CN108847477B - Nickel cobalt lithium manganate ternary positive electrode material and preparation method thereof - Google Patents

Nickel cobalt lithium manganate ternary positive electrode material and preparation method thereof Download PDF

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CN108847477B
CN108847477B CN201810515488.XA CN201810515488A CN108847477B CN 108847477 B CN108847477 B CN 108847477B CN 201810515488 A CN201810515488 A CN 201810515488A CN 108847477 B CN108847477 B CN 108847477B
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nickel cobalt
deionized water
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CN108847477A (en
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王迪
李崇
张云鹏
王慧萍
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Shaanxi rainbow new material Co., Ltd.
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Caihong Group New Energy Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
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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
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    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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    • 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
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    • 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
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    • Y02E60/10—Energy storage using batteries

Abstract

A double-coated doped modified high-performance nickel cobalt lithium manganate ternary positive electrode material and a preparation method thereof are provided, wherein the material comprises Li (Ni)aCobMnc)1‑xMxO2And a double coating layer attached to the surface thereof; the inner layer of the double coating layer is RyO, the outer layer is Al2O3(ii) a The molar ratio of the lithium to the nickel to the cobalt to the manganese to the doping element M is 1.02-1.12: a: b: c: 0-0.12, wherein a is more than or equal to 0.5, and a + b + c is 1; the invention is achieved by attaching Li (Ni)aCobMnc)1‑xMxO2The double coating layer on the surface improves the rate capability and the cycle performance in the electrical property; the preparation method comprises the steps of synthesizing a Ti-doped nickel-cobalt-manganese ternary material precursor, preparing a Ti-doped sample and preparing a double-coated sample; the material has the advantages of high energy density, good rate capability and obviously improved normal-temperature cycle performance of the battery.

Description

Nickel cobalt lithium manganate ternary positive electrode material and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a nickel cobalt lithium manganate ternary cathode material and a preparation method thereof.
Background
Since the discovery of the ternary cathode material (NCM), the lithium ion battery has attracted much attention of researchers due to its high capacity (up to 270mAh/g theoretical capacity), excellent safety performance, low cost and other factors. However, the nickel-cobalt-manganese ternary material generally has the following problems: firstly, cations are easy to mix and discharge, so that lithium is separated out; secondly, the rate performance is slightly poorer than that of materials such as lithium cobaltate and the like, and the cycle performance needs to be improved; and poor compatibility with electrolytes. The main methods currently used to solve these problems are doping modification and surface coating. The nickel-cobalt-manganese ternary material is modified only by doping, but certain defects exist, namely, the capacity loss of the battery is caused by doping of non-active substance elements, and the problem that the battery is matched with the electrolyte is not fundamentally solved because active particles are contacted with the electrolyte in the charging and discharging processes, oxide erosion occurs on the surface of the battery, and transition metal ions are dissolved to form surface structure collapse and the cycle performance is poor. The nickel-cobalt-manganese ternary material is modified only by surface coating, so that the dissolution of metal ions can be effectively relieved, the corrosion of HF to active substances is reduced, and the cycle performance of the battery is improved, but the nickel-cobalt-manganese ternary material has no effect on the improvement of the capacity of the battery. Therefore, how to play the synergistic effect of doping modification and surface coating is to improve the energy density of the battery by applying the nickel-cobalt-manganese ternary material, and meanwhile, the nickel-cobalt-manganese ternary material has excellent rate performance and good cycle performance, and is a hot problem in the research of the anode material in the lithium battery industry at present. Therefore, how to select effective doping and coating materials to prepare the nickel-cobalt-manganese ternary material with excellent performance becomes a bottleneck for solving the various problems.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a nickel cobalt manganese lithium ternary positive electrode material and a preparation method thereof, and the nickel cobalt manganese ternary material with high capacity, high cycle retention rate and good rate capability can be manufactured.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the nickel cobalt lithium manganate ternary positive electrode material comprises Li (Ni)aCobMnc)1-xMxO2And a double coating layer attached to the surface thereof; the inner layer of the double coating layer is RyO, the outer layer is Al2O3(ii) a The molar ratio of the lithium to the nickel to the cobalt to the manganese to the doping element M is 1.02-1.12: a: b: c:0 to 0.12, wherein a is not less than 0.5, and a + b + c is 1.
SaidInner layer R of the coating layeryO has a thickness of 0.01-50nm, and the coating layer contains Li (Ni)aCobMnc)1-xMxO2And 0.01 to 10%, preferably 0.05 to 5% by mass of the total mass fraction of the double coating layer attached to the surface thereof.
The inner layer R of the coating layeryO is WO3、Y2O3、La2O3One kind of (1).
