CN117594783A - Layered composite lithium-rich manganese-based positive electrode material, and preparation method and application thereof - Google Patents

Layered composite lithium-rich manganese-based positive electrode material, and preparation method and application thereof Download PDF

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CN117594783A
CN117594783A CN202410072980.XA CN202410072980A CN117594783A CN 117594783 A CN117594783 A CN 117594783A CN 202410072980 A CN202410072980 A CN 202410072980A CN 117594783 A CN117594783 A CN 117594783A
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lithium
manganese
positive electrode
rich manganese
electrode material
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任志敏
梁展硕
王建涛
杨容
齐小鹏
于冰
李国华
王翠凤
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China Automotive Battery Research Institute Co Ltd
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China Automotive Battery Research Institute Co Ltd
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Abstract

The invention relates to a lithium ion battery, in particular to a layered composite lithium-rich manganese-based positive electrode material, and a preparation method and application thereof. The positive electrode material comprises a lithium-rich manganese-based matrix and an oxygen ion conductor coated on the lithium-rich manganese-based matrix. The invention can improve the compaction density and the circulation stability of the material, obviously improve the multiplying power performance and effectively inhibit the oxygen precipitation.

Description

Layered composite lithium-rich manganese-based positive electrode material, and preparation method and application thereof
Technical Field
The invention relates to a lithium ion battery, in particular to a layered composite lithium-rich manganese-based positive electrode material, and a preparation method and application thereof.
Background
The lithium ion battery anode material with high energy density, high safety and low cost is a key for realizing the sustainable development of the novel lithium ion battery. The lithium-rich positive electrode material generally has higher specific capacity (> 250 mAh/g), higher voltage platform (> 3.6V), better thermal stability and safety, lower cost and no great pollution or harm to the environment, and becomes a next-generation novel lithium ion battery positive electrode material with great development potential. However, the lithium-rich material still has the problems of fast capacity fade, low compaction density, oxygen release and the like, which hinders the commercialization application of the lithium-rich cathode material. The single crystal structure generally has higher crystallinity and lattice integrity and fewer grain boundaries and defects, and can inhibit particle breakage during pole piece mixing, improve energy density of the battery and inhibit generation of particle microcracks during circulation.
Currently, single crystal anodes mainly have two modes, namely high-temperature synthesis and molten salt synthesis, the high temperature can increase the grain growth speed, but can lead to increased volatilization of lithium salt, and additional lithium salt is required to be added to counteract the volatilization, and grinding and cleaning and annealing are required to reduce agglomeration. The molten salt synthesis is mainly based on a dissolution-recrystallization mechanism, the growth of micron-sized grains can be realized at a lower temperature, and chloride salt, chlorate, ferrous chloride and the like are added as auxiliary agents in the mixing process of a lithium-rich precursor and a lithium source, for example, the single crystal lithium-rich manganese-based positive electrode material is obtained by adopting peracetic acid as the auxiliary agent in Chinese patent CN 109537054A. Conventional methods using additives usually require a large amount of additives, and require complicated process flows, and have high production cost and high cost.
However, the monocrystalline lithium-rich manganese-based material still has the technical problems of larger grain size, poor multiplying power performance, lattice oxygen release and the like, and the monocrystalline lithium-rich manganese-based material needs to be subjected to surface modification to improve the performance. For example, chinese patent CN114094080A adopts Co 3 O 4 The single crystal type lithium-rich layered-spinel composite positive electrode material is prepared as an additive, so that the single crystal rate performance is improved.
The manganese-based cathode material is still to be further improved.
Disclosure of Invention
The present invention aims to solve, at least to some extent, one of the technical problems in the prior art, or at least to provide a commercial choice.
The invention firstly provides a layered composite lithium-rich manganese-based positive electrode material, which comprises the following components: a lithium-rich manganese-based matrix and an oxygen ion conductor coated on the lithium-rich manganese-based matrix;
the molecular formula of the lithium-rich manganese-based matrix is Li x Mn a Co b Ni c O 2 ；1＜x≤1.3，0.4≤a≤0.8，0＜b≤0.5，0≤c≤0.5；
The molecular formula of the oxygen ion conductor is A α B β O γ The method comprises the steps of carrying out a first treatment on the surface of the Alpha is more than or equal to 0.5 and less than or equal to 1, beta is more than or equal to 0 and less than or equal to 0.4, alpha+beta is more than or equal to 1, gamma is more than or equal to 1 and less than or equal to 2, wherein element A is at least one of Ce, zr and Bi, and element B is at least one of Cs, mo, dy, Y, nb, ba, la, al, ca, rb, sr.
The invention relates to a layered composite lithium-rich manganese-based positive electrode materialThe formula of (C) may be represented by Li x Mn a Co b Ni c O 2 @A α B β O γ 。
In the layered composite lithium-rich manganese-based positive electrode material, the oxygen ion conductor has oxygen ion storage and migration characteristics, and the oxygen ion conductor is coated on the surface of the lithium-rich manganese-based material, so that the release of lithium-rich lattice oxygen can be effectively inhibited, and the multiplying power performance of the material is improved. The lithium-rich manganese-based material coated by the oxygen ion conductor is in a single crystal shape, the crystallinity of single crystal particles is higher, the surface is more stable, the specific surface area is smaller, the compaction density and the circulation stability of the material can be improved, and the oxygen precipitation can be effectively inhibited.
Further, x=1.18, a=0.52, b=0.15, c=0.15, α=0.9, β=0.1, γ=1.9.
