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CN111916730A - Preparation method of WO3 modified nickel-rich ternary lithium ion battery positive electrode material - Google Patents

Preparation method of WO3 modified nickel-rich ternary lithium ion battery positive electrode material Download PDF

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CN111916730A
CN111916730A CN202010796571.6A CN202010796571A CN111916730A CN 111916730 A CN111916730 A CN 111916730A CN 202010796571 A CN202010796571 A CN 202010796571A CN 111916730 A CN111916730 A CN 111916730A
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lithium ion
ion battery
nickel
ternary lithium
rich ternary
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张小洪
付微婷
苟敏涛
王畅
唐立成
张亮
唐月娇
陈晓涛
刘富亮
石斌
王庆杰
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Guizhou Meiling Power Supply 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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M4/52—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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The application discloses a preparation method of a WO3 modified nickel-rich ternary lithium ion battery anode material in the technical field of preparation of battery anode materials, which comprises the following steps: mixing a tungsten source compound with absolute ethyl alcohol, and stirring and mixing uniformly to form a mixed solution A; adding the nickel-rich ternary lithium ion battery anode material powder into a mixed solution of absolute ethyl alcohol and deionized water, stirring for 1-5 hours at a stirring speed of 700-900 r/min, and dispersing uniformly to form a solution B; step three, dripping the solution A into the solution B by using a peristaltic pump, stirring the solution A and the solution B evenlyDrying the mixed solution to obtain mixed powder; step four, calcining the mixed powder in the air atmosphere, cooling, taking out, grinding by using an agate mortar, and screening to obtain WO3The modified nickel-rich ternary lithium ion battery anode material. The preparation method can improve the stability of the structure of the battery anode material, thereby improving the electrochemical stability of the battery.

Description

Preparation method of WO3 modified nickel-rich ternary lithium ion battery positive electrode material
Technical Field
The invention relates to the technical field of battery anode material manufacturing, in particular to a preparation method of a WO3 modified nickel-rich ternary lithium ion battery anode material.
Background
With the increasing demand for energy in today's energy storage and power systems, especially electric vehicles, rechargeable Lithium Ion Batteries (LIBs) are widely used in consumer electronics and Electric Vehicles (EVs) due to their high energy density, light weight, and long cycle life. Despite the great progress made in lithium ion batteries, increasing the energy density, power performance, range and safety of lithium ion batteries still represent a great challenge worldwide, and in order to meet these requirements, researchers have made great efforts to find positive electrode materials for lithium ion batteries having high discharge capacity and high operating voltage.
In recent years, a nickel-rich layered positive electrode material LiNixMnyCozO2(x is more than or equal to 0.6) because of being more than the traditional laminar anode material LiCoO2(energy density of 570Wh/kg) and a spinel-type cathode material LiMn2O4(energy density of 440Wh/kg) has higher discharge capacity (200-220 mAh/g) and higher energy density (>800Wh/kg) and the lower Co content in the nickel-rich material reduces the production cost, so the material becomes the most competitive lithium ion battery candidate positive electrode material.
However, the higher the nickel content in the nickel-rich ternary material is, the structural stability of the material shows a descending trend, the capacity of the material is rapidly attenuated, the cycle performance and the thermal stability are reduced in proportion, the Ni in the material is difficult to maintain at a valence of +3 due to the inherent Li/Ni cation mixed discharge, and the Ni2+More lithium occupation is formed, the cation mixed-arrangement degree is increased, and the disorder degree of the material is increased; the rapid capacity fade is caused by phase change in a high charge state, significant volume change occurs during lithium ion deintercalation, microstrain and crack formation of the material are caused, the microcracks promote electrolyte to penetrate into the particles, and the penetrated electrolyte passes unstable Ni4+Reaction, accelerating the surface deterioration of primary particles, and forming a NiO-like rock salt impurity phase, thereby increasing the impedance of the battery and influencing the electrochemical performance of the material; in addition, the severe thermal reaction between the delithiated nickel-rich ternary cathode material and the organic carbonate electrolyte can also cause the safety problem of the battery.