The outer layer Al of the coating layer2O3Has a thickness of 20-100nm, and the outer layer of the coating layer is Li (Ni)aCobMnc)1-xMxO2And the total mass fraction of the double coating layer attached to the surface thereof is 0.05 to 15%, preferably 0.1 to 10%.
The doping element M is one of Ti and Cr.
A preparation method of a double-coated doped modified high-performance nickel cobalt lithium manganate ternary cathode material comprises the following steps:
the method comprises the following steps: synthesis of M-doped nickel-cobalt-manganese ternary material precursor
According to the formula (n) (Ni): n (Co): n (Mn): weighing the oxysalt of the substance with the mass ratio of (a), (b) and (c) being 0-0.12, wherein a is more than or equal to 0.5, and a + b + c is 1, and adding deionized water, wherein the mass ratio of the oxysalt to the deionized water is 1: (1-6), heating and stirring the solution in water bath at the temperature of 60-80 ℃ for 0.5-2 hours after preparing the solution, and adding Na with the concentration of 0.5-2 mol/L2CO30.2-2L of the solution, simultaneously dripping 0.1-2 mol/L of ammonia water to control the pH value of the solution to be 8-12, aging for 12-25 hours after the reaction is fully performed, performing vacuum filtration and washing, and placing the precipitate in a drying oven at 100-120 ℃ for vacuum drying for 4-8 hours to obtain a precursor of the M-doped nickel-cobalt-manganese ternary material;
step two: preparation of M-doped samples
Mixing the precursor obtained in the step one and LiOH according to the mass ratio of 1.02-1.12: 1, uniformly ball-milling, collecting, and sintering in a muffle furnace in two stages: the first stage is a pre-sintering stage, the temperature is increased from room temperature to 350-550 ℃, and sintering is carried out in the air for 6-10 hours; the second stage is a solid phase reaction stage, the temperature is increased to 800-980 ℃, the mixture is sintered for 8-12 hours in an oxygen atmosphere, the mixture is cooled to room temperature along with a furnace, and an M-doped sample is obtained after crushing and 300-mesh sieving;
step three: preparation of double-coated samples:
the dry preparation process comprises the following steps:
and (3) mixing the M-doped sample obtained in the step (II) with the metal oxide nano powder according to a molar ratio (0-0.12): (0.01-0.15), placing the mixture into a ball milling tank for mixing, grinding for 4-8 hours at the rotating speed of 300-1000 r/min, calcining the obtained powder again, heating to 450-750 ℃ from room temperature, sintering in the air for 8-10 hours, cooling to room temperature along with a furnace, crushing and sieving to obtain a coated sample I;
adding the first coated sample into deionized water, adding a lithium source, wherein the weight ratio of the first coated sample: ionized water: the mass ratio of the lithium source is 1: 50-200: 1.02-1.12 to obtain a mixed solution A; adding an aluminum source into deionized water, wherein the adding ratio of the aluminum source to the deionized water is 0.1-1.2: 10, fully stirring by using a magnetic stirrer until the aluminum source and the deionized water are completely dissolved, mixing with the mixed solution A to generate a precipitate, wherein the mixing volume ratio is 1:1, filtering, drying and calcining the precipitate at 450-650 ℃ for 4-6 hours, and then sieving the calcined precipitate with a 300-mesh sieve to obtain the double-coated doped modified high-performance nickel cobalt lithium manganate ternary cathode material.
The wet preparation process comprises the following steps:
preparation of RCl with hydrochloride saltyPreparing 0.5-2 mol/L of dispersant, adding 0.035-0.42 g/mL of dispersant, adding the M doped sample in the second step, and ultrasonically dispersing uniformly, wherein RCl is prepared by hydrochlorideyThe mass ratio of the dispersing agent to the M doped sample is (0.1-0.15): (2-6): (80-200); dropwise adding a precipitator sodium carbonate with the concentration of 0.5-2 mol/L under magnetic stirring to generate a precipitate, filtering, and washing with deionized water; drying at 60-120 ℃, calcining the obtained powder again, heating the powder to 450-750 ℃ from room temperature, sintering the powder in air for 8-10 hours, cooling the powder to room temperature along with the furnace, crushing the powder, and sieving the powder with a 300-mesh sieve to obtain a coated sample I;
adding the first coated sample into deionized water, adding a lithium source, coating the first coated sample: ionized water: the mass ratio of the lithium source is 1: 50-200: 1.02-1.12 to obtain a mixed solution A; adding an aluminum source into deionized water, wherein the adding ratio of the aluminum source to the deionized water is 0.1-1.2: 10, fully stirring by using a magnetic stirrer until the aluminum source and the deionized water are completely dissolved, mixing with the mixed liquid A to generate a precipitate, wherein the mixing ratio is 1:1, filtering, drying and calcining the precipitate at 450-650 ℃ for 4-6 hours, and then sieving the calcined precipitate with a 300-mesh sieve to obtain the double-coated doped modified high-performance nickel cobalt lithium manganate ternary cathode material.
