CN113823786A - Modified lithium-rich manganese-based positive electrode material and preparation method thereof - Google Patents

Modified lithium-rich manganese-based positive electrode material and preparation method thereof Download PDF

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CN113823786A
CN113823786A CN202111168120.9A CN202111168120A CN113823786A CN 113823786 A CN113823786 A CN 113823786A CN 202111168120 A CN202111168120 A CN 202111168120A CN 113823786 A CN113823786 A CN 113823786A
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lithium
solution
positive electrode
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张梦霞
王萌
初茉
陈林
左玲立
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China University of Mining and Technology Beijing CUMTB
Beijing National Innovation Institute of Lightweight Ltd
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China University of Mining and Technology Beijing CUMTB
Beijing National Innovation Institute of Lightweight Ltd
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Abstract

The invention provides a preparation method of a modified lithium-rich manganese-based positive electrode material, and belongs to the technical field of lithium ion battery positive electrode materials and preparation thereof. The single crystal fast lithium ion conductor coated lithium-rich manganese-based positive electrode material obtained by simultaneously carrying out single crystal and surface coating treatment through a ball milling method has the advantages of high coulombic efficiency, high capacity retention rate and high tap density, and meanwhile, the coating layer can inhibit a lamellar phase from being converted into a spinel phase, so that the structural stability of the lithium-rich positive electrode material is improved. The modification method can be applied to modification of most of anode materials, and has the advantages of simple modification process and convenient operation.

Description

Modified lithium-rich manganese-based positive electrode material and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials and preparation thereof, and particularly relates to a preparation method of a single-crystal-form fast lithium ion-coated layered lithium-rich manganese-based anode material.
Background
Lithium-rich cathode material due to its high specific discharge capacity ()>250mAhg-1) The method becomes a hot research topic in the research field of lithium ion cathode materials. The precursor prepared by taking carbonate as a precipitator releases a large amount of CO in the pre-sintering stage2Leading to the material being loose and porous and the tap density being reduced. The single crystal modification treatment is carried out on the traditional lithium-rich manganese-based cathode material in a polycrystalline form, so that the tap density of the material can be improved, but the increased specific surface area enables the material to easily generate side reaction with electrolyte, the first-cycle coulombic efficiency of the material is reduced, the irreversible release of oxygen in the first-cycle charging and discharging process is aggravated, the migration of transition metal ions from the surface to the bulk phase is accelerated, the material is converted from a lamellar phase to a spinel phase, and the capacity retention rate and the structural stability of the material are reduced. Aiming at the problem, the single crystal material is coated with the lithium ion conductor quickly, so that the structural stability of the material can be improved, the migration rate of lithium ions can be improved, and the electrochemical performance of the material can be enhanced.
The surface coating modification and the preparation of the single crystal form cathode material generally increase the experimental steps, and the experimental complexity is high. Therefore, the development of a lithium-rich manganese-based material which is simple and convenient in modification preparation process, easy to operate, excellent in electrochemical performance and good in structural stability is an urgent need of the current lithium ion battery anode material market.
Disclosure of Invention
In view of the above, the present invention provides a modified lithium-rich manganese-based positive electrode material and a preparation method thereof, and the method provided by the invention is simple and easy to operate, and the obtained modified lithium-rich manganese-based positive electrode material has good electrochemical properties and structural stability.
The invention provides a preparation method of a modified lithium-rich manganese-based positive electrode material, which comprises the following specific process steps:
(1) dissolving bivalent soluble salts of transition metals of nickel, cobalt and manganese into deionized water according to a stoichiometric ratio to prepare 1.0-6.0 molL-1The transition metal salt mixed solution A; dissolving the precipitator powder in deionized water to prepare a precipitator solution B with the same concentration and the same volume as the transition metal salt mixed solution; adding a certain amount of ammonia water, concentrated ammonia water or ammonium salt into deionized water to prepare 0.2-1.2 mol L-1The chelating assistant C is prepared by mixing a transition metal salt mixed solution and a complexing assistant, wherein the volume of the transition metal salt mixed solution is the same as that of the complexing assistant, and the concentration ratio of the transition metal salt mixed solution to the complexing assistant is 1: 0.2; lithium salt with stoichiometric ratio is dissolved in deionized water with the same volume to prepare a lithium salt solution D. The divalent soluble salt of transition metal manganese, cobalt and nickel is one or more of sulfate, chloride, nitrate and acetate. The raw material of the precipitator is one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate and ammonium bicarbonate; the chelating auxiliary agent is 0.2-1.2 mol L prepared by adding deionized water into one or more of liquid ammonia, concentrated ammonia water and ammonium salt-1The lithium salt is one or more of lithium carbonate, lithium hydroxide, lithium nitrate and lithium acetate.