Therefore, in order to solve the above problems, a method of using WO3The modification method modifies the nickel-rich ternary material to prepare the lithium ion battery anode material with good cycle performance, stable material structure and excellent thermal safety performance, and has certain fundamental significance for the application in the field of lithium ion battery energy storage.
Disclosure of Invention
The invention aims to provide a preparation method of a WO3 modified nickel-rich ternary lithium ion battery cathode material, so as to prepare a lithium ion battery cathode material with good cycle performance, stable material structure and excellent thermal safety performance.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a WO3 modified nickel-rich ternary lithium ion battery positive electrode material comprises the following steps:
mixing a tungsten source compound with absolute ethyl alcohol, stirring for 1-5 hours at a stirring speed of 700-900 r/min, and uniformly mixing to form a mixed solution A;
adding the nickel-rich ternary lithium ion battery anode material powder into a mixed solution of absolute ethyl alcohol and deionized water, stirring for 1-5 hours at a stirring speed of 700-900 r/min, and dispersing uniformly to form a solution B;
step three, dripping the solution A into the solution B by using a peristaltic pump, stirring, and drying the uniformly stirred mixed solution to obtain mixed powder;
step four, calcining the mixed powder in the air atmosphere, cooling, taking out, grinding by using an agate mortar, and screening to obtain WO3The modified nickel-rich ternary lithium ion battery anode material.
The working principle and the beneficial effects of the invention are as follows: the invention adopts the nickel-rich ternary lithium ion battery anode material to improve the nickel content and increase the gram specific capacity of the material, thereby improving the energy density of the battery, simultaneously reducing the cobalt content and reducing the production cost, and the key point is WO3The modification is used for improving the structural stability of the nickel-rich ternary lithium ion battery anode material, inhibiting the side reaction of the anode material and electrolyte, and protecting anode material particles, so that the electrochemical stability of the battery is improved.
Further, in the first step, the tungsten source compound is one of ammonium metatungstate, sodium tungstate and tungsten acetate. The soluble tungsten salt is selected to be hydrolyzed in solution, because the valence state of tungsten ions is higher, the introduction of the soluble tungsten salt can reduce the cation arrangement degree of the material, so that a structure with better crystal lattice is formed, lithium ions are more favorably deintercalated between layers, and the electrochemical performance is improved.
Further, the weight ratio of the tungsten source compound to the absolute ethyl alcohol in the first step is 0.1-0.1875. The ethanol can better disperse the tungsten source compound in the solution to form a more uniform mixed solution.
Further, the positive electrode material of the nickel-rich ternary lithium ion battery in the second step is LiNixCoyMnzO2Wherein x is more than or equal to 0.6 and less than or equal to 0.95, y is more than or equal to 0.01 and less than or equal to 0.2, z is more than or equal to 0.01 and less than or equal to 0.2, and x + y + z is 1. Because the transition metal elements comprise three types of Ni, Co and Mn, the higher the content of Ni, the higher the specific discharge capacity, and the molar ratio of Ni + Co + Mn is 1 (the molar ratio), the nickel-rich ternary lithium ion battery anode material has the nickel content of Ni which is more than or equal to 0.6.
Further, the weight ratio of the nickel-rich ternary lithium ion battery anode material to the absolute ethyl alcohol in the second step is 0.5-1, and the weight ratio of the absolute ethyl alcohol to the deionized water is 1-2. The tungsten source compound and the nickel-rich ternary lithium ion battery anode material are uniformly dispersed through the combined action of solvents such as absolute ethyl alcohol, deionized water and the like to form in-situ coated WO3The coating layer is arranged on the surface of the nickel-rich ternary lithium ion battery anode material.