The oxysalt is two or three of sulfate, acetate and nitrate.
The metal oxide nano powder is WO3、Y2O3、La2O3One kind of (1).
The dispersing agent is polyvinylpyrrolidone.
The invention has the beneficial effects that:
the invention is achieved by attaching Li (Ni)aCobMnc)1-xMxO2The double coating layer on the surface improves the rate capability and the cycle performance in the electrical property; m metal ion has multiple valence states, and is mixed with Ni in the charge-discharge process after being doped into the matrix2+And meanwhile, the catalyst is oxidized, so that higher first charge-discharge specific capacity can be obtained, and large current discharge is allowed. Nano state RyO has good dielectric property, can obviously split the double peaks of (006)/(012) and (018)/(110), forms a more perfect layered structure and improves the rate capability of the material; and Al coated with the outer layer2O3Can form a protective film to reduce the corrosion of the electrolyte to the base material, thereby improving the cycle performance of the material. The material prepared by the method has high energy density and good rate capability, and simultaneously, the normal-temperature cycle performance of the battery is obviously improved.
Detailed Description
In the following, in connection with the examples, bulk doped Ti, inner layer coated WO3And Al is coated on the outer layer2O3For example, NCM523, NCM622, NCM811 are prepared using dry and wet processes, respectively.
Example one
A preparation method of a double-coated doped modified high-performance nickel cobalt lithium manganate ternary cathode material comprises the following steps:
the method comprises the following steps: synthesizing a Ti-doped nickel-cobalt-manganese ternary material precursor:
taking sulfate of nickel sulfate, cobalt acetate, manganese acetate and M as raw materials, and adding the raw materials into a reaction kettle according to the ratio of n (Ni): n (Co): n (Mn): the amount of n (Ti) 0.5:0.2:0.3:0.08 was determined by accurately weighing 0.475mol of nickel sulfate, 0.19mol of cobalt acetate, 0.285mol of manganese acetate, and 0.076mol of titanium sulfate in a beaker, preparing a solution with 25mL of deionized water, heating in a water bath at 80 ℃ with stirring for 2 hours, and adding 1.0mol/L of Na2CO3Mixing the solution by 0.2L, simultaneously dripping 1.5mol/L ammonia water to control the pH value of the solution to be 9-10, aging for 20 hours after the reaction is fully performed, performing vacuum filtration and washing, and placing the precipitate in a drying oven at 100 ℃ for vacuum drying for 4 hours to obtain a Ti-doped nickel-cobalt-manganese ternary material precursor;
step two: preparation of Ti-doped samples:
mixing the Ti-doped nickel-cobalt-manganese ternary material precursor obtained in the step one with LiOH according to the mass ratio of 1.08:1, uniformly ball-milling, preferably in a planetary ball mill at the rotating speed of 1000r/min for 2 hours; after being uniformly ground, the mixture is collected and sintered in a muffle furnace in two sections: the first stage is a pre-sintering stage, the temperature is raised from room temperature to 550 ℃, and sintering is carried out in the air for 6 hours; the second stage is a solid phase reaction stage, the temperature is raised to 920 ℃, the mixture is sintered for 12 hours in an oxygen atmosphere, the mixture is cooled to room temperature along with a furnace, and a Ti doped sample is obtained after crushing and 300-mesh sieving;
step three: preparation of double-coated samples:
the dry preparation process comprises the following steps:
adding WO into the Ti-doped sample in the second step3Nanopowder, Ti-doped sample and WO3The nanometer powder with the molar ratio of 0.12:0.15 is put into a ball milling tank to be mixed, the rotating speed is 300r/min, the mixture is ground for 4 hours, then the obtained powder is calcined again, the temperature is raised to 650 ℃ from the room temperature, the sintering is carried out in the air for 10 hours, the sintering is carried out along with the furnace to the room temperature, and a coating sample I is obtained after the crushing and the sieving;
adding a first coating sample into deionized water, adding a lithium source, coating the first coating sample: ionized water: the mass ratio of the lithium source is 1: 200: 1.12, obtaining a mixed solution A, adding an aluminum source into deionized water, wherein the adding ratio of the aluminum source to the deionized water is 0.1:10, fully stirring the mixture by using a magnetic stirrer until the aluminum source and the deionized water are completely dissolved, mixing the mixture with the mixed solution A to generate a precipitate, filtering, drying and calcining the precipitate at 450 ℃ for 4 hours, and then sieving the precipitate with a 300-mesh sieve to obtain a coated sample II, namely a final product.