(2) And (2) quickly mixing the solution B and the solution C prepared in the step (1) to obtain a solution E, slowly dripping the solution A and the solution D into the solution E to prepare a mixed solution F, transferring the mixed solution F into a 100mL stainless steel autoclave lined with polytetrafluoroethylene (the volume filling rate is 80%), heating to 100-300 ℃, preserving the heat for 5-24 hours, and cooling to room temperature. Centrifugally cleaning, and then placing in a vacuum drying oven at 30-100 ℃ for drying for 5-24 h to obtain precursor powder.
(3) And (3) pouring the precursor powder prepared in the step (2) into a corundum ark, placing the corundum ark in a tube furnace, keeping air circulation or in a flowing atmosphere, controlling the heating rate to be 2-10 ℃/min, heating to 300-700 ℃, calcining for 3-10 h, and cooling to room temperature to obtain the black transition metal oxide powder.
(4) And (4) placing the transition metal oxide in the step (3) in a tube furnace in an oxygen atmosphere, controlling the heating rate to be 2-10 ℃/min, heating to 750-1050 ℃, sintering for 10-24 h, and cooling to room temperature to obtain the polycrystalline lithium-rich manganese-based positive electrode material.
(5) Weighing the polycrystalline lithium-rich manganese-based positive electrode material obtained in the step (4) to obtain a weighed mass m1Weighing the corresponding substances according to the weight percentage of 1-5 percentMixing and grinding fast lithium ion conductor salt in a mortar simply, and weighing the mass m2And (3) according to the mass ratio of ball materials of 5-15: 1, putting 1g of anhydrous ethanol and 1-5 ml of material in a zirconia ball milling tank for ball milling for 0.5-5 h. The fast lithium ion conductor coating salt is one or more of lithium phosphate, lithium lanthanum, lithium zirconate, lithium aluminate, lithium chromate, lithium cerate, lithium titanate, lithium molybdate and lithium titanate, or is formed by calcining and combining lithium salt, phosphate, lanthanum salt, zirconate, aluminate, chromate, cerate, molybdate and titanate at high temperature.
(6) And (5) putting the ball-milled material in the step (5) into a vacuum drying oven at the temperature of 50-80 ℃, and performing vacuum drying for 2-12 hours. And (3) placing the dried powder in a corundum ark, controlling the heating rate to be 2-10 ℃/min, heating to 300-700 ℃, and tempering for 3-12 h to obtain the quick lithium ion coated single crystal lithium-rich manganese-based positive electrode material.
The lithium-rich manganese-based cathode material synthesized by the method, acetylene black and polyvinylidene fluoride are mixed according to the weight ratio of 85: 10: and 5, mixing and coating on an aluminum foil current collector in a mass ratio, tabletting by using a scraper with the specification of 150um, drying in a drying oven at the temperature of 30-100 ℃ for 5-24 h, and cutting into a circular pole piece with the diameter of 12.00mm by using a slicing machine. In a glove box filled with argon, the cut pole piece is a positive pole, the metal lithium piece is a negative pole, a Celgard 2500 type diaphragm and 1M LiPF prepared from ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate according to the proportion of 1:1:1 are used6And assembling the electrolyte into a CR2025 button cell. The charge-discharge cycle performance and the rate capability under the voltage of 2.0V-4.8V are tested on a Land test system (CT2001A), and the test result is shown in figure 3.
The invention has the characteristics and advantages that: the invention combines the surface coating treatment and the single crystal treatment into a process, can simplify the experimental process, selects the fast lithium ion conductor as the coating material while obtaining the high tap density single crystal material, can inhibit the structural phase change of the surface, supports the lithium ion channel, improves the migration rate of lithium ions, and promotes the cycling stability, the multiplying power stability and the structural stability of the material.
Description of the drawings:
FIG. 1 is a process for preparing single crystal Li according to the present invention3PO4Coated lithium-rich manganese-based positive electrode material Li1.2Mn0.54Ni0.13Co0.13O2Scanning Electron Microscope (SEM) photographs at ten thousand times magnification.