Further, x=1.18, a=0.52, b=0.15, c=0.15, α=0.8, β=0.2, γ=1.9.
Further, in the oxygen ion conductor, the element A is one of Ce and Zr, and the element B is one of Cs, mo, dy, Y, nb.
Further, in the layered composite lithium-rich manganese-based positive electrode material, the oxygen ion conductor is coated on the surface of the lithium-rich manganese-based substrate.
Further, in the layered composite lithium-rich manganese-based positive electrode material, the molar ratio of the lithium-rich manganese-based matrix to the oxygen ion conductor is 1000:1-30, for example, 1000:1, 1000:5, 1000:10, 1000:15, 1000:20, 1000:25, 1000:30.
Further, the oxygen ion conductor has a specific structure, the space group is Fm-3m, and diffraction peaks are arranged at angles of 25 and 35 when the Cu-K alpha is adopted as an incident light source for carrying out X-ray powder diffraction test.
Further, the microstructure of the layered composite lithium-rich manganese-based positive electrode material is single crystal particles, and the median particle diameter (D50) is 0.1um-10um, for example 0.1um, 0.5um, 1um, 1.5um, 1.8um, 2um, 2.5um, 3um, 3.5um, 3.8um, 4um, 4.5um, 5um, 6um, 7um, 8um, 9um, 10um.
The invention also provides a preparation method of the layered composite lithium-rich manganese-based positive electrode material, which comprises the following steps:
weighing a manganese salt compound, a cobalt salt compound and a nickel salt compound according to the stoichiometric ratio of the lithium-rich manganese-based matrix, and dissolving the manganese salt compound, the cobalt salt compound and the nickel salt compound in deionized water to obtain a metal salt solution; dissolving a precipitator in deionized water to obtain a precipitator solution; uniformly mixing the metal salt solution and the precipitant solution, reacting at 50-60 ℃ to obtain suspension, washing, filtering and drying to obtain a manganese cobalt nickel coprecipitation precursor;
according to the stoichiometric ratio of the oxygen ion conductor, dissolving the compound of the element A and the compound of the element B into a solvent to obtain a first solution, wherein the solvent is one of deionized water, ethanol and acetone;
uniformly mixing the manganese cobalt nickel coprecipitation precursor with the first solution, and evaporating to dryness to obtain a modified precursor;
and uniformly mixing the modified precursor with a lithium source according to the stoichiometric ratio of the layered composite lithium-rich manganese-based anode material, and calcining under an oxygen-containing atmosphere to obtain the layered composite lithium-rich manganese-based anode material.
Specifically, the manganese salt compound is selected from at least one of manganese sulfate, manganese chloride, manganese acetate or manganese nitrate; the cobalt salt compound is at least one selected from cobalt sulfate, cobalt chloride, cobalt acetate or cobalt nitrate; the nickel salt compound is selected from at least one of nickel sulfate, nickel chloride, nickel acetate or nickel nitrate.
Specifically, the concentration of the metal salt solution is 0.5-2mol/L.
Specifically, the precipitant is at least one selected from sodium carbonate, potassium carbonate, sodium hydroxide or potassium hydroxide.
Specifically, the compound Ce (NO 3 ) 3 、CeCl 3 、Ce(SO 4 ) 3 、Zr(NO 3 ) 4 、ZrCl 4 、Zr(SO 4 ) 4 、Bi(NO 3 ) 3 、BiCl 3 At least one of (a) and (b); the compound of the element B is at least one of soluble sulfate, nitrate or chloride containing Y, cs, ba, la, dy, al, mo, nb, ca, rb, sr.
Specifically, the solvent comprises one of deionized water, ethanol and acetone.
Specifically, the manganese cobalt nickel coprecipitation precursor is added to the first solution and then mixed (e.g., stirred).
Specifically, the lithium source is at least one of lithium hydroxide, lithium carbonate, lithium nitrate, lithium chloride or lithium acetate.
Specifically, the calcination conditions are: heating to 200-600 ℃ at a heating rate of 0.5-10 ℃/min, and preserving heat for 4-24 h; then heating to 600-1000 ℃ at a heating rate of 0.5-10 ℃/min, and calcining for 6-40 h.
Specifically, the method further comprises the step of cooling (to room temperature) after calcination.
The invention also comprises the layered composite lithium-rich manganese-based positive electrode material prepared by the method.
The invention also comprises application of the layered composite lithium-rich manganese-based positive electrode material in a lithium ion battery.
The invention also provides a lithium ion battery, which comprises a positive electrode, a negative electrode and an electrolyte, wherein the positive electrode comprises the layered composite lithium-rich manganese-based positive electrode material.
According to the preparation method, the precursor is modified, the compound containing the elements A and B is introduced, and the monocrystalline lithium-rich manganese-based positive electrode material coated by the oxygen ion conductor can be directly obtained through sintering, so that the monocrystalline lithium-rich material coated by the oxygen ion conductor with the Fm-3m space group is formed in situ, meanwhile, the compaction density and the circulation stability of the material are improved, the multiplying power performance is obviously improved, and the oxygen precipitation is effectively inhibited. The compound containing the elements A and B adopted by the invention has extremely small dosage and no need of subsequent washing and purification, can directly form the oxygen ion conductor with oxygen ion storage and migration characteristics, has simple process and low equipment requirements, is efficient and is convenient for batch amplification and industrialized production. The synthesized monocrystal lithium-rich material prepared by the method has good particle dispersibility, uniform particles and controllable size.