The wet preparation process comprises the following steps:
preparation of WCl with hydrochloride6Preparing 1.0mol/L of dispersant PVP, adding 0.035g/mL of dispersant PVP, adding the Ti-doped sample obtained in the step two, dispersing uniformly by ultrasonic, and dropwise adding 0.5mol/L of precipitator Na under magnetic stirring2CO3Filtering to obtain precipitate, and washing with deionized water; drying at 100 ℃, then calcining the obtained powder again, heating the powder to 650 ℃ from room temperature, sintering the powder in the air for 8 hours, cooling the powder to room temperature along with a furnace, crushing the powder, and sieving the powder by using a 300-mesh sieve to obtain a coated sample I;
adding the first coated sample into deionized water, adding a lithium source, wherein the weight ratio of the first coated sample: ionized water: the mass ratio of the lithium source is 1: 200: 1.12, obtaining a mixed solution A; adding an aluminum source into deionized water, wherein the adding ratio of the aluminum source to the deionized water is 0.1:10, fully stirring by using a magnetic stirrer until the aluminum source and the deionized water are completely dissolved, mixing with the mixed liquid A to generate a precipitate, filtering, drying and calcining the precipitate at 450 ℃ for 4 hours, and then sieving the precipitate with a 300-mesh sieve to obtain a coating sample II, namely a final product.
Example two
A preparation method of a double-coated doped modified high-performance nickel cobalt lithium manganate ternary cathode material comprises the following steps:
the method comprises the following steps: synthesizing a Ti-doped nickel-cobalt-manganese ternary material precursor:
nickel sulfate, cobalt acetate, manganese acetate and titanium sulfate are used as raw materials, and the raw materials are mixed according to the formula of n (Ni): n (Co): n (Mn): the amount of n (Ti) was 0.6:0.2:0.2:0.08 to accurately weigh 0.57mol of nickel sulfate, 0.19mol of cobalt acetate, and 0.08 mol of cobalt acetate19mol of manganese acetate and 0.076mol of titanium sulfate are put into a beaker, prepared into solution by 100mL of deionized water and heated and stirred in a water bath at 80 ℃ for 2 hours, and then mixed with 0.2L of 1.0mol/L of Na2CO3Mixing the solutions, simultaneously dripping 1.5mol/L ammonia water to control the pH value of the solution to be 9-10, aging for 20 hours after the reaction is fully carried out, carrying out vacuum filtration and washing, and putting the precipitate into a drying oven at 100 ℃ for vacuum drying for 4 hours to obtain a Ti-doped nickel-cobalt-manganese ternary material precursor;
step two: preparation of Ti-doped samples
Mixing the Ti-doped nickel-cobalt-manganese ternary material precursor obtained in the step one with LiOH according to the mass ratio of 1.08:1, uniformly ball-milling, preferably in a planetary ball mill at the rotating speed of 800r/min, and grinding for 4 hours; grinding, uniformly collecting and sintering in a muffle furnace in two sections: the first stage is a pre-sintering stage, the temperature is raised from room temperature to 450 ℃, and sintering is carried out in the air for 6 hours; the second stage is a solid phase reaction stage, the temperature is raised to 870 ℃, the mixture is sintered for 12 hours in an oxygen atmosphere, the mixture is cooled to room temperature along with a furnace, and a Ti-doped sample is obtained after crushing and 300-mesh sieving;
step three: preparation of double-coated samples:
the dry preparation process comprises the following steps:
adding WO into the Ti-doped sample prepared in the step two3Nano powder, the molar ratio is 0.10: 0.08, placing the mixture into a ball milling tank for mixing, grinding for 4 hours at the rotating speed of 300r/min, then calcining the obtained powder again, heating the powder to 650 ℃ from the room temperature, sintering the powder in the air for 10 hours, cooling the powder to the room temperature along with a furnace, crushing and sieving the powder to obtain a coated sample I;
adding the prepared first coated sample into deionized water, adding a lithium source, coating the first sample: ionized water: the mass ratio of the lithium source is 1: 50: 1.02, obtaining a mixed solution A, adding an aluminum source into deionized water, wherein the adding ratio of the aluminum source to the deionized water is 0.1:10, fully stirring the mixture by using a magnetic stirrer until the aluminum source and the deionized water are completely dissolved, mixing the mixture with the mixed solution A to generate a precipitate, filtering, drying and calcining the precipitate at 450 ℃ for 4 hours, and then sieving the precipitate with a 300-mesh sieve to obtain a coated sample II, namely a final product.
