CN113215647B - High-voltage single crystal ternary cathode material - Google Patents

High-voltage single crystal ternary cathode material Download PDF

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CN113215647B
CN113215647B CN202110416541.2A CN202110416541A CN113215647B CN 113215647 B CN113215647 B CN 113215647B CN 202110416541 A CN202110416541 A CN 202110416541A CN 113215647 B CN113215647 B CN 113215647B
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cobalt
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sodium
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CN113215647A (en
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欧星
李欢
明磊
张佳峰
张宝
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Pawa Lanxi New Energy Technology Co ltd
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Central South University
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    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B1/00—Single-crystal growth directly from the solid state
    • C30B1/10—Single-crystal growth directly from the solid state by solid state reactions or multi-phase diffusion
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
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    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

A high-voltage single crystal ternary anode material. The general formula of the material is LiNixCoyMnzNaaBbO2@mAl2O3Wherein x is more than or equal to 0.5<1，0<y≤0.3，0<z≤0.3，x+y+z＝1；0≤a≤0.05，0≤b≤0.05，0<m is less than or equal to 0.05. The method comprises the following steps: ni is synthesized by taking nickel salt, cobalt salt and manganese salt as raw materials and adopting a coprecipitation methodxCoyMnz(OH)2A spherical hydroxide precursor; mixing the precursor powder with a lithium source, a boron source and a sodium source through a high-energy mixer, roasting at 530 ℃ for 4-6 hours, and roasting at 820 ℃ for 12 hours; dispersing the sintered agglomerated particles by adopting a flat impact type jet mill to obtain a dispersed nickel-cobalt-manganese single crystal material; and calcining the single crystal material and an aluminum source at the high temperature of 500-600 ℃ in the air environment. The invention is tested by experiments, the voltage is improved to 4.6V, the high-voltage cycle performance is stable, and the first charge-discharge specific capacity reaches 184 mAh/g.

Description

High-voltage single crystal ternary cathode material
Technical Field
The invention relates to the field of battery materials, in particular to a high-voltage single crystal ternary cathode material and a preparation method thereof.
Background
With the development and utilization of new energy, lithium ion batteries have attracted extensive attention due to their advantages of high energy density, long service life, low self-discharge degree, no memory effect, environmental protection, and the like. The nickel-cobalt-manganese ternary cathode material has the advantages of excellent thermal stability, higher reversible capacity, low cost and the like, and is one of the most promising lithium ion battery cathode materials.
However, the charge-discharge voltage performance of the nickel-cobalt-manganese ternary positive electrode material battery is unstable, and further research on how to improve the performance of the nickel-cobalt-manganese ternary positive electrode material battery is needed.
CN 109065880A discloses an alumina-coated single crystal nickel-cobalt-manganese ternary material and a preparation method thereof. The chemical formula of the anode material is LiNi0.5Co0.2Mn0.3Mx02Wherein x is 0.01-0.1. The preparation method comprises the following steps: (1) preparing a doped nickel-cobalt manganese hydroxide precursor precipitate by a coprecipitation method; (2) and (3) mixing the hydroxide precursor with lithium carbonate or lithium hydroxide in a weight ratio of 100: 42-43, forming a pasty mixture, drying, crushing, and sieving with a 160-mesh sieve; (3) loading into an alumina crucible, and performing high-temperature roasting in an oxidation furnace, wherein the roasting procedure is carried out in two steps, namely, the temperature is increased to 8000 ℃ at the first step, and the temperature is kept for 5-10 hours; secondly, continuously and slowly heating to 900-; (4) crushing the sintered body, classifying the crushed body by air flow to obtain lithium nickel manganese oxide powder with the center granularity of 4-8 microns, adding the lithium nickel manganese oxide powder into weak acid pure water, heating to 30-50 ℃, stirring for 60 minutes, standing, and pouring supernatant; preparing alumina sol, slowly adding a certain amount of aluminum nitrate solution pure water into dilute ammonia water to adjust the pH of a system, and forming translucent alumina sol; adding the alumina sol into lithium nickel cobalt manganese oxide powder slurry, wherein the weight ratio of the alumina sol to the lithium nickel cobalt manganese oxide is 1-2:100, stirring for 60 minutes, performing suction filtration, drying and sieving for later use; (5) and carrying out secondary low-temperature atmosphere heat treatment on the powder, wherein the roasting heat treatment temperature is about 400-7000 ℃, the treatment time is 3-5 hours, and the powder is subjected to neutral atmosphere such as nitrogen or hydrogen to obtain the high-voltage single crystal nickel-cobalt manganese ternary material powder. The charging voltage reaches 4.5V, the energy density of the electrode is higher than 25% of that of lithium cobalt oxide, and the cost is lower than more than 25% of that of lithium cobalt oxide.