FIG. 2 shows the preparation of single crystal Li according to the present invention3PO4And Scanning Electron Microscope (SEM) pictures of the coated lithium-rich manganese-based cathode material with magnification of forty thousand times.
Fig. 3 is an XRD chart of the single-crystal coated lithium-rich manganese-based positive electrode material prepared in example one, two, and three.
FIG. 4 shows a single crystal Li prepared in the first example3PO4First cycle charge-discharge diagram of the coated lithium-rich manganese-based positive electrode material.
FIG. 5 shows a single crystal Li prepared in the first example3PO4And the multiplying power of 0.1C, 1C, 2C, 3C, 4C, 5C, 6C and 7C of the lithium-rich manganese-based cathode material is shown.
FIG. 6 shows a single crystal Li prepared in the first example3PO4And (3) a 100-cycle discharge specific capacity graph at 1.0 ℃ of the coated lithium-rich manganese-based positive electrode material.
FIG. 7 shows a single crystal LiLaO prepared in example two2First cycle charge-discharge diagram of the coated lithium-rich manganese-based positive electrode material.
FIG. 8 shows a single crystal LiLaO prepared in example II2And the multiplying power of 0.1C, 1C, 2C, 3C, 4C, 5C, 6C and 7C of the lithium-rich manganese-based cathode material is shown.
FIG. 9 shows a single crystal LiLaO prepared in example two2And (3) a 100-cycle discharge specific capacity graph at 1.0 ℃ of the coated lithium-rich manganese-based positive electrode material.
FIG. 10 is a single crystal LiAlO prepared in example III2First cycle charge-discharge diagram of the coated lithium-rich manganese-based positive electrode material.
FIG. 11 is a single crystal LiAlO prepared in example III2And the multiplying power of 0.1C, 1C, 2C, 3C, 4C, 5C, 6C and 7C of the lithium-rich manganese-based cathode material is shown.
FIG. 12 is a single crystal LiAlO prepared in example III2Coated lithium-rich manganese-based positive electrode materialThe specific capacity of the material discharged in 100 cycles under 1.0C.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings, specific examples and comparative examples, but the present invention is not limited thereto.
Example one
(1) 4.5635g of MnSO4·H2O，1.7085g NiSO4·6H2O，1.8265g CoSO4·7H2O in 40ml of deionized water to give a transparent transition metal salt solution A, 4.3244g of Na2CO3Dissolving in 40ml deionized water to obtain transparent precipitant solution B, diluting with 0.60ml 25% concentrated ammonia water in 40ml deionized water to obtain 0.2mol L-1The ammonia chelating assistant C (2.5176 g LiOH. H)2And dissolving O in 40mL of deionized water to obtain a lithium salt solution D.
(2) And (2) quickly mixing the solution B and the solution C prepared in the step (1) to obtain a solution E, slowly dripping the solution A and the solution D into the solution E to prepare a mixed solution F, transferring the mixed solution F into a 100mL stainless steel autoclave lined with polytetrafluoroethylene (the volume filling rate is 80%), heating to 160 ℃, preserving heat for 12 hours and cooling to room temperature. Centrifugally cleaning, placing in a vacuum drying oven at 80 ℃, and drying for 12h to obtain precursor powder.
(3) And (3) placing the precursor powder obtained in the step (2) in a corundum ark, then placing the corundum ark in a tube furnace, heating to 550 ℃ at a heating rate of 5 ℃/min in the air atmosphere, preserving the temperature for 5 hours, and cooling at room temperature to obtain 1.0109g of black transition metal oxide.
(4) And (3) placing the mixture obtained in the step (3) in a corundum square boat, then placing the square boat in a tube furnace, introducing oxygen, controlling the heating rate to be 5 ℃/min, heating to 900 ℃, preserving heat for 10 hours, and then cooling at room temperature to obtain 1.2550g of the lithium-rich polycrystalline anode material.
(5) Calculating to obtain Li required for coating according to 1% of the mass of the lithium-rich polycrystalline material prepared in the step (4)3PO4Mixing the materials in a mortar, weighing the materials according to the ball material mass ratio of 9:1, and adding absolute ethyl alcohol into the materials1g in a ratio of 1.6ml to 1g, and placing the mixture into a zirconia ball milling tank for ball milling for 1 hour.
