CN113488634B - Double-layer coated modified high-nickel cobalt-free single crystal ternary cathode material and preparation method thereof - Google Patents

Double-layer coated modified high-nickel cobalt-free single crystal ternary cathode material and preparation method thereof Download PDF

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CN113488634B
CN113488634B CN202110867246.9A CN202110867246A CN113488634B CN 113488634 B CN113488634 B CN 113488634B CN 202110867246 A CN202110867246 A CN 202110867246A CN 113488634 B CN113488634 B CN 113488634B
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cathode material
nickel cobalt
ternary cathode
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CN113488634A (en
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张宝
邓鹏�
程诚
林可博
周亚楠
邓梦轩
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Zhejiang Power New Energy Co Ltd
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Abstract

A double-layer coated modified high-nickel cobalt-free single crystal ternary positive electrode material and a preparation method thereof are provided, wherein the chemical formula of the positive electrode material is LiNi x Mn y W z O 2 @TMO 2 @ C, where: x is more than or equal to 0.9<1，0<y≤0.06，0<z≤0.04，x+y+z＝1，TMO 2 Is one or more of Al, Mg, Cu and Ti oxides. The preparation method comprises the following steps: (1) carrying out coprecipitation reaction on a nickel source, a manganese source, a tungsten source, a NaOH solution and an ammonia water solution to obtain a precursor; (2) uniformly mixing the precursor with a lithium source, and calcining to obtain a ternary cathode material; (3) mixing a TM source with a cobalt-free ternary cathode material, and calcining to obtain a single-layer coated ternary cathode material; (4) and mixing the single-layer coated ternary cathode material with a carbon source, and calcining to obtain the lithium ion battery. The double-layer coated modified high-nickel cobalt-free single crystal ternary cathode material has good electrochemical performance, simple preparation method and low production cost.

Description

Double-layer coated modified high-nickel cobalt-free single crystal ternary positive electrode material and preparation method thereof
Technical Field
The invention relates to a lithium ion battery anode material and a preparation method thereof, in particular to a double-layer coated modified high-nickel cobalt-free single crystal ternary anode material and a preparation method thereof.
Background
The lithium ion battery plays an important role in the field of new energy automobiles which are developed at a high speed and the field of electronic products such as mobile phones and notebooks. The positive electrode material is one of the key materials of the lithium ion battery, and directly influences the electrochemical properties of the lithium ion battery, such as charge and discharge capacity, cycle performance, rate performance, thermal stability and the like. With the increasing demand for energy density of lithium ion batteries and the rising price of Co-containing resources, the development of Co-containing cathode materials of lithium ion batteries is hindered, and people are further promoted to focus on the high-nickel cathode materials of lithium ion batteries. However, at present, the commonly used high nickel materials in the market have the problems of unstable structure, low capacity retention rate, poor cycle stability and the like, and still contain cobalt element, so that the production cost is high.
CN107516731A discloses a modified lithium ion battery anode material and a preparation method thereof, wherein the modified lithium ion battery anode material comprises an anode material core and a composite coating layer coated on the surface of the anode material core, and the composite coating layer is made of a material containing Li 0.5 La 0.5 TiO 3 And a first coating layer comprising LiTaO 3 The structural formula of the core of the anode material is Li 1±ε Ni x Co y Mn z M 1-x-y-z O 2 Wherein epsilon is more than-0.1 and less than 0.1, x is more than 0, Y and z are less than 1, and M is one of Mg, Sr, Ba, Al, In, Ti, V, Mn, Co, Ni, Y, Zr, Nb, Mo, W, La, Ce, Nd, Sm and other elements. However, the cathode material obtained by the method still contains cobalt element and La element, so that the production cost is high.