Further, the weight ratio of the tungsten source compound to the nickel-rich ternary lithium ion battery anode material is 0.01-0.2. In small amounts of WO3The nickel-rich ternary lithium ion battery anode material is modified, so that the crystal structure of the nickel-rich ternary lithium ion battery anode material can be stabilized, the interface stability of the nickel-rich ternary lithium ion battery anode material is improved, and the side reaction of the anode material and electrolyte is inhibited, so that the anode material particles are protected, and the electrochemical stability of the battery is improved.
Furthermore, the dropping speed of the peristaltic pump in the third step is 2-5 ml/min, the drying temperature is 60-100 ℃, and the drying time is 5-10 hours. The dropping speed of the tungsten source compound is controlled by a peristaltic pump, the aim is to control the hydrolysis nucleation rate of the tungsten source compound, and the WO finally generated3The core is more uniformly formed on the surface of the nickel-rich ternary lithium ion battery anode material to form a uniform and compact surface coating layer.
Further, the calcination in the fourth step is carried out in a tubular furnace, the calcination temperature is 400-900 ℃, the calcination time is 8-20 hours, and the standard sieve for sieving is 150-300 meshes. By high-temperature calcination to form WO3Can be uniformly coated on the surface of the nickel-rich ternary cathode material, further improves the cycle performance and improves the rate capability.
Drawings
FIG. 1 shows WO prepared in example 1 of the present invention3Comparing XRD patterns of the modified nickel-rich ternary lithium ion battery positive electrode material and an unmodified material;
FIG. 2 shows WO prepared in example 1 of the present invention3SEM comparison of modified nickel-rich ternary lithium ion battery cathode material and unmodified material;
FIG. 3 shows WO prepared in example 1 of the present invention3The modified nickel-rich ternary lithium ion battery positive electrode material and the unmodified material have a charge-discharge curve within a range of 2.75-4.3V and under a multiplying power of 0.5C;
FIG. 4 shows WO prepared in example 1 of the present invention3The modified nickel-rich ternary lithium ion battery anode material and the unmodified material are in a cycle performance diagram within the range of 2.75-4.3V and under the multiplying power of 0.5C;
FIG. 5 shows WO prepared in example 1 of the present invention3The modified nickel-rich ternary lithium ion battery anode material and the unmodified material have a rate performance curve in a range of 2.75-4.3V under different rates.
Detailed Description
The following is further detailed by way of specific embodiments:
example 1
A preparation method of a WO3 modified nickel-rich ternary lithium ion battery positive electrode material comprises the following steps:
(1) stirring the tungsten compound and absolute ethyl alcohol together, stirring for 1.5h at the stirring speed of 800r/min, and dispersing uniformly to form a mixed solution A; the tungsten compound is sodium tungstate, and the weight ratio of the sodium tungstate to the absolute ethyl alcohol is 1: 9;
(2) adding nickel-rich ternary lithium ion battery anode material powder into a mixed solution of absolute ethyl alcohol and deionized water, stirring for 1.5 hours at a stirring speed of 800r/min, and dispersing uniformly to form a solution B; the nickel-rich ternary lithium ion battery anode material powder is LiNi0.85Co0.1Mn0.05O2The weight ratio of the nickel-rich ternary lithium ion battery anode material to the absolute ethyl alcohol is 1: 1.7, the weight ratio of the absolute ethyl alcohol to the deionized water is 1: 0.8; the addition amount of the nickel-rich ternary lithium ion battery anode material is equal toIn the first step, the weight ratio of the added sodium tungstate is 1: 0.05;
(3) dripping the solution A into the solution B by using a peristaltic pump, stirring, and drying the mixed solution after uniformly stirring to obtain mixed powder; the dropping speed of the peristaltic pump is 3ml/min, the drying temperature is 80 ℃, and the drying time is 10 h.
(4) Calcining the mixed powder in air atmosphere, cooling, taking out, grinding by using an agate mortar, and screening to obtain WO3Modified nickel-rich ternary lithium ion battery anode material; the calcining temperature is 700 ℃; the calcination time is 10 h; the standard sieve for sieving is 250 mesh.