(6) And (3) putting the ball-milled material into a vacuum drying box at the temperature of 80 ℃, and performing vacuum drying for 5 hours. Placing the dried powder in a corundum ark, controlling the heating rate to be 5 ℃/min, heating to 500 ℃, and tempering for 5h to obtain Li3PO4Coated single crystal lithium-rich manganese-based positive electrode material Li1.2Mn0.54Ni0.13Co0.13O2And is denoted as LR 1.
Li synthesized in this example1.2Mn0.54Ni0.13Co0.13O2The cathode materials, acetylene black and polyvinylidene fluoride were mixed in a ratio of 85: 10: 5 mass ratio mixing coating on the aluminium foil current collector, use the scraper of 150um specification to carry out the preforming, dry 12h in the drying cabinet is placed in to 80 ℃, use the slicer to cut into the circular pole piece of diameter 12.00 mm. In a glove box filled with argon, the cut pole piece is a positive pole, the metal lithium piece is a negative pole, a Celgard 2500 type diaphragm and 1M LiPF prepared from ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate according to the proportion of 1:1:1 are used6And assembling the electrolyte into a CR2025 button cell. The charge-discharge cycle performance and the rate capability under the voltage of 2.0V-4.8V are tested on a Land test system (CT2001A), and the test result is shown in figure 3.
Example two
(1) 4.5635g of MnSO4·H2O，1.7085g NiSO4·6H2O，1.8265g CoSO4·7H2O in 40ml of deionized water to give a transparent transition metal salt solution A, 4.3244g of Na2CO3Dissolving in 40ml deionized water to obtain transparent precipitant solution B, diluting with 0.60ml 25% concentrated ammonia water in 40ml deionized water to obtain 0.2mol L-1The ammonia water complexing assistant C, 2.5176g LiOH is dissolved in 40mL deionized water to obtain a lithium salt solution D.
(2) And (2) quickly mixing the solution B and the solution C prepared in the step (1) to obtain a solution E, slowly dripping the solution A and the solution D into the solution E to prepare a mixed solution F, transferring the mixed solution F into a 100mL stainless steel autoclave lined with polytetrafluoroethylene (the volume filling rate is 80%), heating to 180 ℃, preserving heat for 12 hours and cooling to room temperature. Centrifugally cleaning, placing in a vacuum drying oven at 80 ℃, and drying for 12h to obtain precursor powder.
(3) And (3) placing the precursor powder obtained in the step (2) in a corundum ark, then placing the corundum ark in a tube furnace, heating to 550 ℃ at a heating rate of 5 ℃/min in an air atmosphere, preserving the temperature for 5 hours, and cooling at room temperature to obtain 3.1247g of black transition metal oxide.
(4) And (4) placing the transition metal oxide in the step (3) in a tube furnace, introducing oxygen, controlling the heating rate to be 5 ℃/min, heating to 900 ℃, keeping the temperature for 12h, cooling at room temperature to obtain the lithium-rich polycrystalline anode material, and weighing the mass.
(5) Obtaining LiLaO required for coating by calculating according to 1% of the mass of the lithium-rich polycrystalline positive electrode material obtained in the step (4)2The weight of the mixture is 0.0312g, the mixture is mixed and ground in a mortar for 30min, and the weight is weighed.
(6) And (3) placing the mixture ground in the step (5) in a zirconia ball milling tank for ball milling for 1.5h according to the ball-material mass ratio of 9:1 and the anhydrous ethanol-material mass ratio of 1.6ml:1 g.
(7) And (3) putting the ball-milled material into a vacuum drying box at the temperature of 80 ℃, and performing vacuum drying for 5 hours. Placing the dried powder in a corundum ark, controlling the heating rate to be 5 ℃/min, heating to 500 ℃, and tempering for 3h to obtain LiLaO2Coated single crystal lithium-rich manganese-based positive electrode material Li1.2Mn0.54Ni0.13Co0.13O2And is denoted as LR 2.
Li synthesized in this example1.2Mn0.54Ni0.13Co0.13O2The cathode materials, acetylene black and polyvinylidene fluoride were mixed in a ratio of 85: 10: 5 mass ratio mixing coating on the aluminium foil current collector, use the scraper of 150um specification to carry out the preforming, dry 12h in the drying cabinet is placed in to 80 ℃, use the slicer to cut into the circular pole piece of diameter 12.00 mm. In a glove box filled with argon, the cut pole piece is a positive pole, the metal lithium piece is a negative pole, a Celgard 2500 type diaphragm is used, and the diaphragm is prepared from ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate according to the proportion of 1:1:1To form 1M LiPF6And assembling the electrolyte into a CR2025 button cell. The charge-discharge cycle performance and the rate capability under the voltage of 2.0V-4.8V are tested on a Land test system (CT2001A), and the test result is shown in figure 3.