CN108682843A discloses a preparation method of a rock salt type lithium ion battery anode material, which comprises the following steps: (1) grinding and uniformly mixing a lithium source, a high-valence state manganese source and a low-valence state manganese source, calcining in an inert atmosphere, and cooling and grinding along with a furnace to obtain LiMnO 2 A precursor; (2) the LiMnO obtained in the step (1) is 2 Grinding and uniformly mixing the precursor and lithium peroxide, calcining in an inert atmosphere, annealing, and cooling along with the furnace to obtain the rock salt type lithium ion battery cathode material Li 4 Mn 2 O 5 . The cathode material obtained by the method does not contain cobalt element, but the electrochemical performance of the cathode material is poor.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a double-layer coating modified high-nickel cobalt-free single crystal ternary cathode material which is simple in preparation method, low in production cost and good in electrochemical performance.
The invention further aims to solve the technical problem of providing a preparation method of the double-layer coating modified high-nickel cobalt-free single crystal ternary cathode material, which is simple and convenient to operate.
The invention adopts the technical scheme that a double-layer coating modified high-nickel cobalt-free single crystal ternary positive electrode material with a chemical formula of LiNi is adopted for solving the technical problem x Mn y W z O 2 @ TMO @ C, where: x is more than or equal to 0.9<1，0<y≤0.06，0<z is less than or equal to 0.04, x + y + z =1, and TMO is one or more of Al, Mg, Cu and Ti oxides.
The invention further solves the technical problem by adopting the technical scheme that the preparation method of the double-layer coating modified high-nickel cobalt-free single crystal ternary cathode material comprises the following steps:
(1) adding a nickel source, a manganese source and a tungsten source into deionized water, and uniformly stirring to obtain a mixed salt solution; mixing the mixed salt solution, a precipitator NaOH solution and a complexing agent NH 3 ·H 2 Adding the O solution into a reaction kettle together, continuously stirring, and carrying out coprecipitation reaction to obtain solid-liquid mixed slurry;
(2) carrying out solid-liquid separation on the solid-liquid mixed slurry obtained in the step (1), collecting solids, washing, drying and demagnetizing the solids to obtain a high-nickel cobalt-free ternary cathode material precursor Ni x Mn y W z (OH) 2 ；
(3) The high nickel cobalt-free ternary anode material precursor Ni obtained in the step (2) x Mn y W z (OH) 2 Evenly mixing with a lithium source, and calcining in a pure oxygen atmosphere to obtain the high-nickel cobalt-free ternary cathode material LiNi x Mn y W z O 2 ；
(4) Uniformly dispersing soluble salt of a TM source in an organic solvent, and then adding the high-nickel cobalt-free ternary cathode material LiNi obtained in the step (3) x Mn y W z O 2 Continuously stirring, heating to evaporate solvent, collecting solid, and vacuum dryingDrying and calcining to obtain the single-layer coated high-nickel cobalt-free ternary cathode material LiNi x Mn y W z O 2 @TMO；
(5) The single-layer coated high-nickel cobalt-free ternary cathode material LiNi obtained in the step (4) x Mn y W z O 2 @ TMO and a carbon source are dispersed in an organic solvent, are uniformly stirred and are dried to obtain powder; calcining the powder to obtain the double-layer coated modified high-nickel cobalt-free single crystal ternary cathode material LiNi x Mn y W z O 2 @TMO@C。
Preferably, in the step (1), the nickel source is one or more of nickel acetate, nickel nitrate and nickel sulfate; the manganese source is one or more of manganese acetate, manganese nitrate and manganese sulfate; the tungsten source is one or more of tungsten acetate, tungsten nitrate, tungsten sulfate and tungsten carbonate.
Preferably, in the step (1), the concentration of the mixed salt solution is 2-10 mol/L, and more preferably 4-6 mol/L; the concentration of the precipitator NaOH solution is 2-10 mol/L, and more preferably 4-8 mol/L; the complexing agent NH 3 ·H 2 The concentration of the O solution is 2-12 mol/L, and the more preferable concentration is 4-10 mol/L; the stirring speed of the coprecipitation reaction is 500-800rpm, the pH value of the reaction solution is 11.5-13.5, the ammonia value is 5-15 g/L, and the reaction temperature is 60-70 ℃.