The wet preparation process comprises the following steps:
preparation of WCl with hydrochloride6Preparing 1.0mol/L concentration, adding a dispersant PVP, adding the Ti doped sample obtained in the second step, performing ultrasonic dispersion uniformly, and preparing WCl by using hydrochloride6The mass ratio of the dispersing agent PVP to the M doped sample is 0.1: 2: 80 under magnetic stirring, 0.5mol/L precipitant Na is added dropwise2CO3Filtering to obtain precipitate, and washing with deionized water; and drying at 100 ℃, then calcining the obtained powder again, heating the powder to 650 ℃ from room temperature, sintering the powder in the air for 8 hours, cooling the powder to room temperature along with the furnace, crushing the powder, and sieving the powder by using a 300-mesh sieve to obtain a coated sample I.
Adding the first coated sample into deionized water, and adding a lithium source to obtain a mixed solution A, wherein the first coated sample: ionized water: the mass ratio of the lithium source is 1: 200: 1.10, adding an aluminum source into deionized water, wherein the adding ratio of the aluminum source to the deionized water is 0.1-1.2, fully stirring by using a magnetic stirrer until the aluminum source and the deionized water are completely dissolved, mixing with the mixed solution A to generate a precipitate, filtering, drying and calcining the precipitate at 450 ℃ for 4 hours, and then sieving the precipitate with a 300-mesh sieve to obtain a second coating sample, namely a final product.
EXAMPLE III
A preparation method of a coated, doped and modified high-performance nickel cobalt lithium manganate ternary cathode material comprises the following steps:
the method comprises the following steps: synthesizing a Ti-doped nickel-cobalt-manganese ternary material precursor:
taking sulfate of nickel sulfate, cobalt acetate, manganese acetate and M as raw materials, and adding the raw materials into a reaction kettle according to the ratio of n (Ni): n (Co): n (Mn); the quantitative ratio of n (Ti) to 0.8:0.1:0.1:0.08 (in terms of mass ratio), 0.76mol of nickel sulfate, 0.095mol of cobalt acetate, 0.095mol of manganese acetate, and 0.076mol of titanium sulfate were weighed out accurately, and the weighed materials were placed in a beaker, and 150mL of deionized water was added to prepare a solution, which was then heated in a water bath at 80 ℃ under stirring for 2 hours, and then mixed with 0.2L, 1mol/L of Na2CO3Mixing the solutions, simultaneously dripping 1.5mol/L ammonia water to control the pH value of the solution to be 9-10, aging for 20 hours after the reaction is fully carried out, carrying out vacuum filtration and washing, and putting the precipitate into a drying oven at 100 ℃ for vacuum drying for 4 hours to obtain the productTi is doped with a nickel-cobalt-manganese ternary material precursor;
step two: preparation of Ti-doped samples
Mixing the Ti-doped nickel-cobalt-manganese ternary material precursor obtained in the step one with LiOH according to the mass ratio of 1.08:1, uniformly ball-milling, preferably in a planetary ball mill at the rotating speed of 600r/min, and grinding for 6 hours; grinding, uniformly collecting and sintering in a muffle furnace in two sections: the first stage is a pre-sintering stage, the temperature is raised from room temperature to 350 ℃, and sintering is carried out in the air for 6 hours; the second stage is a solid phase reaction stage, the temperature is raised to 800 ℃, the mixture is sintered for 12 hours in an oxygen atmosphere, the mixture is cooled to room temperature along with a furnace, and a Ti-doped sample is obtained after crushing and 300-mesh sieving;
step three: preparation of double-coated samples:
the dry preparation process comprises the following steps:
adding WO into the Ti-doped sample prepared in the step two3Nano powder, the molar ratio is 0.06: 0.08, placing the mixture into a ball milling tank for mixing, grinding for 4 hours at the rotating speed of 300r/min, then calcining the obtained powder again, heating the powder to 650 ℃ from the room temperature, sintering the powder in the air for 10 hours, cooling the powder to the room temperature along with a furnace, crushing and sieving the powder to obtain a coated sample I;
adding the first coated sample into deionized water, adding a lithium source, and coating the first coated sample: ionized water: the mass ratio of the lithium source is 1: 200: 1.12, obtaining a mixed solution A; adding an aluminum source into deionized water, wherein the adding ratio of the aluminum source to the deionized water is 1.2:10, fully stirring by using a magnetic stirrer until the aluminum source and the deionized water are completely dissolved, mixing with the mixed liquid A to generate a precipitate, filtering, drying and calcining the precipitate at 450 ℃ for 4 hours, and then sieving the precipitate with a 300-mesh sieve to obtain a coating sample II, namely a final product.