EXAMPLE III
(1) 4.5635g of MnSO4·H2O，1.7085g NiSO4·6H2O，1.8265g CoSO4·7H2O in 40ml of deionized water to give a transparent transition metal salt solution A, 4.3244g of Na2CO3Dissolving in 40ml deionized water to obtain transparent precipitant solution B, diluting with 0.60ml 25% concentrated ammonia water in 40ml deionized water to obtain 0.2mol L-1The ammonia chelating agent C, 2.5176g LiOH was dissolved in 40mL deionized water to obtain a lithium salt solution D.
(2) And (2) quickly mixing the solution B and the solution C prepared in the step (1) to obtain a solution E, slowly dripping the solution A and the solution D into the solution E to prepare a mixed solution F, transferring the mixed solution F into a 100mL stainless steel autoclave lined with polytetrafluoroethylene (the volume filling rate is 80%), heating to 170 ℃, preserving heat for 12 hours and cooling to room temperature. Centrifugally cleaning, placing in a vacuum drying oven at 80 ℃, and drying for 12h to obtain precursor powder.
(3) And (3) placing the precursor powder obtained in the step (2) in a corundum ark, then placing the corundum ark in a tube furnace, heating to 550 ℃ at a heating rate of 5 ℃/min in an air atmosphere, preserving the temperature for 5 hours, and cooling at room temperature to obtain 3.1247g of black transition metal oxide.
(4) And (4) placing the transition metal oxide in the step (3) in a tube furnace, introducing oxygen, controlling the heating rate to be 5 ℃/min, heating to 900 ℃, keeping the temperature for 11h, cooling at room temperature to obtain the lithium-rich polycrystalline anode material, and weighing the mass.
(5) Calculating to obtain LiAlO required for coating according to 1% of the mass of the lithium-rich polycrystalline positive electrode material obtained in the step (4)2And (3) mixing and grinding the two materials in a mortar for 30min, and weighing the materials.
(6) And (3) placing the mixture ground in the step (5) in a zirconia ball milling tank for ball milling for 2 hours according to the ball-material mass ratio of 9:1 and the anhydrous ethanol-material mass ratio of 1.6ml:1 g.
(7) Placing the material subjected to ball milling and drying in the step (6) in a corundum ark, controlling the heating rate to be 5 ℃/min, heating to 400 ℃, and tempering for 5h to obtain LiAlO2Coated single crystal lithium-rich manganese-based positive electrode material Li1.2Mn0.54Ni0.13Co0.13O2。
Li synthesized in this example1.2Mn0.54Ni0.13Co0.13O2The cathode materials, acetylene black and polyvinylidene fluoride were mixed in a ratio of 85: 10: 5 mass ratio mixing coating on the aluminium foil current collector, use the scraper of 150um specification to carry out the preforming, dry 12h in the drying cabinet is placed in to 80 ℃, use the slicer to cut into the circular pole piece of diameter 12.00 mm. In a glove box filled with argon, the cut pole piece is a positive pole, the metal lithium piece is a negative pole, a Celgard 2500 type diaphragm and 1M LiPF prepared from ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate according to the proportion of 1:1:1 are used6And assembling the electrolyte into a CR2025 button cell. The charge-discharge cycle performance and the rate capability under the voltage of 2.0V-4.8V are tested on a Land test system (CT2001A), and the test result is shown in figure 3.
Comparative example 1
(1) 4.5635g of MnSO4·H2O，1.7085g NiSO4·6H2O，1.8265g CoSO4·7H2O in 40ml of deionized water to give a transparent transition metal salt solution A, 4.3244g of Na2CO3Dissolving in 40ml deionized water to obtain transparent precipitant solution B, diluting with 0.60ml 25% concentrated ammonia water in 40ml deionized water to obtain 0.2mol L-1The ammonia chelating agent C, 2.5176g LiOH was dissolved in 40mL deionized water to obtain a lithium salt solution D.