Preferably, in the step (3), the molar ratio of the lithium source to the high-nickel cobalt-free ternary cathode material precursor is 1.02-1.08: 1.0; the calcination is divided into two-stage sintering, the calcination temperature of the first-stage sintering is 250-600 ℃, the calcination time is 4-7 hours, the calcination temperature of the second-stage calcination is 650-850 ℃, and the calcination time is 12-30 hours.
Preferably, in step (4), the soluble salt of the TM source is one or more of acetate, nitrate, sulfate and organic salt; the solvent is one or more of ethanol, glycol and methanol.
Preferably, in the step (4), the temperature of the evaporated solvent is 75-90 ℃; the time for evaporating the solvent is 4-6 hours, and the temperature for vacuum drying is 110-130 ℃; and the vacuum drying time is 10-15 h.
Preferably, in the step (4), the calcining temperature is 500-700 ℃; and the calcining time is 5-12 h.
Preferably, in the step (5), the carbon source is one or more of carbon nanotube, graphene, glucose and citric acid; the carbon source is mixed with LiNi x Mn y W z O 2 @ TMO mass ratio of 1: 5-15, more preferably 1: 8-10; the drying temperature is 60-120 ℃; and the drying time is 5-10 h.
Preferably, in the step (5), the calcining temperature is 250-650 ℃, and more preferably 400-550 ℃; the calcining time is 2-10 hours, and preferably 4-6 hours; the calcining atmosphere is argon or nitrogen.
Compared with the prior art, the invention has the following beneficial effects:
(1) research shows that W element replaces cobalt element in the traditional ternary anode material, the stability of the ternary anode layered structure can be maintained, the mechanical strength of the anode material is enhanced, and the W-containing compound is low in price, so that the production cost is reduced, and industrialization is realized;
(2) according to the invention, the high-nickel cobalt-free single crystal ternary cathode material is synthesized by a coprecipitation method, and then a layer of metal oxide is coated on the high-nickel cobalt-free single crystal ternary cathode material, so that the direct contact between the high-nickel cobalt-free single crystal ternary cathode material and an electrolyte is effectively isolated, the corrosion of the electrolyte to the cathode material is reduced, the conductivity of the cathode material is further improved by coating of a carbon layer, and the cycle performance and the rate performance of the high-nickel cobalt-free single crystal ternary cathode material are improved;
(3) research shows that except W element, the electrochemical performance of the lithium ion battery assembled by the anode material prepared by using other elements to replace Co element is inferior to that of the W element; in the invention, W element is used for replacing cobalt element in the traditional ternary cathode material, and the prepared double-layer coating modified high-nickel cobalt-free single crystal ternary cathode material LiNi x Mn y W z O 2 In @ TMO @ C, the doped W element has synergistic effect with the coating layer metal oxide TMO and the C layer, so that the structure of the high-nickel cobalt-free single crystal ternary cathode material can be maintainedThe stability is realized, the occurrence of side reactions in the circulating process is inhibited, a rapid channel is provided for the insertion/extraction of lithium ions, and the generation of microcracks on the surface of the material is inhibited;
(4) the preparation method is simple, simple and convenient to operate, low in production cost and suitable for industrial production.
Drawings
FIG. 1 shows a precursor Ni of a double-layer-coated modified high-nickel cobalt-free single-crystal ternary cathode material in example 1 of the present invention 0.90 Mn 0.07 W 0.03 (OH) 2 SEM image of (d).
FIG. 2 is LiNi, a double-layer coated modified high-nickel cobalt-free single crystal ternary positive electrode material in embodiment 1 of the invention 0.90 Mn 0.07 W 0.03 O 2 SEM image of (d).
Detailed Description
The invention is further described with reference to the following figures and specific examples.