The WO obtained above3Adding N-methyl pyrrolidone accounting for 70% of the total weight of the three materials into the modified nickel-rich ternary lithium ion battery positive electrode material, polyvinylidene fluoride and conductive carbon black according to the weight ratio of 90% to 5%, uniformly stirring, coating on an aluminum foil, drying at 90 ℃, cutting into positive active electrode pieces with phi of 16mm by using a sheet punching machine, slicing, weighing, transferring into a vacuum drying oven, and carrying out vacuum drying at 80 ℃. 1mol/L LiPF with metallic lithium sheet as negative electrode6As electrolyte, Cegard 2325 was used for the separator, assembled into CR2025 button cells in an argon glove box. The assembled battery is tested for charge and discharge performance on a Xinwei battery detector system, and is charged and discharged at 0.5C within the voltage range of 2.75-4.3V, and the discharge specific capacity is 188 mAh/g.
Adopts pure nickel-rich ternary lithium ion battery anode material LiNi0.85Co0.1Mn0.05O2And via WO3Modified LiNi0.85Co0.1Mn0.05O2The phase structure, the morphology characteristics and the electrochemical performance are characterized and tested, and XRD patterns of the two materials in figure 1 show classical alpha-NaFeO2Layered structure, without other impurities, described in WO3The modified anode material does not change the original structure, and the peak intensity ratio I (003)/I (104) is more than 1.2, which indicates that the two materials have lower cation mixed arrangement degree and higher ordering degree;
the SEM image of FIG. 2 shows that both materials exhibit a standard quadratic spheroidal shapeThe size is about 8-10 μm, and WO is observed3The appearance of the unmodified material is changed to a certain extent by the modified anode material, and the modified anode material is processed by WO3The particle edge of the modified anode material is gradually blurred, the spherical surface is more compact, and WO3Uniformly distributed on the surface of the nickel-rich ternary lithium ion battery anode material particles.
FIG. 3 shows the results of electrochemical performance tests of WO3The first discharge specific capacity of the modified cathode material is 188mAh/g which is slightly lower than that of an unmodified raw material (the discharge specific capacity is 193 mAh/g); FIG. 4 is a cycle performance curve of two materials circulating for 100 weeks at 0.5C rate in a voltage range of 2.75-4.3V, and the capacity retention rate of an unmodified positive electrode material after 100 weeks circulation is 80.25%, compared with the capacity retention rate of the unmodified positive electrode material after WO3The modified cathode material reaches 91.63%, and shows excellent cycling stability, and is illustrated by adopting WO in combination with an SEM image in figure 23The modified positive electrode material can inhibit the cracking of particles, maintain the mechanical integrity of the active particle material in the circulation process, and prevent the sudden contraction and expansion of crystal lattices, so as to protect the interior of the particles from being corroded by electrolyte, inhibit the permeation of the electrolyte and enhance the electrochemical stability of the material;
FIG. 5 is a graph of rate performance for two materials cycled at 0.5C, 1C, 2C, 3C, 5C for 10 weeks, respectively, and the results are shown via WO3The rate capability of the modified anode material is obviously superior to that of an unmodified material, and particularly, the specific discharge capacity of the modified anode material is higher than that of the unmodified material by about 20mAh/g under high rates of 3C, 5C and the like, which is mainly WO3The modified nickel-rich ternary lithium ion battery cathode material effectively inhibits the reaction of electrolyte and cathode material particles, is more favorable for the de-intercalation of lithium ions in the charge-discharge process, and greatly improves the electrochemical reversibility of the nickel-rich ternary lithium ion battery cathode material under high magnification.