The wet preparation process comprises the following steps:
preparation of WCl with hydrochloride6Preparing 1.0mol/L concentration, adding 0.42g/mL dispersant PVP, adding the Ti doped sample prepared in the step two, and preparing WCl by using hydrochloride6The mass ratio of the dispersing agent PVP to the M doped sample is 0.15: 6: 200, ultrasonically dispersing uniformly, and dropwise adding 0.5mol/L sediment under magnetic stirringStarch Na2CO3Filtering to obtain precipitate, and washing with deionized water; drying at 100 ℃, then calcining the obtained powder again, heating the powder to 650 ℃ from room temperature, sintering the powder in the air for 8 hours, cooling the powder to room temperature along with a furnace, crushing the powder, and sieving the powder by using a 300-mesh sieve to obtain a coated sample I;
adding the first coated sample into deionized water, adding a lithium source, and coating the first coated sample: ionized water: the mass ratio of the lithium source is 1: 200: 1.12, obtaining a mixed solution A; adding an aluminum source into deionized water, wherein the adding ratio of the aluminum source to the deionized water is 1.2:10, fully stirring by using a magnetic stirrer until the aluminum source and the deionized water are completely dissolved, mixing with the mixed liquid A to generate a precipitate, filtering, drying and calcining the precipitate at 450 ℃ for 4 hours, and then sieving the precipitate with a 300-mesh sieve to obtain a coating sample II, namely a final product.
Comparative example 1
(1) Synthesizing a conventional nickel-cobalt-manganese ternary material precursor:
nickel sulfate, cobalt acetate and manganese acetate are used as raw materials, and the raw materials are mixed according to the formula of n (Ni): n (Co): the amount of n (Mn) ═ 0.5:0.2:0.3 nickel sulfate, 0.19mol cobalt acetate, and 0.285mol manganese acetate were weighed out accurately and placed in a beaker, and 150mL of deionized water was added to prepare a solution, which was then heated in a water bath at 80 ℃ with stirring for 2 hours, and then mixed with 1mol/L Na2CO3Mixing 20ml of the solution, simultaneously dripping 1.0mol/L ammonia water to control the pH of the solution to be 9-10, and aging for 20 hours after the reaction is full. After vacuum filtration and washing, the precipitate is placed in a drying oven with the temperature of 100 ℃ for vacuum drying for 4 hours, and the precursor Ni of the conventional nickel-cobalt-manganese ternary material is obtained0.5Co0.2Mn0.3CO3；
(2) Preparing a conventional nickel-cobalt-manganese ternary material:
step one, mixing the precursor obtained in the step (1) and LiOH according to the mass ratio of 1.08:1, uniformly ball-milling, preferably in a planetary ball mill, at the rotating speed of 1000r/min, and grinding for 2 hours;
step two, collecting the uniformly mixed materials and sintering the materials in a muffle furnace in two sections: the first stage is pre-sintering stage, which is to heat from room temperature to 550 deg.c and sinter in air for 6 hr(ii) a The second stage is a solid phase reaction stage, the temperature is raised to 920 ℃, the mixture is sintered for 12 hours in an oxygen atmosphere, the mixture is cooled to room temperature along with the furnace, and the conventional nickel-cobalt-manganese ternary material Li (Ni) is obtained after crushing and 300-mesh sieving0.5Co0.2Mn0.3)O2。
Comparative example No. two
(1) Synthesizing a conventional nickel-cobalt-manganese ternary material precursor:
nickel sulfate, cobalt acetate and manganese acetate are used as raw materials, and the raw materials are mixed according to the formula of n (Ni): n (Co): the amount of n (Mn) ═ 0.6:0.2:0.2 substances was determined by accurately weighing 0.57mol of nickel sulfate, 0.19mol of cobalt acetate, and 0.19mol of manganese acetate in a beaker, preparing a solution with 150mL of deionized water, heating and stirring in a water bath at 80 ℃ for 2 hours, and mixing with 1mol/L of Na2CO3Mixing 20ml of the solution, simultaneously dripping 1.0mol/L ammonia water to control the pH of the solution to be 9-10, and aging for 20 hours after the reaction is full. After vacuum filtration and washing, the precipitate is placed in a drying oven with the temperature of 100 ℃ for vacuum drying for 4 hours, and the precursor Ni of the conventional nickel-cobalt-manganese ternary material is obtained0.6Co0.2Mn0.2CO3；
(2) Preparing a conventional nickel-cobalt-manganese ternary material:
step one, the precursor obtained in the step (1) and Li2OH is mixed and ball-milled uniformly according to the mass ratio of 1.08:1, preferably in a planetary ball mill, the rotating speed is 800r/min, and the grinding is carried out for 4 hours;