Example 1
The chemical formula of the double-layer coated modified high-nickel cobalt-free single crystal ternary cathode material in the embodiment is LiNi 0.90 Mn 0.07 W 0.03 O 2 @TiO 2 @C。
The preparation method of the double-layer-coated modified high-nickel cobalt-free single crystal ternary cathode material comprises the following steps of:
(1) adding nickel sulfate, manganese sulfate and tungsten sulfate into deionized water according to the molar ratio of 0.90:0.07:0.03, and uniformly stirring to obtain a mixed salt solution with the total metal ion concentration of 4 mol/L; mixing the mixed salt solution, 4mol/L of precipitator NaOH solution and 5mol/L of complexing agent NH 3 ·H 2 Adding the O solution into a reaction kettle together, continuously stirring at the stirring speed of 400rpm, controlling the temperature of the reaction kettle to be 65 ℃, controlling the ammonia value of the reaction solution to be 8g/L and the pH value to be 12, and reacting for 16 hours by a coprecipitation method to obtain solid-liquid mixed slurry;
(2) carrying out solid-liquid separation on the solid-liquid mixed slurry obtained in the step (1), collecting solids, washing, drying and demagnetizing the solids to obtain a high-nickel cobalt-free ternary cathode material precursor Ni 0.90 Mn 0.07 W 0.03 (OH) 2 ；
(3) Performing Ni treatment on the high-nickel cobalt-free ternary positive electrode material precursor obtained in the step (2) 0.90 Mn 0.07 W 0.03 (OH) 2 Uniformly mixing the lithium hydroxide and lithium hydroxide according to the molar ratio of 1.04:1.0, calcining for 6 hours at 480 ℃ in pure oxygen atmosphere, then heating to 850 ℃ and calcining for 18 hours to obtain the high-nickel cobalt-free ternary cathode material LiNi 0.90 Mn 0.07 W 0.03 O 2 ；
(4) Uniformly dispersing 0.01mol of tetrabutyl titanate in 200ml of absolute ethyl alcohol, and then adding the high-nickel cobalt-free ternary cathode material LiNi obtained in the step (3) 0.90 Mn 0.07 W 0.03 O 2 Continuously stirring, evaporating the solvent at 80 ℃, collecting the solid, vacuum drying at 110 ℃ for 12h, calcining at 700 ℃ for 10h to obtain the single-layer coated high-nickel cobalt-free ternary cathode material LiNi 0.90 Mn 0.07 W 0.03 O 2 @TiO 2 ；
(5) The single-layer coated high-nickel cobalt-free ternary cathode material LiNi obtained in the step (4) is subjected to LiNi 0.90 Mn 0.07 W 0.03 O 2 @TiO 2 Mixing with carbon nanotubes at a mass ratio of 10:1, dispersing in absolute ethyl alcohol, stirring uniformly, and drying at 90 ℃ to obtain powder; calcining the powder for 4 hours at 500 ℃ in an argon atmosphere to obtain the double-layer coated modified high-nickel cobalt-free single crystal ternary cathode material LiNi 0.90 Mn 0.07 W 0.03 O 2 @TiO 2 @C。
For the precursor Ni obtained in this example 0.90 Mn 0.07 W 0.03 (OH) 2 Performing characterization and detection, as shown in FIG. 1, on the precursor Ni obtained in step (2) of this example 0.90 Mn 0.07 W 0.03 (OH) 2 The shape of the particles is spherical, the particles are uniformly distributed, and the particle size of the particles is 2-4 mu m. The double-layer coating modified high-nickel cobalt-free single crystal ternary positive electrode material LiNi of the embodiment 0.90 Mn 0.07 W 0.03 O 2 The characterization and detection were carried out, and the particles were very small, as shown in FIG. 2, and were in a single crystal state. The lithium ion battery is assembled by adopting the double-layer coating modified high-nickel cobalt-free single crystal ternary cathode material to prepare the cathode, and the electrochemical test is carried out on the lithium ion batteryIn the voltage range of 4.3V, the first discharge gram capacity under 0.1C (1C =200 mA/g) reaches 210.2mAh/g, the first discharge gram capacity under 1C multiplying power reaches 191.7mAh/g, the discharge capacity after 100 cycles under 1C is 173.3mAh/g, and the capacity retention rate reaches 90.4%.