Drawings
Fig. 1 is an SEM image of a layered composite lithium-rich manganese-based positive electrode material prepared in example 1 of the present invention.
Fig. 2 is an XRD pattern of the layered composite lithium-rich manganese-based positive electrode material prepared in example 1 of the present invention.
Fig. 3 is an SEM image of a conventional polycrystalline morphology lithium-rich material prepared according to comparative example 1 of the present invention.
Fig. 4 is an XRD pattern of a conventional polycrystalline morphology lithium-rich material prepared according to comparative example 1 of the present invention.
Fig. 5 is an SEM image of the modified polycrystalline lithium-rich material prepared in comparative example 2 according to the present invention.
Fig. 6 is an XRD pattern of the modified polycrystalline lithium-rich material prepared in comparative example 2 in the present invention.
Fig. 7 is an SEM image of the modified polycrystalline lithium-rich material prepared in comparative example 3 in the present invention.
Fig. 8 is an XRD pattern of the modified polycrystalline lithium-rich material prepared in comparative example 3 in the present invention.
Fig. 9 is an SEM image of the layered composite lithium-rich manganese-based positive electrode material prepared in example 2 of the present invention.
Fig. 10 is an XRD pattern of the layered composite lithium-rich manganese-based positive electrode material prepared in example 2 of the present invention.
Fig. 11 is an SEM image of the layered composite lithium-rich manganese-based positive electrode material prepared in example 3 of the present invention.
Fig. 12 is an XRD pattern of the layered composite lithium-rich manganese-based positive electrode material prepared in example 3 of the present invention.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention. The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications. The reagents or equipment used were conventional products available for purchase by regular vendors without the manufacturer's attention.
Example 1
Layered composite lithium-rich manganese-based positive electrode material with molecular formula of Li 1.18 Mn 0.52 Co 0.15 Ni 0.15 O 2 @Ce 0.9 Cs 0.1 O 1.9 。
The preparation method comprises the following steps:
(1) Weighing manganese sulfate, nickel sulfate and cobalt sulfate according to stoichiometric ratio, dissolving in deionized water to obtain a metal salt solution, and dissolving sodium hydroxide in deionized water to obtain a precipitant solution; mixing the metal salt solution and the sodium hydroxide solution uniformly, reacting at 50 ℃ to obtain suspension, washing, filtering and drying to obtain a manganese cobalt nickel coprecipitation precursor;
(2) Ce (NO) 3 ) 3 And CsNO 3 Dissolving in deionized water to obtain a first solution; uniformly mixing the manganese cobalt nickel coprecipitation precursor with the first solution, evaporating to dryness, and drying to obtain a modified precursor; wherein the manganese cobalt nickel coprecipitation precursor and Ce (NO) are controlled 3 ) 3 And CsNO 3 The molar ratio of (2) is 1000:9:1;
(3) And uniformly mixing the modified precursor and lithium carbonate (calculated by lithium) according to a molar ratio of 1:1.18, heating to 550 ℃ at a heating rate of 3 ℃/min after mixing, continuously heating to 900 ℃ at the same heating rate after heat preservation for 5 hours, and carrying out heat preservation for 12 hours, wherein the sintering process is carried out in an air atmosphere, and cooling to room temperature to obtain the layered composite lithium-rich manganese-based positive electrode material.
Preparing a lithium ion battery: mixing the layered composite lithium-rich manganese-based positive electrode material prepared in the embodiment 1, acetylene black, polyvinylidene fluoride and N-methyl pyrrolidone to form slurry, uniformly coating the slurry on the surface of an aluminum foil sheet to obtain a positive electrode sheet, and assembling the positive electrode sheet in a glove box by taking a lithium sheet as a negative electrode sheet and taking 1mol/L of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) solution of lithium hexafluorophosphate (the volume ratio of EC to DMC is 1:1) as electrolyte.
Comparative example 1
A conventional polycrystalline morphology lithium-rich material has a molecular formula of Li 1.18 Mn 0.52 Co 0.15 Ni 0.15 O 2 。
The preparation method comprises the following steps:
(1) Weighing manganese sulfate, nickel sulfate and cobalt sulfate according to stoichiometric ratio of lithium-rich manganese base, dissolving in deionized water to obtain a metal salt solution, and dissolving sodium hydroxide in deionized water to obtain a precipitant solution; mixing the metal salt solution and the sodium hydroxide solution uniformly, reacting at 50 ℃ to obtain suspension, washing, filtering and drying to obtain a manganese cobalt nickel coprecipitation precursor;
(2) Weighing a manganese cobalt nickel coprecipitation precursor and lithium carbonate (calculated by lithium) according to a molar ratio of 1:1.18, uniformly mixing, heating to 550 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 5 hours, continuously heating to 900 ℃ at the same heating rate, keeping the temperature for 12 hours, performing a sintering process in an air atmosphere, and cooling to room temperature to obtain the polycrystalline lithium-rich material Li 1.18 Mn 0.52 Co 0.15 Ni 0.15 O 2 。
The layered composite lithium-rich manganese-based positive electrode material prepared in example 1 was replaced with the conventional polycrystalline morphology lithium-rich material prepared in comparative example 1, and a lithium ion battery was prepared in the same manner as in example 1.