In the scheme, the aluminum oxide is selected to coat the single crystal nickel-cobalt-manganese ternary material, so that the performance of the material is improved to a certain extent, but the voltage, the high-temperature performance and the cycle performance of the material have a further improved space.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing a high-voltage single crystal ternary cathode material. The battery assembled by the anode material has high initial discharge capacity, high charge and discharge voltage and good cycle stability.
The invention further aims to solve the technical problem of overcoming the defects in the prior art and providing a preparation method of the high-voltage single-crystal ternary cathode material. The preparation method is simple and reasonable, and the cost is low.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a high-voltage single-crystal ternary positive electrode material with chemical formula LiNi and its preparation methodxCoyMnzNaaBbO2@mAl2O 3. Wherein x is more than or equal to 0.5<1，0<y≤0.3，0<z≤0.3，x+y+z＝1；0≤a≤0.05，0≤b≤0.05，0<m≤0.05。
The technical scheme adopted for further solving the technical problems is as follows:
a high-voltage single crystal ternary anode material and a preparation method thereof comprise the following steps:
(1) ni is synthesized by taking nickel salt, cobalt salt and manganese salt as raw materialsxCoyMnz(OH)2A spherical hydroxide precursor;
(2) mixing the precursor powder in the step (1) with a lithium source, a boron source and a sodium source through a high-energy mixer, roasting for 4-6 hours at 530 ℃, and roasting for 12 hours at 820 ℃;
(3) dispersing the sintered agglomerated particles in the step (2) by adopting a flat impact type jet mill to obtain a dispersed nickel-cobalt-manganese single crystal material;
(4) calcining the single crystal material and the aluminum source in the step (3) at the air environment of 500-600 ℃ for 10-12 hours to obtain the LiNixCoyMnzNaaBbO2@mAl2O3A material;
wherein x is more than or equal to 0.5 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.3, z is more than 0 and less than or equal to 0.3, and x + y + z is equal to 1; a is more than or equal to 0 and less than or equal to 0.05, b is more than or equal to 0 and less than or equal to 0.05, and m is more than 0 and less than or equal to 0.05.
Preferably, in the step (1), the nickel salt is selected from one or more of nickel sulfate, nickel nitrate and halides of nickel.
Preferably, in the step (1), the cobalt salt is selected from one or more of cobalt sulfate, cobalt nitrate and cobalt halide.
Preferably, in the step (1), the manganese salt is selected from one or more of manganese sulfate, manganese nitrate and manganese halide.
Preferably, in the step (2), the lithium source is one or more selected from lithium hydroxide, lithium carbonate and lithium nitrate.
Preferably, in the step (2), the boron source is selected from one or more of diboron trioxide, boric acid and sodium borate.
Preferably, in the step (2), the sodium source is selected from one or more of sodium nitrate, sodium sulfate, sodium carbonate, sodium chloride and sodium phosphate.
Preferably, in the step (4), the aluminum source is selected from one or more of aluminum nitrate, aluminum sulfate and aluminum chloride.
The invention has the beneficial effects that
(1) The anode material is single crystal particles, has excellent electrochemical performance, and the first discharge specific capacity of the battery assembled by the anode material reaches 184mAh/g under 1C, and the charge-discharge voltage reaches 4.6V under 0.2C.