Example 2
The chemical formula of the double-layer coated modified high-nickel cobalt-free single crystal ternary cathode material in the embodiment is LiNi 0.90 Mn 0.05 W 0.05 O 2 @ Al 2 O 3 @C。
The preparation method of the double-layer-coated modified high-nickel cobalt-free single crystal ternary cathode material comprises the following steps of:
(1) adding nickel sulfate, manganese sulfate and tungsten sulfate into deionized water according to the mol ratio of 0.90:0.05:0.05, and uniformly stirring to obtain a mixed salt solution with the total metal ion concentration of 4 mol/L; mixing the mixed salt solution, 5mol/L of precipitator NaOH solution and 8mol/L of complexing agent NH 3 ·H 2 Adding the O solution into a reaction kettle together, stirring continuously at the stirring speed of 500rpm, controlling the temperature of the reaction kettle at 60 ℃, controlling the ammonia value of the reaction solution at 9g/L and the pH value at 11.8, reacting for 16h by a coprecipitation method to obtain solid-liquid mixed slurry,
(2) carrying out solid-liquid separation on the solid-liquid mixed slurry obtained in the step (1), collecting solids, washing, drying and demagnetizing the solids to obtain a high-nickel cobalt-free ternary cathode material precursor Ni 0.90 Mn 0.05 W 0.05 (OH) 2 ；
(3) Performing Ni treatment on the high-nickel cobalt-free ternary positive electrode material precursor obtained in the step (2) 0.90 Mn 0.05 W 0.05 (OH) 2 And lithium carbonate according to a molar ratio of Li: uniformly mixing (Ni + Mn + W) =1.04:1.0, calcining at 500 ℃ for 5h in pure oxygen atmosphere, heating to 850 ℃ and calcining for 20h to obtain the high-nickel cobalt-free ternary cathode material LiNi 0.90 Mn 0.05 W 0.05 O 2 ；
(4) Uniformly dispersing 0.01mol of aluminum nitrate into 200ml of absolute ethyl alcohol, and then adding the high-nickel cobalt-free ternary cathode material LiNi obtained in the step (3) 0.90 Mn 0.05 W 0.05 O 2 The stirring is continuously carried out,evaporating the solvent at 90 ℃, collecting the solid, drying in vacuum at 120 ℃ for 10h, calcining at 650 ℃ for 12h to obtain the single-layer coated high-nickel cobalt-free ternary cathode material LiNi 0.90 Mn 0.05 W 0.05 O 2 @ Al 2 O 3 ；
(5) The single-layer coated high-nickel cobalt-free ternary cathode material LiNi obtained in the step (4) is subjected to LiNi 0.90 Mn 0.05 W 0.05 O 2 @ Al 2 O 3 Mixing with citric acid at a mass ratio of 8:1, dispersing in anhydrous ethanol, stirring, and oven drying at 80 deg.C to obtain powder; calcining the powder for 6 hours at 450 ℃ in an argon atmosphere to obtain the double-layer coated modified high-nickel cobalt-free single crystal ternary cathode material LiNi 0.90 Mn 0.05 W 0.05 O 2 @ Al 2 O 3 @C。
The lithium ion battery is assembled by adopting the double-layer coated modified high-nickel cobalt-free single crystal ternary cathode material to prepare the cathode, and electrochemical tests are carried out, wherein the first discharge gram capacity at 0.1C (1C =200 mA/g) reaches 208.4mAh/g, the first discharge gram capacity at 1C multiplying power reaches 189.7mAh/g, the discharge capacity after 100 cycles at 1C reaches 171.3mAh/g, and the capacity retention rate reaches 90.3 percent in the voltage range of 3-4.3V.