Comparative example 2
Modified polycrystalline lithium-rich material with molecular formula of Li 1.18 Mn 0.52 Co 0.15 Ni 0.15 O 2 @Ce 1.0 O 1.9 。
The preparation method comprises the following steps: (1) Weighing manganese sulfate, nickel sulfate and cobalt sulfate according to stoichiometric ratio of lithium-rich manganese base, dissolving in deionized water to obtain a metal salt solution, and dissolving sodium hydroxide in deionized water to obtain a precipitant solution; mixing the metal salt solution and the sodium hydroxide solution uniformly, reacting at 50 ℃ to obtain suspension, washing, filtering and drying to obtain a manganese cobalt nickel coprecipitation precursor; (2) The precursor and Ce (NO) are respectively weighed according to the mol ratio of 1000:10 3 ) 3 Adding the mixture into deionized water, uniformly stirring, evaporating to dryness, and drying to obtain a modified precursor P1; (3) And (3) weighing the modified precursor and lithium carbonate (calculated by lithium) according to a molar ratio of 1:1.18, uniformly mixing, heating to 550 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 5 hours, continuously heating to 900 ℃ at the same heating rate, keeping the temperature for 12 hours, performing the sintering process in an air atmosphere, and cooling to room temperature to obtain the modified precursor.
The layered composite lithium-rich manganese-based positive electrode material prepared in example 1 was replaced with the modified polycrystalline lithium-rich material prepared in comparative example 2, and a lithium ion battery was prepared in the same manner as in example 1.
Comparative example 3
Modified polycrystalline lithium-rich material Li 1.18 Mn 0.52 Co 0.15 Ni 0.15 O 2 @Cs 1.0 O 1.9 The method comprises the following specific steps: (1) Weighing manganese sulfate, nickel sulfate and cobalt sulfate according to stoichiometric ratio of lithium-rich manganese base, dissolving in deionized water to obtain a metal salt solution, and dissolving sodium hydroxide in deionized water to obtain a precipitant solution; mixing the metal salt solution and the sodium hydroxide solution uniformly, reacting at 50 ℃ to obtain suspension, washing, filtering and drying to obtain a manganese cobalt nickel coprecipitation precursor; (2) according to a molar ratio of 1000:10 respectively weighing the precursor and Cs (NO) 3 ) 3 Adding the mixture into deionized water, uniformly stirring, evaporating to dryness, and drying to obtain a modified precursor P1; (3) And (3) weighing the modified precursor and lithium carbonate (calculated by lithium) according to a molar ratio of 1:1.18, uniformly mixing, heating to 550 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 5 hours, continuously heating to 900 ℃ at the same heating rate, keeping the temperature for 12 hours, performing the sintering process in an air atmosphere, and cooling to room temperature to obtain the modified precursor.
The layered composite lithium-rich manganese-based positive electrode material prepared in example 1 was replaced with the modified polycrystalline lithium-rich material prepared in comparative example 3, and a lithium ion battery was prepared in the same manner as in example 1.
Example 2
Layered composite lithium-rich manganese-based positive electrode material with molecular formula of Li 1.18 Mn 0.52 Co 0.15 Ni 0.15 O 2 @Zr 0.9 Mo 0.1 O 1.9 。
The preparation method comprises the following steps:
(1) Weighing manganese sulfate, nickel sulfate and cobalt sulfate according to stoichiometric ratio of lithium-rich manganese base, dissolving in deionized water to obtain a metal salt solution, and dissolving sodium hydroxide in deionized water to obtain a precipitant solution; mixing the metal salt solution and sodium hydroxide solution, reacting at 50deg.C to obtain suspension, washingFiltering and drying to obtain a manganese cobalt nickel coprecipitation precursor; (2) Mixing the precursor with Zr (NO) 3 ) 4 And Mo (NO) 3 ) 3 Weighing and adding the mixture into ethanol according to a molar ratio of 1000:18:2, uniformly stirring, evaporating to dryness, and drying to obtain a modified precursor P1; (3) The modified precursor P1 and lithium carbonate (calculated by lithium) are weighed according to the mol ratio of 1:1.18, uniformly mixed and heated to 550 ℃ at the heating rate of 3 ℃/min, kept warm for 5 hours, then continuously heated to 900 ℃ at the same heating rate, kept warm for 12 hours, the sintering process is carried out in air atmosphere, and the matrix Li is obtained after cooling to room temperature 1.18 Mn 0.52 Co 0.15 Ni 0.15 O 2 Surface is coated with oxygen ion conductor Zr 0.9 Mo 0.1 O 1.9 Is a single crystal lithium-rich manganese-based positive electrode material.
Using the layered composite lithium-rich manganese-based positive electrode material prepared in this example 2, a lithium ion battery was prepared in the same manner as in example 1.
Example 3
Layered composite lithium-rich manganese-based positive electrode material with molecular formula of Li 1.18 Mn 0.52 Co 0.15 Ni 0.15 O 2 @Ce 0.8 Dy 0.2 O 1.9 。
The preparation method comprises the following steps:
(1) Weighing manganese sulfate, nickel sulfate and cobalt sulfate according to stoichiometric ratio of lithium-rich manganese base, dissolving in deionized water to obtain a metal salt solution, and dissolving sodium hydroxide in deionized water to obtain a precipitant solution; mixing the metal salt solution and the sodium hydroxide solution uniformly, reacting at 50 ℃ to obtain suspension, washing, filtering and drying to obtain a manganese cobalt nickel coprecipitation precursor; (2) Combining the precursor with Ce (NO) 3 ) 3 And Dy (NO) 3 ) 3 According to the mole ratio of 1000:8:2, weighing and adding the mixture into acetone, uniformly stirring, evaporating to dryness, and drying to obtain a modified precursor P1; (3) The modified precursor P1 and lithium carbonate (calculated by lithium) are weighed according to the mol ratio of 1:1.18, uniformly mixed and heated to 550 ℃ at the heating rate of 3 ℃/min, kept for 5 hours, then continuously heated to 900 ℃ at the same heating rate, kept for 12 hours, and sintered in the air atmosphereCooling to room temperature to obtain Li as matrix 1.18 Mn 0.52 Co 0.15 Ni 0.15 O 2 Surface-coated oxygen ion conductor Ce 0.8 Dy 0.2 O 1.9 Is a single crystal lithium-rich manganese-based positive electrode material.