Example 2
A preparation method of a WO3 modified nickel-rich ternary lithium ion battery positive electrode material comprises the following steps:
(1) stirring the tungsten compound and absolute ethyl alcohol together, stirring for 2 hours at the stirring speed of 800r/min, and dispersing uniformly to form a mixed solution A; the tungsten compound is ammonium metatungstate, and the weight ratio of the ammonium metatungstate to the absolute ethyl alcohol is 1: 7;
(2) adding nickel-rich ternary lithium ion battery anode material powder into a mixed solution of absolute ethyl alcohol and deionized water, stirring for 2 hours at a stirring speed of 800r/min, and dispersing uniformly to form a solution B; the nickel-rich ternary lithium ion battery anode material powder is LiNi0.9Co0.05Mn0.05O2The weight ratio of the nickel-rich ternary lithium ion battery anode material to the absolute ethyl alcohol is 1: 1.5, the weight ratio of the absolute ethyl alcohol to the deionized water is 1: 0.5; the weight ratio of the adding amount of the nickel-rich ternary lithium ion battery anode material to the adding amount of the ammonium metatungstate in the first step is 1: 0.02;
(3) dripping the solution A into the solution B by using a peristaltic pump, stirring, and drying the mixed solution after uniformly stirring to obtain mixed powder; the dropping speed of the peristaltic pump is 5ml/min, the drying temperature is 100 ℃, and the drying time is 5 h.
(4) Calcining the mixed powder in air atmosphere, cooling, taking out, grinding by using an agate mortar, and screening to obtain WO3Modified nickel-rich ternary lithium ion battery anode material; the calcining temperature is 500 ℃; the calcination time is 15 h; the standard sieve for sieving is 200 mesh.
The WO obtained above3Adding N-methyl pyrrolidone accounting for 70% of the total weight of the three materials into the modified nickel-rich ternary lithium ion battery positive electrode material, polyvinylidene fluoride and conductive carbon black according to the weight ratio of 90% to 5%, uniformly stirring, coating on an aluminum foil, drying at 90 ℃, cutting into positive active electrode pieces with phi of 16mm by using a sheet punching machine, slicing, weighing, transferring into a vacuum drying oven, and carrying out vacuum drying at 80 ℃. 1mol/L LiPF with metallic lithium sheet as negative electrode6As electrolyte, Cegard 2325 was used for the separator, assembled into CR2025 button cells in an argon glove box. The assembled battery is tested for charge and discharge performance on a Xinwei battery detector system, and is charged and discharged at 0.5C within the voltage range of 2.75-4.3V, and the discharge specific capacity is 191 mAh/g.
Example 3
A preparation method of a WO3 modified nickel-rich ternary lithium ion battery positive electrode material comprises the following steps:
(1) stirring the tungsten compound and absolute ethyl alcohol together, stirring for 2.5 hours at the stirring speed of 900r/min, and dispersing uniformly to form a mixed solution A; the tungsten compound is ammonium metatungstate; the weight ratio of ammonium metatungstate to absolute ethyl alcohol is 1: 6;
(2) adding nickel-rich ternary lithium ion battery anode material powder into a mixed solution of absolute ethyl alcohol and deionized water, stirring for 2.5 hours at a stirring speed of 900r/min, and dispersing uniformly to form a solution B; the nickel-rich ternary lithium ion battery anode material powder is LiNi0.7Co0.2Mn0.1O2The weight ratio of the nickel-rich ternary lithium ion battery anode material to the absolute ethyl alcohol is 1: 1.6, the weight ratio of the absolute ethyl alcohol to the deionized water is 1: 0.7; the weight ratio of the adding amount of the nickel-rich ternary lithium ion battery anode material to the adding amount of the ammonium metatungstate in the first step is 1: 0.1;
(3) dripping the solution A into the solution B by using a peristaltic pump, stirring, and drying the mixed solution after uniformly stirring to obtain mixed powder; the dropping speed of the peristaltic pump is 4ml/min, the drying temperature is 70 ℃, and the drying time is 9 h.
(4) Calcining the mixed powder in air atmosphere, cooling, taking out, grinding by using an agate mortar, and screening to obtain WO3Modified nickel-rich ternary lithium ion battery anode material; the calcining temperature is 650 ℃; the calcination time is 18 h; the standard sieve for sieving is 200 mesh.