(2) And (2) quickly mixing the solution B and the solution C prepared in the step (1) to obtain a solution E, slowly dripping the solution A and the solution D into the solution E to prepare a mixed solution F, transferring the mixed solution F into a 100mL stainless steel autoclave lined with polytetrafluoroethylene (the volume filling rate is 80%), heating to 180 ℃, preserving heat for 12 hours and cooling to room temperature. Centrifugally cleaning, placing in a vacuum drying oven at 80 ℃, and drying for 12h to obtain precursor powder.
(3) And (3) placing the precursor powder obtained in the step (2) in a corundum ark, then placing the corundum ark in a tube furnace, heating to 550 ℃ at a heating rate of 5 ℃/min in an air atmosphere, preserving the temperature for 5 hours, and cooling at room temperature to obtain 3.1247g of black transition metal oxide.
(4) Putting the transition metal oxide in the step (3) into a tube furnace, introducing oxygen, controlling the heating rate to be 5 ℃/min, heating to 900 ℃, preserving the temperature for 12h, and cooling at room temperature to obtain the lithium-rich polycrystalline anode material Li1.2Mn0.54Ni0.13Co0.13O2。
Li synthesized in this example1.2Mn0.54Ni0.13Co0.13O2The cathode materials, acetylene black and polyvinylidene fluoride were mixed in a ratio of 85: 10: 5 mass ratio mixing coating on the aluminium foil current collector, use the scraper of 150um specification to carry out the preforming, dry 12h in the drying cabinet is placed in to 80 ℃, use the slicer to cut into the circular pole piece of diameter 12.00 mm. In a glove box filled with argon, the cut pole piece is a positive pole, the metal lithium piece is a negative pole, a Celgard 2500 type diaphragm and 1M LiPF prepared from ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate according to the proportion of 1:1:1 are used6And assembling the electrolyte into a CR2025 button cell. The charge-discharge cycle performance and the rate capability under the voltage of 2.0V-4.8V are tested on a Land test system (CT2001A), and the test result is shown in figure 3.
The above-described embodiments are merely examples of the present invention, and although the preferred embodiments of the present invention and the accompanying drawings are disclosed for illustrative purposes, they are not intended to limit the present invention, and various alternatives, variations and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims. Therefore, the present invention should not be limited to the disclosure of the preferred embodiments and the accompanying drawings.

Claims (7)

1. Modified richesThe preparation method of the lithium-manganese-based cathode material is characterized in that the chemical composition of the cathode material is xLi2MnO3·(1-x)LiMO2Wherein, 0<x<1, M is one or more of Mn, Ni, Co, Al, Ce, Cr, La, Zr, Nb, Sn, Ti and Mg, and is in the form of micron-sized single crystal particles with uniform particle size, the surfaces of which are coated with fast lithium ion conductors.
2. A preparation method of the micron-sized single-crystal fast lithium ion conductor coated lithium-rich cathode material as claimed in claim 1 is characterized by comprising the following steps:
(1) dissolving bivalent soluble salts of transition metals of nickel, cobalt and manganese into deionized water according to a stoichiometric ratio to prepare 1.0-6.0 mol L-1The transition metal salt mixed solution A; dissolving the precipitator powder in deionized water to prepare a precipitator solution B with the same concentration and the same volume as the solution A; adding a certain amount of ammonia water, concentrated ammonia water or ammonium salt into deionized water to prepare 0.2-1.2 mol L-1The volume of the solution A is the same as that of the chelating assistant C, and the concentration ratio of the solution A to the chelating assistant C is 1: 0.2; lithium salt with stoichiometric ratio is dissolved in deionized water with the same volume to prepare a lithium salt solution D.
(2) And (2) quickly mixing the solution B and the solution C prepared in the step (1) to obtain a solution E, slowly dripping the solution A and the solution D into the solution E to prepare a mixed solution F, transferring the mixed solution F into a 100mL stainless steel autoclave lined with polytetrafluoroethylene (the volume filling rate is 80%), heating to 100-300 ℃, preserving the heat for 5-24 hours, and cooling to room temperature. Centrifugally cleaning, and then placing in a vacuum drying oven at 30-100 ℃ for drying for 5-24 h to obtain precursor powder.
(3) And (3) pouring the precursor powder prepared in the step (2) into a corundum ark, placing the corundum ark in a tube furnace, keeping air circulation or in a flowing atmosphere, controlling the heating rate to be 2-10 ℃/min, heating to 300-700 ℃, calcining for 3-10 h, and cooling to room temperature to obtain the black transition metal oxide powder.