Using the layered composite lithium-rich manganese-based positive electrode material prepared in this example 3, a lithium ion battery was prepared in the same manner as in example 1.
Example 4
Layered composite lithium-rich manganese-based positive electrode material with molecular formula of Li 1.18 Mn 0.52 Co 0.15 Ni 0.15 O 2 @Zr 0.9 Y 0.1 O 1.9 。
The preparation method comprises the following steps:
(1) Weighing manganese sulfate, nickel sulfate and cobalt sulfate according to stoichiometric ratio of lithium-rich manganese base, dissolving in deionized water to obtain a metal salt solution, and dissolving sodium hydroxide in deionized water to obtain a precipitant solution; mixing the metal salt solution and the sodium hydroxide solution uniformly, reacting at 50 ℃ to obtain suspension, washing, filtering and drying to obtain a manganese cobalt nickel coprecipitation precursor; (2) Mixing the precursor with Zr (NO) 3 ) 4 And Y (NO) 3 ) 3 According to the mole ratio of 1000:9:1, weighing and adding the mixture into deionized water, uniformly stirring, evaporating to dryness, and drying to obtain a modified precursor P1; (3) The modified precursor P1 and lithium carbonate (calculated by lithium) are weighed according to the mol ratio of 1:1.18, uniformly mixed and heated to 550 ℃ at the heating rate of 3 ℃/min, kept warm for 5 hours, then continuously heated to 900 ℃ at the same heating rate, kept warm for 12 hours, the sintering process is carried out in air atmosphere, and the matrix Li is obtained after cooling to room temperature 1.18 Mn 0.52 Co 0.15 Ni 0.15 O 2 Surface is coated with oxygen ion conductor Zr 0.9 Y 0.1 O 1.9 Is a single crystal lithium-rich manganese-based positive electrode material.
Using the layered composite lithium-rich manganese-based positive electrode material prepared in this example 4, a lithium ion battery was prepared in the same manner as in example 1.
Example 5
The method comprises the following steps ofLayered composite lithium-rich manganese-based positive electrode material with molecular formula of Li 1.18 Mn 0.52 Co 0.15 Ni 0.15 O 2 @Zr 0.9 Nb 0.1 O 1.9 。
The preparation method comprises the following steps:
(1) Weighing manganese sulfate, nickel sulfate and cobalt sulfate according to stoichiometric ratio of lithium-rich manganese base, dissolving in deionized water to obtain a metal salt solution, and dissolving sodium hydroxide in deionized water to obtain a precipitant solution; mixing the metal salt solution and the sodium hydroxide solution uniformly, reacting at 50 ℃ to obtain suspension, washing, filtering and drying to obtain a manganese cobalt nickel coprecipitation precursor; (2) Mixing the precursor with Zr (NO) 3 ) 4 And Nb (NO) 3 ) 3 According to the mole ratio of 1000:9:1, weighing and adding the mixture into deionized water, uniformly stirring, evaporating to dryness, and drying to obtain a modified precursor P1; (3) The modified precursor P1 and lithium carbonate (calculated by lithium) are weighed according to the mol ratio of 1:1.18, uniformly mixed and heated to 550 ℃ at the heating rate of 3 ℃/min, kept warm for 5 hours, then continuously heated to 900 ℃ at the same heating rate, kept warm for 12 hours, the sintering process is carried out in air atmosphere, and the matrix Li is obtained after cooling to room temperature 1.18 Mn 0.52 Co 0.15 Ni 0.15 O 2 Surface is coated with oxygen ion conductor Zr 0.9 Nb 0.1 O 1.9 Is a single crystal lithium-rich manganese-based positive electrode material.
Using the layered composite lithium-rich manganese-based positive electrode material prepared in this example 5, a lithium ion battery was prepared in the same manner as in example 1.
Example 6
Layered composite lithium-rich manganese-based positive electrode material with molecular formula of Li 1.18 Mn 0.52 Co 0.15 Ni 0.15 O 2 @Ce 0.9 Nb 0.1 O 1.9 。
The preparation method comprises the following steps:
(1) Weighing manganese sulfate, nickel sulfate and cobalt sulfate according to stoichiometric ratio of lithium-rich manganese base, dissolving in deionized water to obtain a metal salt solution, and dissolving sodium hydroxide in deionized water to obtain a precipitant solution; the metal salt is prepared byMixing the solution and sodium hydroxide solution uniformly, reacting at 50 ℃ to obtain suspension, washing, filtering and drying to obtain a manganese cobalt nickel coprecipitation precursor; (2) Combining the precursor with Ce (NO) 3 ) 3 And Nb (NO) 3 ) 3 According to the mole ratio of 1000:9:1, weighing and adding the mixture into deionized water, uniformly stirring, evaporating to dryness, and drying to obtain a modified precursor P1; (3) The modified precursor P1 and lithium carbonate (calculated by lithium) are weighed according to the mol ratio of 1:1.18, uniformly mixed and heated to 550 ℃ at the heating rate of 3 ℃/min, kept warm for 5 hours, then continuously heated to 900 ℃ at the same heating rate, kept warm for 12 hours, the sintering process is carried out in air atmosphere, and the matrix Li is obtained after cooling to room temperature 1.18 Mn 0.52 Co 0.15 Ni 0.15 O 2 Surface-coated oxygen ion conductor Ce 0.9 Nb 0.1 O 1.9 Is a single crystal lithium-rich manganese-based positive electrode material.