The WO obtained above3Adding N-methyl pyrrolidone accounting for 70% of the total weight of the three materials into the modified nickel-rich ternary lithium ion battery positive electrode material, polyvinylidene fluoride and conductive carbon black according to the weight ratio of 90% to 5%, uniformly stirring, coating on an aluminum foil, drying at 90 ℃, cutting into positive active electrode pieces with phi of 16mm by using a sheet punching machine, slicing, weighing, transferring into a vacuum drying oven, and carrying out vacuum drying at 80 ℃. 1mol/L LiPF with metallic lithium sheet as negative electrode6As electrolyte, Cegard 2325 was used for the separator, assembled into CR2025 button cells in an argon glove box. The assembled battery is tested for charging and discharging performance on a Xinwei battery detector system at 2.75 ℃The material is charged and discharged at 0.5C within the voltage range of 4.3V, and the specific discharge capacity is 173 mAh/g.
Example 4
A preparation method of a WO3 modified nickel-rich ternary lithium ion battery positive electrode material comprises the following steps:
(1) stirring the tungsten compound and absolute ethyl alcohol together, stirring for 3 hours at a stirring speed of 750r/min, and dispersing uniformly to form a mixed solution A; the tungsten compound is tungsten acetate; the weight ratio of the tungsten acetate to the absolute ethyl alcohol is 1: 10;
(2) adding nickel-rich ternary lithium ion battery anode material powder into a mixed solution of absolute ethyl alcohol and deionized water, stirring for 3 hours at a stirring speed of 750r/min, and dispersing uniformly to form a solution B; the nickel-rich ternary lithium ion battery anode material powder is LiNi0.6Co0.2Mn0.2O2The weight ratio of the nickel-rich ternary lithium ion battery anode material to the absolute ethyl alcohol is 1: 1.2, the weight ratio of the absolute ethyl alcohol to the deionized water is 1: 0.6; the weight ratio of the adding amount of the nickel-rich ternary lithium ion battery anode material to the adding amount of the tungsten acetate in the first step is 1: 0.2;
(3) dripping the solution A into the solution B by using a peristaltic pump, stirring, and drying the mixed solution after uniformly stirring to obtain mixed powder; the dropping speed of the peristaltic pump is 2ml/min, the drying temperature is 80 ℃, and the drying time is 6 h.
(4) Calcining the mixed powder in air atmosphere, cooling, taking out, grinding by using an agate mortar, and screening to obtain WO3Modified nickel-rich ternary lithium ion battery anode material; the calcining temperature is 500 ℃; the calcination time is 20 h; the standard sieve for sieving is 150 mesh.
The WO obtained above3Adding N-methyl pyrrolidone accounting for 70% of the total weight of the three materials into the modified nickel-rich ternary lithium ion battery positive electrode material, polyvinylidene fluoride and conductive carbon black according to the weight ratio of 90% to 5%, uniformly stirring, coating on an aluminum foil, drying at 90 ℃, cutting into positive active electrode pieces with phi of 16mm by using a sheet punching machine, slicing, weighing, transferring into a vacuum drying oven, and carrying out vacuum drying at 80 ℃. With a metal lithium plate as a negative electrode, 1mol/L of LiPF6As electrolyte, Cegard 2325 was used for the separator, assembled into CR2025 button cells in an argon glove box. The assembled battery is tested for charge and discharge performance on a Xinwei battery detector system, and is charged and discharged at 0.5C within the voltage range of 2.75-4.3V, and the discharge specific capacity is 160 mAh/g.