(4) And (4) placing the transition metal oxide in the step (3) in a tube furnace in an oxygen atmosphere, controlling the heating rate to be 2-10 ℃/min, heating to 750-1050 ℃, sintering for 10-24 h, and cooling to room temperature to obtain the polycrystalline lithium-rich manganese-based positive electrode material.
(5) Weighing the polycrystalline lithium-rich manganese-based positive electrode material obtained in the step (4) to obtain a mass m1Weighing corresponding substances according to 1-5 wt% of quick-acting lithium ion conductor salt, simply mixing and grinding in a mortar, and weighing mass m2And (3) according to the mass ratio of ball materials of 5-15: 1, putting 1g of anhydrous ethanol and 1-5 ml of material in a zirconia ball milling tank for ball milling for 0.5-5 h.
(6) And (5) putting the ball-milled material in the step (5) into a vacuum drying oven at the temperature of 50-80 ℃, and performing vacuum drying for 2-12 hours. And (3) placing the dried powder in a corundum ark, controlling the heating rate to be 2-10 ℃/min, heating to 300-700 ℃, and tempering for 3-12 h to obtain the quick lithium ion coated single crystal lithium-rich manganese-based positive electrode material.
3. The preparation method according to claim 2, wherein the divalent soluble salts of transition metals manganese, cobalt and nickel in step (1) are one or more of sulfate, chloride, nitrate and acetate.
4. The preparation method according to claim 2, wherein the precipitant raw material in step (1) is one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate and ammonium bicarbonate.
5. The preparation method according to claim 2, wherein the chelating agent in step (1) is 0.2-1.2 mol L prepared by adding deionized water to one or more of liquid ammonia, concentrated ammonia water and ammonium salt-1The solution of (1).
6. The method according to claim 2, wherein the lithium salt in step (1) is one or more of lithium carbonate, lithium hydroxide, lithium nitrate and lithium acetate.
7. The method according to claim 2, wherein the fast lithium ion conductor salt in step (5) is one or more selected from lithium phosphate, lithium lanthanate, lithium zirconate, lithium aluminate, lithium chromate, lithium cerate, lithium titanate, lithium molybdate and lithium titanate, or is formed by high-temperature calcination and combination of lithium salt and one or more selected from phosphate, lanthanate, zirconate, aluminate, chromate, cerate, molybdate and titanate.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114284472A (en) * 2021-12-23 2022-04-05 北京理工大学重庆创新中心 Single crystal lithium-rich material with superconducting modification layer and preparation method and application thereof
CN114300664A (en) * 2021-12-29 2022-04-08 北京理工大学 Lithium-rich single crystal positive electrode material with surface coated with lithium selenate and preparation method and application thereof
CN114335470A (en) * 2021-12-29 2022-04-12 北京卫蓝新能源科技有限公司 Modified positive electrode material and preparation method and application thereof
CN114784229A (en) * 2022-03-18 2022-07-22 蜂巢能源科技股份有限公司 Cobalt-free positive electrode material and preparation method and application 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

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103928664A (en) * 2014-04-29 2014-07-16 哈尔滨工业大学 Lithium-enriched manganese-based anode material with fast ion conductor coating layer and surface heterostructure and preparation method of lithium-enriched manganese-based anode material
CN105428637A (en) * 2014-09-18 2016-03-23 宁德时代新能源科技有限公司 Lithium ion battery, positive electrode material of lithium ion battery and preparation method for positive electrode material
CN106920959A (en) * 2015-12-28 2017-07-04 机械科学研究总院先进制造技术研究中心 A kind of lithium-rich manganese-based polynary positive pole material of monocrystalline and preparation method thereof
CN109537054A (en) * 2018-11-26 2019-03-29 江西理工大学 A kind of high-rate lithium-rich manganese-based anode material monocrystalline and preparation method thereof
CN110890541A (en) * 2019-11-21 2020-03-17 国联汽车动力电池研究院有限责任公司 Preparation method of surface-modified lithium-rich manganese-based positive electrode material and lithium ion battery