Using the layered composite lithium-rich manganese-based positive electrode material prepared in this example 6, a lithium ion battery was prepared in the same manner as in example 1.
Example 7
Layered composite lithium-rich manganese-based positive electrode material with molecular formula of Li 1.18 Mn 0.52 Co 0.15 Ni 0.15 O 2 @Ce 0.9 Cs 0.1 O 1.9 。
The preparation method comprises the following steps:
(1) Weighing manganese sulfate, nickel sulfate and cobalt sulfate according to stoichiometric ratio of lithium-rich manganese base, dissolving in deionized water to obtain a metal salt solution, and dissolving sodium hydroxide in deionized water to obtain a precipitant solution; mixing the metal salt solution and the sodium hydroxide solution uniformly, reacting at 50 ℃ to obtain suspension, washing, filtering and drying to obtain a manganese cobalt nickel coprecipitation precursor; (2) Precursor and Ce 2 （SO 4 ) 3 And Cs 2 SO 4 According to the mole ratio of 2000:9:1, weighing and adding the mixture into deionized water, uniformly stirring, evaporating to dryness, and drying to obtain a modified precursor P1; (3) The modified precursor P1 and lithium carbonate (calculated by lithium) are weighed according to the mol ratio of 1:1.18, and are evenly mixed and then heated to the temperature rising rate of 3 ℃/minHeat-preserving for 5h at 550 ℃, then continuously heating to 900 ℃ at the same heating rate, heat-preserving for 12h, sintering in air atmosphere, cooling to room temperature to obtain Li as a matrix 1.18 Mn 0.52 Co 0.15 Ni 0.15 O 2 Surface-coated oxygen ion conductor Ce 0.9 Cs 0.1 O 1.9 Is a single crystal lithium-rich manganese-based positive electrode material.
Using the layered composite lithium-rich manganese-based positive electrode material prepared in this example 7, a lithium ion battery was prepared in the same manner as in example 1.
Example 8
Layered composite lithium-rich manganese-based positive electrode material with molecular formula of Li 1.18 Mn 0.52 Co 0.15 Ni 0.15 O 2 @Ce 0.9 Cs 0.1 O 1.9 。
The preparation method comprises the following steps:
(1) Weighing manganese sulfate, nickel sulfate and cobalt sulfate according to stoichiometric ratio of lithium-rich manganese base, dissolving in deionized water to obtain a metal salt solution, and dissolving sodium hydroxide in deionized water to obtain a precipitant solution; mixing the metal salt solution and the sodium hydroxide solution uniformly, reacting at 50 ℃ to obtain suspension, washing, filtering and drying to obtain a manganese cobalt nickel coprecipitation precursor; (2) Precursor and CeCl 3 And CsCl is weighed according to the molar ratio of 1000:9:1 and added into deionized water, and the mixture is stirred uniformly, evaporated to dryness and dried to obtain a modified precursor P1; (3) The modified precursor P1 and lithium carbonate (calculated by lithium) are weighed according to the mol ratio of 1:1.18, uniformly mixed and heated to 550 ℃ at the heating rate of 3 ℃/min, kept warm for 5 hours, then continuously heated to 900 ℃ at the same heating rate, kept warm for 12 hours, the sintering process is carried out in air atmosphere, and the matrix Li is obtained after cooling to room temperature 1.18 Mn 0.52 Co 0.15 Ni 0.15 O 2 Surface-coated oxygen ion conductor Ce 0.9 Cs 0.1 O 1.9 Is a single crystal lithium-rich manganese-based positive electrode material.
Using the layered composite lithium-rich manganese-based positive electrode material prepared in this example 8, a lithium ion battery was prepared in the same manner as in example 1.
Experiment 1
The microcosmic morphology of the lithium-rich materials of examples 1 to 3 and comparative examples 1 to 2 was tested using a scanning electron microscope and X-ray powder diffraction was performed using Cu-kα as an incident light source. SEM and XRD patterns are shown in fig. 1-10, respectively.
As can be seen from the scanning electron microscope photograph of FIG. 1, the lithium-rich material obtained in example 1 has a single crystal morphology, uniform particle distribution, smooth surface and a particle size D50 of 3.8 um. As can be seen from the X-ray diffraction pattern of FIG. 2, the diffraction peaks of the material of example 1 can be marked as lamellar phases, and have characteristic peaks of lithium-rich materials and characteristic peaks of Fm-3m space groups of oxygen ion conductors.
As can be seen from the scanning electron microscope photograph of FIG. 3, the lithium-rich material of comparative example 1 has a polycrystalline morphology, and the phenomenon that particles are agglomerated into spheres is obvious. As can be seen from the X-ray diffraction pattern of fig. 4, the diffraction peaks of the lithium-rich material of comparative example 1 can be marked as lamellar phases, and have characteristic peaks of the lithium-rich material. As can be seen from comparative example 1, only a lithium-rich manganese-based material having a polycrystalline morphology can be obtained without any treatment.