step two, collecting the uniformly mixed materials and sintering the materials in a muffle furnace in two sections: the first stage is a pre-sintering stage, the temperature is raised from room temperature to 550 ℃, and sintering is carried out in the air for 6 hours; the second stage is a solid phase reaction stage, the temperature is raised to 870 ℃, the mixture is sintered for 12 hours in an oxygen atmosphere, the mixture is cooled to room temperature along with a furnace, and the mixture is crushed and sieved by a 300-mesh sieve to obtain the conventional nickel-cobalt-manganese ternary material Li (Ni)0.6Co0.2Mn0.2)O2。
Comparative example No. three
(1) Synthesizing a conventional nickel-cobalt-manganese ternary material precursor:
nickel sulfate, cobalt acetate and manganese acetate are used as raw materials, and the raw materials are mixed according to the formula of n (Ni): n (Co): substances having n (Mn) of 0.8:0.1:0.1Accurately weighing 0.76mol of nickel sulfate, 0.095mol of cobalt acetate and 0.095mol of manganese acetate according to the weight ratio, placing the nickel sulfate, the cobalt acetate and the manganese acetate into a beaker, preparing a solution by using 150mL of deionized water, heating and stirring the solution in a water bath at 80 ℃ for 2 hours, and mixing the solution with 1mol/L of Na2CO3Mixing 20ml of the solution, simultaneously dripping 1.0mol/L ammonia water to control the pH of the solution to be 9-10, and aging for 20 hours after the reaction is full. After vacuum filtration and washing, the precipitate is placed in a drying oven with the temperature of 100 ℃ for vacuum drying for 4 hours, and the precursor Ni of the conventional nickel-cobalt-manganese ternary material is obtained0.8Co0.1Mn0.1CO3；
(2) Preparing a conventional nickel-cobalt-manganese ternary material:
step one, mixing the precursor obtained in the step (1) and LiOH according to the mass ratio of 1.08:1, uniformly ball-milling, preferably in a planetary ball mill, rotating at 600r/min, and milling for 6 hours.
Step two, collecting the uniformly mixed materials and sintering the materials in a muffle furnace in two sections: the first stage is a pre-sintering stage, the temperature is raised from room temperature to 550 ℃, and sintering is carried out in the air for 6 hours; the second stage is a solid phase reaction stage, the temperature is raised to 800 ℃, the mixture is sintered for 12 hours in an oxygen atmosphere, the mixture is cooled to room temperature along with the furnace, and the conventional nickel-cobalt-manganese ternary material Li (Ni) is obtained after crushing and 300-mesh sieving0.8Co0.1Mn0.1)O2。
2025 buckling electricity manufacturing test was performed on the above examples and comparative examples, and the test voltage condition (3.0-4.3) V, the rate performance test condition: 0.2C, 0.5C, 1C, 2C, 5C charge and discharge for two circles respectively, and the multiplying power performance calculation method comprises the following steps: 5C discharge capacity/0.2C discharge capacity.
The first discharge specific capacity, rate capability and cycle performance data of 0.1C of the charging of the ternary samples of comparative examples 1-3 and examples 1-3 are given in the table I.
First discharge specific capacity of 0.2C, rate capability and cycle performance of the samples in Table I, comparative example and example
Figure BDA0001673970190000151
Results tableObviously, through bulk phase doping M and surface coating RyO&Al2O3Compared with the 0.1C initial specific discharge capacity of a conventional (undoped and uncoated) sample, the initial specific discharge capacity of the ternary material is greatly improved; meanwhile, the rate capability and the cycle performance in the electrical property of the ternary material after double-cladding doping are also obviously improved.

Claims (2)

1. A preparation method of a double-coated doped modified nickel cobalt lithium manganate ternary positive electrode material is characterized by comprising the following steps:
the method comprises the following steps: synthesis of M-doped nickel-cobalt-manganese ternary material precursor
According to the formula (n) (Ni): n (Co): n (Mn): weighing the oxysalt of the substance with the mass ratio of n (M) = a: b: c: 0-0.12, wherein a is more than or equal to 0.5, and a + b + c =1, and adding deionized water, wherein the mass ratio of the oxysalt to the deionized water is 1: (1-6), heating and stirring the solution in water bath at the temperature of 60-80 ℃ for 0.5-2 hours after preparing the solution, and adding Na with the concentration of 0.5-2 mol/L2CO30.2-2L of the solution, simultaneously dripping 0.1-2 mol/L of ammonia water to control the pH value of the solution to be 8-12, aging for 12-25 hours after the reaction is fully performed, performing vacuum filtration and washing, and placing the precipitate in a drying oven at 100-120 ℃ for vacuum drying for 4-8 hours to obtain a precursor of the M-doped nickel-cobalt-manganese ternary material;
step two: preparation of M-doped nickel cobalt lithium manganate material