Example 3
The chemical formula of the double-layer coated modified high-nickel cobalt-free single crystal ternary cathode material in the embodiment is LiNi 0.90 Mn 0.03 W 0.07 O 2 @CuO@C。
The preparation method of the double-layer coated modified high-nickel cobalt-free single crystal ternary cathode material comprises the following steps:
(1) adding nickel sulfate, manganese sulfate and tungsten sulfate into deionized water according to the mol ratio of 0.90:0.03:0.07, and uniformly stirring to obtain a mixed salt solution with the total metal ion concentration of 4 mol/L; mixing the mixed salt solution, 6mol/L of precipitator NaOH solution and 10mol/L of complexing agent NH 3 ·H 2 Adding the O solution into a reaction kettle together, stirring continuously at the stirring speed of 400rpm, controlling the temperature of the reaction kettle to be 65 ℃, controlling the ammonia value of reaction liquid to be 8g/L and the pH value to be 11.5, reacting for 16h by a coprecipitation method to obtain solid-liquid mixed slurry,
(2) carrying out solid-liquid separation on the solid-liquid mixed slurry obtained in the step (1), collecting solids, washing, drying and demagnetizing the solids to obtain a high-nickel cobalt-free ternary cathode material precursor Ni 0.90 Mn 0.03 W 0.07 (OH) 2 ；
(3) Performing Ni treatment on the high-nickel cobalt-free ternary positive electrode material precursor obtained in the step (2) 0.90 Mn 0.03 W 0.07 (OH) 2 Uniformly mixing the lithium hydroxide and lithium hydroxide according to the molar ratio of 1.03:1.0, calcining for 6 hours at 480 ℃ in pure oxygen atmosphere, then heating to 850 ℃ and calcining for 18 hours to obtain the high-nickel cobalt-free ternary cathode material LiNi 0.90 Mn 0.07 W 0.03 O 2 ；
(4) Uniformly dispersing 0.01mol of copper nitrate into 200ml of absolute ethyl alcohol, and then adding 1mol of the high-nickel cobalt-free ternary cathode material LiNi obtained in the step (3) 0.90 Mn 0.03 W 0.07 O 2 Continuously stirring, evaporating the solvent at 80 ℃, collecting the solid, vacuum drying at 120 ℃ for 10h, calcining at 650 ℃ for 12h to obtain the single-layer coated high-nickel cobalt-free ternary cathode material LiNi 0.90 Mn 0.03 W 0.07 O 2 @CuO；
(5) The single-layer coated high-nickel cobalt-free ternary cathode material LiNi obtained in the step (4) 0.90 Mn 0.03 W 0.07 O 2 Mixing @ CuO and graphene according to a mass ratio of 10:1, dispersing in absolute ethyl alcohol, uniformly stirring, and then drying at 90 ℃ to obtain powder; calcining the powder for 4 hours at 400 ℃ in an argon atmosphere to obtain the double-layer coated modified high-nickel cobalt-free single crystal ternary cathode material LiNi 0.90 Mn 0.03 W 0.07 O 2 @CuO@C。
The lithium ion battery is assembled by adopting the double-layer coated modified high-nickel cobalt-free single crystal ternary cathode material to prepare the cathode, and electrochemical tests are carried out, wherein the first discharge gram capacity under 0.1C (1C =200 mA/g) reaches 208.1mAh/g, the first discharge gram capacity under 1C multiplying power reaches 187.5mAh/g, the discharge capacity after 100 cycles under 1C is 169.4mAh/g, and the capacity retention rate reaches 90.3% in the voltage range of 3-4.3V.
Comparative example 1
Comparative example 1 was compared with example 1, except that copper sulfate was used instead of tungsten sulfate, and other reaction raw materials and preparation conditions were not changed.
Using the cobalt-free ternary cathode Material LiNi of comparative example 1 0.90 Mn 0.07 Cu 0.03 O 2 @TiO 2 The anode material of the lithium ion battery manufactured by @ C is assembled into a button battery for electrochemical test, and the comparative example 1 is cobalt-free ternary anode material LiNi 0.90 Mn 0.07 Cu 0.03 O 2 @TiO 2 @ C is in a voltage range of 3-4.3V, the first discharge gram capacity under 0.1C multiplying power reaches 206.3mAh/g, the discharge specific capacity under 1C is 182.4mAh/g, and the capacity retention rate reaches 82.7% after 100 cycles of circulation.
Comparative example 2
Comparative example 2 is compared with example 1 except that the metal oxide layer coating is not performed and only the carbon layer is coated, and other reaction raw materials and preparation conditions are not changed.