As can be seen from the scanning electron microscope photograph of FIG. 5, the lithium-rich material of comparative example 2 has a polycrystalline morphology, the phenomenon that particles are agglomerated into spheres is obvious, and the size is in the nanometer scale. As can be seen from the X-ray diffraction pattern of fig. 6, the diffraction peaks of the lithium-rich material of comparative example 2 can be marked as lamellar phases, and have characteristic peaks of the lithium-rich material.
As can be seen from the scanning electron microscope photograph of FIG. 7, the lithium-rich material of comparative example 3 has a polycrystalline morphology, and the phenomenon that particles are agglomerated into spheres is obvious, and the size is in the nanometer scale. As can be seen from the X-ray diffraction pattern of fig. 8, the diffraction peaks of the lithium-rich material of comparative example 3 can be marked as lamellar phases, and have characteristic peaks of the lithium-rich material.
As is clear from comparative examples 2 and 3, no surface-coated lithium-rich single crystal positive electrode material could be obtained by adding only either element A or element B.
As can be seen from the sem photograph of fig. 9, the lithium-rich material obtained in example 2 has a single crystal morphology, uniform particle distribution, smooth surface, and a particle size D50 of 1.8 um. As can be seen from the X-ray diffraction pattern of fig. 10, the diffraction peaks of the lithium-rich material of example 2 can be marked as lamellar phases, having characteristic peaks of the lithium-rich material and characteristic peaks of Fm-3m space group.
As can be seen from the sem photograph of fig. 11, the lithium-rich material obtained in example 3 has a single crystal morphology, uniform particle distribution, smooth surface, and a particle size D50 of 2.0 um. As can be seen from the X-ray diffraction chart of fig. 12, the diffraction peak of the lithium-rich material of example 3 can be marked as a lamellar phase, and has a characteristic peak of the lithium-rich material and a characteristic peak of Fm-3m space group.
Experiment 2
Electrochemical performance tests were performed on the lithium ion batteries of examples 1 to 8 and comparative examples 1 to 3 using an electrochemical tester. The test temperature was 25 ℃. The battery was tested for its initial charge and discharge performance at a current density of 0.1C (1c=200 mA/g) and a charge voltage range of 4.8 to 2V. The detailed results are shown in Table 1.
TABLE 1
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.

Claims (10)

1. A layered composite lithium-rich manganese-based positive electrode material, characterized by comprising: a lithium-rich manganese-based matrix and an oxygen ion conductor coated on the lithium-rich manganese-based matrix;
the molecular formula of the lithium-rich manganese-based matrix is Li x Mn a Co b Ni c O 2 ；1＜x≤1.3，0.4≤a≤0.8，0＜b≤0.5，0≤c≤0.5；
The molecular formula of the oxygen ion conductor is A α B β O γ The method comprises the steps of carrying out a first treatment on the surface of the Alpha is more than or equal to 0.5 and less than or equal to 1, beta is more than or equal to 0 and less than or equal to 0.4, alpha+beta is more than or equal to 1, gamma is more than or equal to 1 and less than or equal to 2, wherein element A is at least one of Ce, zr and Bi, and element B is at least one of Cs, mo, dy, Y, nb, ba, la, al, ca, rb, sr.
2. The layered composite lithium-rich manganese-based positive electrode material according to claim 1, wherein x=1.18, a=0.52, b=0.15, c=0.15, α=0.9, β=0.1, γ=1.9;
alternatively, x=1.18, a=0.52, b=0.15, c=0.15, α=0.8, β=0.2, γ=1.9.
3. The layered composite lithium-rich manganese-based positive electrode material according to claim 1 or 2, wherein in the layered composite lithium-rich manganese-based positive electrode material, the molar ratio of the lithium-rich manganese-based matrix to the oxygen ion conductor is 1000:1-30.
4. The layered composite lithium-rich manganese-based positive electrode material according to claim 1 or 2, wherein the space group of the oxygen ion conductor is Fm-3m; when the Cu-K alpha is adopted as an incident light source for X-ray powder diffraction test, diffraction peaks are arranged at angles 25 and 35; and/or the number of the groups of groups,
the layered composite lithium-rich manganese-based positive electrode material has a microstructure of single crystal particles, and the median particle diameter is 0.1um-10um.
5. The method for preparing the layered composite lithium-rich manganese-based positive electrode material according to any one of claims 1 to 4, comprising the steps of:
weighing a manganese salt compound, a cobalt salt compound and a nickel salt compound according to the stoichiometric ratio of the lithium-rich manganese-based matrix, and dissolving the manganese salt compound, the cobalt salt compound and the nickel salt compound in deionized water to obtain a metal salt solution; dissolving a precipitator in deionized water to obtain a precipitator solution; uniformly mixing the metal salt solution and the precipitant solution, reacting at 50-60 ℃ to obtain suspension, washing, filtering and drying to obtain a manganese cobalt nickel coprecipitation precursor;
according to the stoichiometric ratio of the oxygen ion conductor, dissolving the compound of the element A and the compound of the element B into a solvent to obtain a first solution, wherein the solvent is one of deionized water, ethanol and acetone;
uniformly mixing the manganese cobalt nickel coprecipitation precursor with the first solution, and evaporating to dryness to obtain a modified precursor;
and uniformly mixing the modified precursor with a lithium source according to the stoichiometric ratio of the layered composite lithium-rich manganese-based anode material, and calcining under an oxygen-containing atmosphere to obtain the layered composite lithium-rich manganese-based anode material.
