mn-Rich Li1.11Ni0.33Mn0.56O2 Positive Electrode Material"", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》, vol. 167 *
庞国耀等: ""无钴高镍锂离子正极材料LiNixMn1-xO2(0.5<x<1）研究进展"", 《稀有金属》, vol. 44 *
王丹: ""高容量富锂正极材料Li[Li0.2Ni0.2Mn0.6]O2的制备与改性研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, no. 3 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114420907A (en) * 2022-01-08 2022-04-29 陕西彩虹新材料有限公司 Semiconductor-doped and oxidant-coated single crystal ternary positive electrode material and preparation method thereof
CN114420907B (en) * 2022-01-08 2023-10-10 陕西彩虹新材料有限公司 Single crystal ternary positive electrode material doped with semiconductor and coated with oxidant and preparation method thereof
CN114551862A (en) * 2022-02-28 2022-05-27 宜宾锂宝新材料有限公司 Cobalt-free binary single crystal material and preparation method thereof
CN114551862B (en) * 2022-02-28 2023-11-17 宜宾锂宝新材料有限公司 Cobalt-free binary single crystal material and preparation method thereof
CN115057487A (en) * 2022-06-30 2022-09-16 蜂巢能源科技股份有限公司 Single-crystal cobalt-free cathode material, preparation method thereof and lithium ion battery

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Application publication date: 20210824