Use of the cobalt-free ternary cathode material LiNi of comparative example 2 0.90 Mn 0.07 W 0.03 O 2 The anode material of the lithium ion battery manufactured by @ C is assembled into a button battery for electrochemical test, and the comparative example 2 is a cobalt-free ternary anode material LiNi 0.90 Mn 0.07 W 0.03 O 2 @ C is in a voltage range of 3-4.3V, the first discharge gram capacity under 0.1C multiplying power reaches 206.8mAh/g, the discharge specific capacity under 1C is 183.7mAh/g, and the capacity retention rate reaches 81.9% after 100 cycles of circulation.
Comparative example 3
Comparative example 3 is compared with example 1, except that no carbon coating is performed, only the metal oxide layer is coated, and other reaction raw materials and preparation conditions are not changed.
Use of the cobalt-free ternary cathode material LiNi of comparative example 3 0.90 Mn 0.07 W 0.03 O 2 @TiO 2 The lithium ion battery anode material is prepared to be assembled into a button battery for electrochemical test, and the comparative example 3 is cobalt-free ternary anode material LiNi 0.90 Mn 0.07 W 0.03 O 2 @TiO 2 Within the voltage range of 3-4.3V, the first discharge gram capacity under 0.1C multiplying power reaches 205.1mAh/g, and the discharge specific capacity under 1C is 180.4mAh/g, and the capacity retention rate reaches 82.5 percent after 100 cycles.

Claims (16)

1. The double-layer coated modified high-nickel cobalt-free single crystal ternary cathode material is characterized in that the chemical formula is LiNi x Mn y W z O 2 @ TMO @ C, where: x is more than or equal to 0.9<1，0<y≤0.06，0<z is less than or equal to 0.04, x + y + z =1, and TMO is one or more of oxides of Al, Mg, Cu and Ti;
the preparation method of the double-layer coated modified high-nickel cobalt-free single crystal ternary cathode material comprises the following steps:
(1) adding a nickel source, a manganese source and a tungsten source into deionized water, and uniformly stirring to obtain a mixed salt solution; mixing the mixed salt solution, a precipitator NaOH solution and a complexing agent NH 3 ·H 2 Adding the O solution into a reaction kettle together, continuously stirring, and carrying out coprecipitation reaction to obtain solid-liquid mixed slurry;
(2) carrying out solid-liquid separation on the solid-liquid mixed slurry obtained in the step (1), collecting solids, washing, drying and demagnetizing the solids to obtain a high-nickel cobalt-free ternary cathode material precursor Ni x Mn y W z (OH) 2 ；
(3) Performing Ni treatment on the high-nickel cobalt-free ternary positive electrode material precursor obtained in the step (2) x Mn y W z (OH) 2 Evenly mixing with a lithium source, and calcining in pure oxygen atmosphere to obtain the high-nickel cobalt-free ternary cathode material LiNi x Mn y W z O 2 ；
(4) Uniformly dispersing soluble salt of a TM source in an organic solvent, and then adding the high-nickel cobalt-free ternary cathode material LiNi obtained in the step (3) x Mn y W z O 2 Continuously stirring, heating to evaporate the solvent, collecting the solid, vacuum drying, and calcining to obtain the single-layer coated high-nickel cobalt-free ternary cathode material LiNi x Mn y W z O 2 @TMO；
(5) The single-layer coated high-nickel cobalt-free ternary cathode material LiNi obtained in the step (4) is subjected to LiNi x Mn y W z O 2 @ TMO and a carbon source are dispersed in an organic solvent,stirring uniformly, and then drying to obtain powder; calcining the powder to obtain the double-layer coated modified high-nickel cobalt-free single crystal ternary cathode material LiNi x Mn y W z O 2 @TMO@C。
2. The preparation method of the double-layer coated modified high-nickel cobalt-free single crystal ternary cathode material according to claim 1, wherein in the step (1), the nickel source is one or more of nickel acetate, nickel nitrate and nickel sulfate; the manganese source is one or more of manganese acetate, manganese nitrate and manganese sulfate; the tungsten source is one or more of tungsten acetate, tungsten nitrate, tungsten sulfate and tungsten carbonate.