Example 5
A preparation method of a WO3 modified nickel-rich ternary lithium ion battery positive electrode material comprises the following steps:
(1) stirring the tungsten compound and absolute ethyl alcohol together, stirring for 5 hours at the stirring speed of 850r/min, and dispersing uniformly to form a mixed solution A; the tungsten compound is tungsten acetate; the weight ratio of the tungsten acetate to the absolute ethyl alcohol is 1: 8;
(2) adding nickel-rich ternary lithium ion battery anode material powder into a mixed solution of absolute ethyl alcohol and deionized water, stirring for 5 hours at a stirring speed of 850r/min, and dispersing uniformly to form a solution B; the nickel-rich ternary lithium ion battery anode material powder is LiNi0.8Co0.1Mn0.1O2The weight ratio of the nickel-rich ternary lithium ion battery anode material to the absolute ethyl alcohol is 1: 2, the weight ratio of the absolute ethyl alcohol to the deionized water is 1: 1; the weight ratio of the adding amount of the nickel-rich ternary lithium ion battery anode material to the adding amount of the tungsten acetate in the step one is 1: 0.01;
(3) dripping the solution A into the solution B by using a peristaltic pump, stirring, and drying the mixed solution after uniformly stirring to obtain mixed powder; the dropping speed of the peristaltic pump is 3.5ml/min, the drying temperature is 90 ℃, and the drying time is 7 hours.
(4) Calcining the mixed powder in air atmosphere, cooling, taking out, grinding by using an agate mortar, and screening to obtain WO3Modified nickel-rich ternary lithium ion battery anode material; the calcining temperature is 850 ℃; the calcination time is 10 h; the standard sieve for sieving is 300 mesh.
The WO obtained above3Adding N-methyl pyrrolidone accounting for 70 percent of the total weight of the three materials into the modified nickel-rich ternary lithium ion battery positive electrode material, polyvinylidene fluoride and conductive carbon black according to the weight ratio of 90 percent to 5 percent, uniformly stirring, and coating the mixture on an aluminum foilDrying at 90 deg.C, cutting into positive electrode slice with diameter of 16mm, weighing, transferring into vacuum drying oven, and vacuum drying at 80 deg.C. 1mol/L LiPF with metallic lithium sheet as negative electrode6As electrolyte, Cegard 2325 was used for the separator, assembled into CR2025 button cells in an argon glove box. The assembled battery is tested for charge and discharge performance on a Xinwei battery detector system, and is charged and discharged at 0.5C within the voltage range of 2.75-4.3V, and the specific discharge capacity of the battery is 195 mAh/g.
Example 6
A preparation method of a WO3 modified nickel-rich ternary lithium ion battery positive electrode material comprises the following steps:
(1) stirring the tungsten compound and absolute ethyl alcohol together, stirring for 4 hours at the stirring speed of 900r/min, and dispersing uniformly to form a mixed solution A; the tungsten compound is sodium tungstate; the weight ratio of sodium tungstate to absolute ethyl alcohol is 1: 9;
(2) adding nickel-rich ternary lithium ion battery anode material powder into a mixed solution of absolute ethyl alcohol and deionized water, stirring for 4 hours at a stirring speed of 900r/min, and dispersing uniformly to form a solution B; the nickel-rich ternary lithium ion battery anode material powder is LiNi0.95Co0.02Mn0.03O2The weight ratio of the nickel-rich ternary lithium ion battery anode material to the absolute ethyl alcohol is 1: 1.8, the weight ratio of the absolute ethyl alcohol to the deionized water is 1: 0.9; the weight ratio of the adding amount of the nickel-rich ternary lithium ion battery anode material to the adding amount of the sodium tungstate in the first step is 1: 0.15;
(3) dripping the solution A into the solution B by using a peristaltic pump, stirring, and drying the mixed solution after uniformly stirring to obtain mixed powder; the dropping speed of the peristaltic pump is 5ml/min, the drying temperature is 80 ℃, and the drying time is 9 h.
(4) Calcining the mixed powder in air atmosphere, cooling, taking out, grinding by using an agate mortar, and screening to obtain WO3Modified nickel-rich ternary lithium ion battery anode material; the calcining temperature is 900 ℃; the calcination time is 8 h; the standard sieve for sieving is 300 mesh.