(2) The preparation method is simple and easy to implement, has little environmental pollution and excellent economic benefit, and has good value.
Drawings
Fig. 1 is an XRD pattern of the positive electrode material obtained in example 2 of the present invention;
FIG. 2 is an SEM image of a positive electrode material obtained in example 2 of the present invention;
fig. 3 is a first charge-discharge curve diagram of the positive electrode material obtained in example 2 of the present invention.
Detailed Description
The invention is further illustrated by the following specific examples and figures.
Example 1
(1) In terms of molar ratio, 1moL/L of 5moL of NiSO4·6H2O, 2moL of CoSO4·7H2O, 3moL MnSO4·H2O (Ni: Co: Mn: 5:2:3) was uniformly mixed, and at the same time, NaOH solution (20moL) was added to the reaction tank. The pH was adjusted to 10.2 and the ammonia concentration was 2.5 mol/L. Coprecipitation reaction is carried out, and pure water is used for filtering, washing and drying to obtain precursor Ni0.5Co0.2Mn0.3(OH)2。
(2) In terms of molar ratio, LiNO3And Ni0.5Co0.2Mn0.3(OH)2Precursor material metal ion ratio Li: (Ni + Co + Mn) ═ 1.05:1 ratio, 1moL of Ni was weighed0.5Co0.2Mn0.3(OH)21.05moL of LiNO3Then 0.001moL of NaNO is weighed3And 0.001moL of B2O3. The obtained Ni0.5Co0.2Mn0.3(OH)2Precursor material and LiNO3、NaNO3、B2O3Uniformly mixing, and mixing for 10 hours in a mixing tank; sintering in air atmosphere for two stages, roasting at 530 deg.C for 4-6 hr, roasting at 820 deg.C for 12 hr, naturally cooling to 90 deg.C, taking out sample to obtain positive electrode material Li (Ni)0.5Co0.2Mn0.3)Na0.001B0.002O2。
(3) In terms of mole ratio, as Al (NO)3)3With Li (Ni) as a positive electrode material0.5Co0.2Mn0.3)Na0.001B0.002O2The ratio of Al: (Ni + Co + Mn) ═ 0.02:1 ratio, 0.02moL of Al (NO) was weighed3)3And the positive electrode material Li (Ni) obtained in the step (2)0.5Co0.2Mn0.3)Na0.001B0.002O2Calcining at high temperature of 500-600 ℃ for 10-12 hours, naturally cooling to 90 ℃ and taking out a sample to obtain Li (Ni)0.5Co0.2Mn0.3)Na0.001B0.002O2@0.02Al2O3A material.
The cathode material obtained in the embodiment is adopted to assemble a battery: under the multiplying power of 1C, the first discharge specific capacity reaches 180.2mAh/g, 50 cycles are carried out under 1C, the capacity is 163.5mAh/g, and the capacity retention rate reaches 90.7%.