6. The method for preparing a layered composite lithium-rich manganese-based positive electrode material according to claim 5, wherein the manganese salt compound is at least one selected from manganese sulfate, manganese chloride, manganese acetate and manganese nitrate; the cobalt salt compound is at least one selected from cobalt sulfate, cobalt chloride, cobalt acetate or cobalt nitrate; the nickel salt compound is at least one selected from nickel sulfate, nickel chloride, nickel acetate or nickel nitrate; and/or the number of the groups of groups,
the precipitant is at least one of sodium carbonate, potassium carbonate, sodium hydroxide or potassium hydroxide; and/or the number of the groups of groups,
the compound Ce (NO) of element A 3 ) 3 、CeCl 3 、Ce(SO 4 ) 3 、Zr(NO 3 ) 4 、ZrCl 4 、Zr(SO 4 ) 4 、Bi(NO 3 ) 3 、BiCl 3 At least one of (a) and (b); the compound of the element B is at least one of soluble sulfate, nitrate or chloride containing Y, cs, ba, la, dy, al, mo, nb, ca, rb, sr.
7. The method for preparing a layered composite lithium-rich manganese-based positive electrode material according to claim 5 or 6, wherein the calcination conditions are: heating to 200-600 ℃ at a heating rate of 0.5-10 ℃/min, and preserving heat for 4-24 h; then heating to 600-1000 ℃ at a heating rate of 0.5-10 ℃/min, and calcining for 6-40 h.
8. A layered composite lithium-rich manganese-based positive electrode material, characterized by being prepared by the method of any one of claims 5 to 7.
9. Use of the layered composite lithium-rich manganese-based positive electrode material according to any one of claims 1-4 and 8 in lithium ion batteries.
10. A lithium ion battery comprising a positive electrode, a negative electrode and an electrolyte, wherein the positive electrode comprises the layered composite lithium-rich manganese-based positive electrode material of any one of claims 1-4, 8.
CN202410072980.XA 2024-01-18 2024-01-18 Layered composite lithium-rich manganese-based positive electrode material, and preparation method and application thereof Pending CN117594783A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180183045A1 (en) * 2016-12-28 2018-06-28 Sichuan FuHua New Energy High-Tech Co., LTD. High-voltage ternary positive electrode material for lithium-ion battery and preparation method thereof
CN109560265A (en) * 2018-11-02 2019-04-02 中国电力科学研究院有限公司 A kind of effective method for coating for inhibiting lithium-rich manganese-based anode material oxygen to be lost
WO2019083157A1 (en) * 2017-10-26 2019-05-02 주식회사 엘지화학 Positive electrode active material comprising lithium-rich lithium manganese oxide having formed thereon coating layer comprising lithium-deficient transition metal oxide, and lithium secondary battery comprising same
CN110707315A (en) * 2019-11-26 2020-01-17 河北省科学院能源研究所 Surface modified nickel-based electrode material
CN113410457A (en) * 2020-03-17 2021-09-17 青岛中科泰新能源材料有限公司 Modification method of lithium-rich oxide positive electrode material
CN114229921A (en) * 2021-12-22 2022-03-25 西南科技大学 Al2O3-ZrO2Coated lithium-rich manganese-based positive electrode material and preparation method thereof
WO2023236068A1 (en) * 2022-06-08 2023-12-14 宁德时代新能源科技股份有限公司 Positive electrode active material and manufacturing method therefor, electrode plate, secondary battery, and electrical apparatus

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180183045A1 (en) * 2016-12-28 2018-06-28 Sichuan FuHua New Energy High-Tech Co., LTD. High-voltage ternary positive electrode material for lithium-ion battery and preparation method thereof
WO2019083157A1 (en) * 2017-10-26 2019-05-02 주식회사 엘지화학 Positive electrode active material comprising lithium-rich lithium manganese oxide having formed thereon coating layer comprising lithium-deficient transition metal oxide, and lithium secondary battery comprising same
CN109560265A (en) * 2018-11-02 2019-04-02 中国电力科学研究院有限公司 A kind of effective method for coating for inhibiting lithium-rich manganese-based anode material oxygen to be lost
CN110707315A (en) * 2019-11-26 2020-01-17 河北省科学院能源研究所 Surface modified nickel-based electrode material
CN113410457A (en) * 2020-03-17 2021-09-17 青岛中科泰新能源材料有限公司 Modification method of lithium-rich oxide positive electrode material
CN114229921A (en) * 2021-12-22 2022-03-25 西南科技大学 Al2O3-ZrO2Coated lithium-rich manganese-based positive electrode material and preparation method thereof
WO2023236068A1 (en) * 2022-06-08 2023-12-14 宁德时代新能源科技股份有限公司 Positive electrode active material and manufacturing method therefor, electrode plate, secondary battery, and electrical apparatus

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
张龙等: "氧离子导体表面包覆对Li2MnO3正极材料性能的影响", 《功能材料》, vol. 54, no. 10, 30 October 2023 (2023-10-30), pages 10136 - 10154 *
蔺佳明;赵桃林;王育华;: "Li_2ZrO_3包覆锂离子电池正极材料Li[Li_(0.2)Ni_(0.2)Mn_(0.6)]O_2的制备及其电化学性能", 材料工程, no. 03, 20 March 2020 (2020-03-20) *

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