The WO obtained above3Modified nickel-rich ternary lithium ionAdding N-methyl pyrrolidone accounting for 70 percent of the total weight of the three materials into the positive electrode material of the sub-battery, polyvinylidene fluoride and conductive carbon black according to the weight ratio of 90 percent to 5 percent, uniformly stirring, coating the mixture on an aluminum foil, drying the aluminum foil at 90 ℃, cutting the aluminum foil into positive active electrode pieces with phi of 16mm by using a sheet punching machine, weighing the pieces, transferring the pieces into a vacuum drying box, and carrying out vacuum drying at 80 ℃. 1mol/L LiPF with metallic lithium sheet as negative electrode6As electrolyte, Cegard 2325 was used for the separator, assembled into CR2025 button cells in an argon glove box. The assembled battery is tested for charge and discharge performance on a Xinwei battery detector system, and is charged and discharged at 0.5C within the voltage range of 2.75-4.3V, and the discharge specific capacity is 169 mAh/g.
WO was obtained in examples 1 to 63The modified nickel-rich ternary lithium ion battery anode material is compared with an unmodified nickel-rich ternary lithium ion battery anode material in a test, and WO3The modified nickel-rich ternary lithium ion battery anode material has higher specific discharge capacity, good cycle performance and rate capability.

Claims (8)

1. A preparation method of a WO3 modified nickel-rich ternary lithium ion battery positive electrode material is characterized by comprising the following steps:
mixing a tungsten source compound with absolute ethyl alcohol, stirring for 1-5 hours at a stirring speed of 700-900 r/min, and uniformly mixing to form a mixed solution A;
adding the nickel-rich ternary lithium ion battery anode material powder into a mixed solution of absolute ethyl alcohol and deionized water, stirring for 1-5 hours at a stirring speed of 700-900 r/min, and dispersing uniformly to form a solution B;
step three, dripping the solution A into the solution B by using a peristaltic pump, stirring, and drying the uniformly stirred mixed solution to obtain mixed powder;
step four, calcining the mixed powder in the air atmosphere, cooling, taking out, grinding by using an agate mortar, and screening to obtain WO3The modified nickel-rich ternary lithium ion battery anode material.
2. The method for preparing the cathode material of the nickel-rich ternary lithium ion battery modified by WO3 according to claim 1, wherein the tungsten source compound in the first step is one of ammonium metatungstate, sodium tungstate and tungsten acetate.
3. The preparation method of the WO3 modified nickel-rich ternary lithium ion battery cathode material according to claim 2, wherein the weight ratio of the tungsten source compound to the absolute ethyl alcohol in the first step is 0.1-0.1875.
4. The method for preparing the cathode material of the nickel-rich ternary lithium ion battery modified by WO3 according to claim 3, wherein the cathode material of the nickel-rich ternary lithium ion battery in the second step is LiNixCoyMnzO2Wherein x is more than or equal to 0.6 and less than or equal to 0.95, y is more than or equal to 0.01 and less than or equal to 0.2, z is more than or equal to 0.01 and less than or equal to 0.2, and x + y + z is 1.
5. The preparation method of the WO3 modified nickel-rich ternary lithium ion battery cathode material according to claim 4, wherein the weight ratio of the nickel-rich ternary lithium ion battery cathode material to absolute ethyl alcohol in the second step is 0.5-1, and the weight ratio of the absolute ethyl alcohol to deionized water is 1-2.
6. The preparation method of the WO3 modified nickel-rich ternary lithium ion battery cathode material according to claim 5, wherein the weight ratio of the tungsten source compound to the nickel-rich ternary lithium ion battery cathode material is 0.01-0.2.
7. The preparation method of the WO3 modified nickel-rich ternary lithium ion battery positive electrode material according to claim 6, wherein the dropping speed of a peristaltic pump in the third step is 2-5 ml/min, the drying temperature is 60-100 ℃, and the drying time is 5-10 h.
8. The preparation method of the WO3 modified nickel-rich ternary lithium ion battery positive electrode material according to claim 7, characterized in that the calcination in the fourth step is performed in a tube furnace, the calcination temperature is 400-900 ℃, the calcination time is 8-20 h, and the standard sieve for sieving is 150-300 meshes.
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