Example 2
(1) In terms of molar ratio, 1moL/L of 5moL of NiSO4·6H2O, 2moL of CoSO4·7H2O, 3moL MnSO4·H2O (Ni: Co: Mn: 5:2:3) was uniformly mixed, and at the same time, NaOH solution (20moL)Adding into a reaction tank. The pH was adjusted to 10.2 and the ammonia concentration was 2.5 mol/L. Coprecipitation reaction is carried out, and pure water is used for filtering, washing and drying to obtain precursor Ni0.5Co0.2Mn0.3(OH)2。
(2) In terms of molar ratio, LiNO3And Ni0.5Co0.2Mn0.3(OH)2Precursor material metal ion ratio Li: (Ni + Co + Mn) ═ 1.05:1 ratio, 1moL of Ni was weighed0.5Co0.2Mn0.3(OH)21.05moL of LiNO3Then 0.001moL of NaNO is weighed3And 0.002moL of B2O3. The obtained Ni0.5Co0.2Mn0.3(OH)2Precursor material and LiNO3、NaNO3、B2O3Uniformly mixing, and mixing for 10 hours in a mixing tank; sintering in air atmosphere for two stages, roasting at 530 deg.C for 4-6 hr, roasting at 820 deg.C for 12 hr, naturally cooling to 90 deg.C, taking out sample to obtain positive electrode material Li (Ni)0.5Co0.2Mn0.3)Na0.001B0.004O2。
(3) In terms of mole ratio, as Al (NO)3)3With Li (Ni) as a positive electrode material0.5Co0.2Mn0.3)Na0.001B0.004O2The ratio of Al: (Ni + Co + Mn) ═ 0.02:1 ratio, 0.02moL of Al (NO) was weighed3)3And the positive electrode material Li (Ni) obtained in the step (2)0.5Co 0.2Mn0.3)Na0.001B0.004O2Calcining at high temperature of 500-600 ℃ for 10-12 hours, naturally cooling to 90 ℃ and taking out a sample to obtain Li (Ni)0.5Co0.2Mn0.3)Na0.001B0.004O2@0.02Al2O3A material.
The cathode material obtained in the embodiment is adopted to assemble a battery: under the multiplying power of 1C, the first discharge specific capacity reaches 184.2mAh/g, 50 cycles are carried out under the multiplying power of 1C, the capacity is 169.88mAh/g, and the capacity retention rate reaches 92.2%.
Example 3
(1) In terms of mole ratioFirstly, 1moL/L of 5moL of NiSO4·6H2O, 2moL of CoSO4·7H2O, 3moL MnSO4·H2O (Ni: Co: Mn: 5:2:3) was uniformly mixed, and at the same time, NaOH solution (20moL) was added to the reaction tank. The pH was adjusted to 10.2 and the ammonia concentration was 2.5 mol/L. Coprecipitation reaction is carried out, and pure water is used for filtering, washing and drying to obtain precursor Ni0.5Co0.2Mn0.3(OH)2。
(2) In terms of molar ratio, LiNO3And Ni0.5Co0.2Mn0.3(OH)2Precursor material metal ion ratio Li: (Ni + Co + Mn) ═ 1.05:1 ratio, 1moL of Ni was weighed0.5Co0.2Mn0.3(OH)21.05moL of LiNO3Then 0.001moL of NaNO is weighed3And 0.003moL of B2O3. The obtained Ni0.5Co0.2Mn0.3(OH)2Precursor material and LiNO3、NaNO3、B2O3Uniformly mixing, and mixing for 10 hours in a mixing tank; sintering in air atmosphere for two stages, roasting at 530 deg.C for 4-6 hr, roasting at 820 deg.C for 12 hr, naturally cooling to 90 deg.C, taking out sample to obtain positive electrode material Li (Ni)0.5Co0.2Mn0.3)Na0.001B0.006O2。
(3) In terms of mole ratio, as Al (NO)3)3With Li (Ni) as a positive electrode material0.5Co0.2Mn0.3)Na0.001B0.006O2The ratio of Al: (Ni + Co + Mn) ═ 0.02:1 ratio, 0.02moL of Al (NO) was weighed3)3. The positive electrode material Li (Ni) obtained in the step (2)0.5Co 0.2Mn0.3)Na0.001B0.006O2Calcining at high temperature of 500-600 ℃ for 10-12 hours, naturally cooling to 90 ℃ and taking out a sample to obtain Li (Ni)0.5Co0.2Mn0.3)Na0.001B0.006O2@0.02Al2O3A material.
The cathode material obtained in the embodiment is adopted to assemble a battery: under the multiplying power of 1C, the first discharge specific capacity reaches 179.5mAh/g, 50 cycles are carried out under 1C, the capacity is 163.8mAh/g, and the capacity retention rate reaches 91.2%.