Mixing the precursor obtained in the step one and LiOH according to the mass ratio of 1.02-1.12: 1, uniformly ball-milling, collecting, and sintering in a muffle furnace in two stages: the first stage is a pre-sintering stage, the temperature is increased from room temperature to 350-550 ℃, and sintering is carried out in the air for 6-10 hours; the second stage is a solid-phase reaction stage, the temperature is increased to 800-980 ℃, the mixture is sintered for 8-12 hours in an oxygen atmosphere, the mixture is cooled to room temperature along with a furnace, and the mixture is crushed and sieved by a 300-mesh sieve to obtain the M-doped nickel cobalt lithium manganate material;
step three: preparing a double-coated lithium nickel cobalt manganese oxide material by adopting a dry preparation process or a wet preparation process;
the dry preparation process comprises the following steps:
and (3) mixing the M-doped nickel cobalt lithium manganate material obtained in the step (II) with metal oxide nano powder according to a molar ratio (0-0.12): (0.01-0.15), placing the mixture into a ball milling tank for mixing, grinding for 4-8 hours at the rotating speed of 300-1000 r/min, calcining the obtained powder again, heating the powder to 450-750 ℃ from room temperature, sintering the powder in the air for 8-10 hours, cooling the powder to room temperature along with a furnace, crushing and sieving the powder to obtain a first nickel cobalt lithium manganate coated material;
adding the first coated lithium nickel cobalt manganese oxide material into deionized water, adding a lithium source, and coating the first lithium nickel cobalt manganese oxide material: ionized water: the mass ratio of the lithium source is 1: 50-200: 1.02-1.12 to obtain a mixed solution A; adding an aluminum source into deionized water, wherein the adding ratio of the aluminum source to the deionized water is 0.1-1.2: 10, fully stirring by using a magnetic stirrer until the aluminum source and the deionized water are completely dissolved, mixing with the mixed solution A to generate a precipitate, wherein the mixing volume ratio is 1:1, filtering and drying the precipitate, calcining at 450-650 ℃ for 4-6 hours, and sieving with a 300-mesh sieve to obtain the double-coated doped modified nickel cobalt lithium manganate ternary positive electrode material;
the wet preparation process comprises the following steps:
preparation of RCl with hydrochloride saltyPreparing 0.5-2 mol/L of dispersant, adding 0.035-0.42 g/mL of dispersant, adding the M-doped nickel cobalt lithium manganate material obtained in the second step, and ultrasonically dispersing uniformly, wherein RCl is prepared by hydrochlorideyThe mass ratio of the dispersing agent to the M-doped nickel cobalt lithium manganate material is (0.1-0.15): (2-6): (80-200); dropwise adding a precipitator sodium carbonate with the concentration of 0.5-2 mol/L under magnetic stirring to generate a precipitate, filtering, and washing with deionized water; drying at 60-120 ℃, calcining the obtained powder again, heating the powder to 450-750 ℃ from room temperature, sintering the powder in air for 8-10 hours, cooling the powder to room temperature along with the furnace, crushing the powder, and sieving the powder with a 300-mesh sieve to obtain a first nickel cobalt lithium manganate coated material;
adding the first coated lithium nickel cobalt manganese oxide material into deionized water, adding a lithium source, coating the first lithium nickel cobalt manganese oxide material: ionized water: the mass ratio of the lithium source is 1: 50-200: 1.02-1.12 to obtain a mixed solution A; adding an aluminum source into deionized water, wherein the adding ratio of the aluminum source to the deionized water is 0.1-1.2: 10, fully stirring by using a magnetic stirrer until the aluminum source and the deionized water are completely dissolved, mixing with the mixed solution A to generate a precipitate, wherein the mixing ratio is 1:1, filtering and drying the precipitate, calcining at 450-650 ℃ for 4-6 hours, and sieving with a 300-mesh sieve to obtain the double-coated doped modified nickel cobalt lithium manganate ternary positive electrode material;
the thickness of the inner layer of the double-coated coating layer is 0.01-50nm, and the inner layer of the coating layer accounts for Li (Ni)aCobMnc）1-xMxO2And the total mass fraction of the double coating layers attached to the surface of the composite material is 0.01-10%;
the inner layer of the double-coated coating layer is WO3、Y2O3、La2O3One of (1); r is one of W, Y, La;
outer layer Al of double-coated coating layer2O3Has a thickness of 20-100nm, and the outer layer of the coating layer is Li (Ni)aCobMnc）1-xMxO2And the total mass fraction of the double coating layers attached to the surface of the double coating layers is 0.05-15%;
the doping element M is one of Ti and Cr, and the oxysalt is two or three of sulfate, acetate and nitrate;
the metal oxide nano powder is WO3、Y2O3、La2O3One kind of (1).
2. The preparation method of the double-coated doped modified nickel cobalt lithium manganate ternary positive electrode material as claimed in claim 1, wherein said dispersant is polyvinylpyrrolidone.
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