KR102144056B1 (en) * 2019-12-24 2020-08-12 주식회사 에스엠랩 A cathode active material, method of preparing the same, and lithium secondary battery comprising a cathode comprising the cathode active material
CN111615496A (en) * 2017-12-22 2020-09-01 尤米科尔公司 Positive electrode material for rechargeable lithium ion batteries
CN112382738A (en) * 2019-11-08 2021-02-19 陕西彩虹新材料有限公司 Preparation method of high-performance lithium-rich single crystal multi-element cathode material
CN112624201A (en) * 2020-11-30 2021-04-09 广东微电新能源有限公司 Preparation method of lithium-rich cathode material
WO2021075942A1 (en) * 2019-10-18 2021-04-22 주식회사 에코프로비엠 Positive electrode active material for lithium secondary battery, preparation method therefor, and lithium secondary battery comprising same
CN112838195A (en) * 2019-11-22 2021-05-25 中国科学院大连化学物理研究所 Surface-coated lithium ion battery positive electrode material and preparation method and application thereof
CN112968150A (en) * 2019-12-12 2021-06-15 比亚迪股份有限公司 Positive electrode material and preparation method thereof

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103928664A (en) * 2014-04-29 2014-07-16 哈尔滨工业大学 Lithium-enriched manganese-based anode material with fast ion conductor coating layer and surface heterostructure and preparation method of lithium-enriched manganese-based anode material
CN105428637A (en) * 2014-09-18 2016-03-23 宁德时代新能源科技有限公司 Lithium ion battery, positive electrode material of lithium ion battery and preparation method for positive electrode material
CN106920959A (en) * 2015-12-28 2017-07-04 机械科学研究总院先进制造技术研究中心 A kind of lithium-rich manganese-based polynary positive pole material of monocrystalline and preparation method thereof
CN111615496A (en) * 2017-12-22 2020-09-01 尤米科尔公司 Positive electrode material for rechargeable lithium ion batteries
CN109537054A (en) * 2018-11-26 2019-03-29 江西理工大学 A kind of high-rate lithium-rich manganese-based anode material monocrystalline and preparation method thereof
WO2021075942A1 (en) * 2019-10-18 2021-04-22 주식회사 에코프로비엠 Positive electrode active material for lithium secondary battery, preparation method therefor, and lithium secondary battery comprising same
CN112382738A (en) * 2019-11-08 2021-02-19 陕西彩虹新材料有限公司 Preparation method of high-performance lithium-rich single crystal multi-element cathode material
CN110890541A (en) * 2019-11-21 2020-03-17 国联汽车动力电池研究院有限责任公司 Preparation method of surface-modified lithium-rich manganese-based positive electrode material and lithium ion battery
CN112838195A (en) * 2019-11-22 2021-05-25 中国科学院大连化学物理研究所 Surface-coated lithium ion battery positive electrode material and preparation method and application thereof
CN112968150A (en) * 2019-12-12 2021-06-15 比亚迪股份有限公司 Positive electrode material and preparation method thereof
KR102144056B1 (en) * 2019-12-24 2020-08-12 주식회사 에스엠랩 A cathode active material, method of preparing the same, and lithium secondary battery comprising a cathode comprising the cathode active material
CN112624201A (en) * 2020-11-30 2021-04-09 广东微电新能源有限公司 Preparation method of lithium-rich cathode material

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114284472A (en) * 2021-12-23 2022-04-05 北京理工大学重庆创新中心 Single crystal lithium-rich material with superconducting modification layer and preparation method and application thereof
CN114284472B (en) * 2021-12-23 2023-11-03 北京理工大学重庆创新中心 Monocrystalline lithium-rich material with superconductive modification layer, and preparation method and application thereof
CN114300664A (en) * 2021-12-29 2022-04-08 北京理工大学 Lithium-rich single crystal positive electrode material with surface coated with lithium selenate and preparation method and application thereof
CN114335470A (en) * 2021-12-29 2022-04-12 北京卫蓝新能源科技有限公司 Modified positive electrode material and preparation method and application thereof
CN114300664B (en) * 2021-12-29 2023-11-07 北京理工大学 Lithium-rich single crystal positive electrode material with surface coated with lithium selenate, and preparation method and application thereof
CN114784229A (en) * 2022-03-18 2022-07-22 蜂巢能源科技股份有限公司 Cobalt-free positive electrode material and preparation method and application thereof
CN114784229B (en) * 2022-03-18 2023-08-11 蜂巢能源科技股份有限公司 Cobalt-free positive electrode material and preparation method and application 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

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