Comparative example 1
(1) In terms of molar ratio, 1moL/L of 5moL of NiSO4·6H2O, 2moL of CoSO4·7H2O, 3moL MnSO4·H2O (Ni: Co: Mn: 5:2:3) was uniformly mixed, and at the same time, NaOH solution (20moL) was added to the reaction tank. The pH was adjusted to 10.2 and the ammonia concentration was 2.5 mol/L. Coprecipitation reaction is carried out, and pure water is used for filtering, washing and drying to obtain precursor Ni0.5Co0.2Mn0.3(OH)2。
(2) In terms of molar ratio, LiNO3And Ni0.5Co0.2Mn0.3(OH)2Precursor material metal ion ratio Li: (Ni + Co + Mn) ═ 1.05:1 ratio, 1moL of Ni was weighed0.5Co0.2Mn0.3(OH)21.05moL of LiNO3The obtained Ni0.5Co0.2Mn0.3(OH)2Precursor material and LiNO3Uniformly mixing the materials, and mixing the materials in a mixing tank for 10 hours; sintering in air atmosphere for two stages, roasting at 530 deg.C for 4-6 hr, roasting at 820 deg.C for 12 hr, naturally cooling to 90 deg.C, taking out sample to obtain positive electrode material LiNi0.5Co0.2Mn0.3O2。
The cathode material obtained in the embodiment is adopted to assemble a battery: under the multiplying power of 1C, the first discharge specific capacity reaches 150.6mAh/g, 50 cycles are carried out under 1C, the capacity is 131.6mAh/g, and the capacity retention rate reaches 87.4%.
In conclusion, the ternary cathode material modified by sodium and boron codoping and aluminum coating is greatly improved in cycle performance, rate performance and charge-discharge voltage.

Claims (3)

1. A high-voltage single-crystal ternary positive electrode material with chemical formula LiNixCoyMnzNaaBbO2@mAl2O3Wherein x is more than or equal to 0.5<1，0<y≤0.3，0<z≤0.3，x+y+z=1；0≤a≤0.05，0≤b≤0.05，0<m≤0.05。
2. The preparation method of the high-voltage single-crystal ternary cathode material according to claim 1, comprising the following steps:
(1) ni is synthesized by taking nickel salt, cobalt salt and manganese salt as raw materialsxCoyMnz(OH)2A spherical hydroxide precursor;
(2) mixing the precursor powder in the step (1) with a lithium source, a boron source and a sodium source through a high-energy mixer, roasting for 4-6 hours at 530 ℃, and roasting for 12 hours at 820 ℃;
(3) dispersing the sintered agglomerated particles in the step (2) by adopting a flat impact type jet mill to obtain a dispersed nickel-cobalt-manganese single crystal material;
(4) calcining the single crystal material and the aluminum source in the step (3) at the air environment of 500-600 ℃ for 10-12 hours to obtain the LiNixCoyMnzNaaBbO2@mAl2O3A material;
wherein x is more than or equal to 0.5 and less than 1, y is more than 0 and less than or equal to 0.3, z is more than 0 and less than or equal to 0.3, and x + y + z = 1; a is more than or equal to 0 and less than or equal to 0.05, b is more than or equal to 0 and less than or equal to 0.05, and m is more than 0 and less than or equal to 0.05.
3. The preparation method of the high-voltage single-crystal ternary cathode material according to claim 2, wherein in the step (1), the nickel salt is selected from one or more of nickel sulfate, nickel nitrate and halides of nickel; the cobalt salt is selected from one or more of cobalt sulfate, cobalt nitrate and halides of cobalt; the manganese salt is selected from one or more of manganese sulfate, manganese nitrate and manganese halide; in the step (2), the lithium source is one or more selected from lithium hydroxide, lithium carbonate and lithium nitrate; the boron source is selected from one or more of diboron trioxide, boric acid and sodium borate; the sodium source is selected from one or more of sodium nitrate, sodium sulfate, sodium carbonate, sodium chloride and sodium phosphate; in the step (4), the aluminum source is selected from one or more of aluminum nitrate, aluminum sulfate and aluminum chloride.
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