3. The preparation method of the double-layer coated modified high-nickel cobalt-free single crystal ternary cathode material as claimed in claim 2, wherein in the step (1), the concentration of the mixed salt solution is 2-10 mol/L; the concentration of the precipitator NaOH solution is 2-10 mol/L; the complexing agent NH 3 ·H 2 The concentration of the O solution is 2-12 mol/L; the stirring speed of the coprecipitation reaction is 500-800rpm, the pH value of the reaction solution is 11.5-13.5, the ammonia value is 5-15 g/L, and the reaction temperature is 60-70 ℃.
4. The preparation method of the double-layer coated modified high-nickel cobalt-free single-crystal ternary cathode material as claimed in claim 2, wherein in the step (3), the molar ratio of the lithium source to the precursor of the high-nickel cobalt-free ternary cathode material is 1.02-1.08: 1.0; the calcination is divided into two-stage sintering, the calcination temperature of the first-stage sintering is 250-600 ℃, the calcination time is 4-7 hours, the calcination temperature of the second-stage calcination is 650-850 ℃, and the calcination time is 12-30 hours.
5. The preparation method of the double-layer coated modified high-nickel cobalt-free single-crystal ternary cathode material as claimed in claim 3, wherein in the step (3), the molar ratio of the lithium source to the precursor of the high-nickel cobalt-free ternary cathode material is 1.02-1.08: 1.0; the calcination is divided into two-stage sintering, the calcination temperature of the first-stage sintering is 250-600 ℃, the calcination time is 4-7 hours, the calcination temperature of the second-stage calcination is 650-850 ℃, and the calcination time is 12-30 hours.
6. The preparation method of the double-layer coated modified high-nickel cobalt-free single-crystal ternary cathode material as claimed in claim 2, wherein in the step (4), the soluble salt of the TM source is one or more of acetate, nitrate, sulfate and organic salt; the solvent is one or more of ethanol, glycol and methanol.
7. The preparation method of the double-layer coated modified high-nickel cobalt-free single-crystal ternary cathode material according to claim 3, wherein in the step (4), the soluble salt of the TM source is one or more of acetate, nitrate, sulfate and organic salt; the solvent is one or more of ethanol, glycol and methanol.
8. The preparation method of the double-layer coated modified high-nickel cobalt-free single crystal ternary cathode material according to claim 2, wherein in the step (4), the temperature of the evaporated solvent is 75-90 ℃; the time for evaporating the solvent is 4-6 hours, and the temperature for vacuum drying is 110-130 ℃; and the vacuum drying time is 10-15 h.
9. The preparation method of the double-layer coated modified high-nickel cobalt-free single crystal ternary cathode material according to claim 3, wherein in the step (4), the temperature of the evaporated solvent is 75-90 ℃; the time for evaporating the solvent is 4-6 hours, and the temperature for vacuum drying is 110-130 ℃; and the vacuum drying time is 10-15 h.
10. The preparation method of the double-layer coated modified high-nickel cobalt-free single crystal ternary cathode material according to claim 2, wherein in the step (4), the calcining temperature is 500-700 ℃; and the calcining time is 5-12 h.
11. The preparation method of the double-layer coated modified high-nickel cobalt-free single crystal ternary cathode material according to claim 3, wherein in the step (4), the calcining temperature is 500-700 ℃; and the calcining time is 5-12 h.
12. The preparation method of the double-layer coated modified high-nickel cobalt-free single crystal ternary cathode material according to claim 2, wherein in the step (5), the carbon source is one or more of carbon nanotube, graphene, glucose and citric acid; the carbon source is mixed with LiNi x Mn y W z O 2 @ TMO mass ratio of 1: 5-15; the drying temperature is 60-120 ℃; and the drying time is 5-10 h.
13. The preparation method of the double-layer coated modified high-nickel cobalt-free single crystal ternary cathode material according to claim 3, wherein in the step (5), the carbon source is one or more of carbon nanotube, graphene, glucose and citric acid; the carbon source is mixed with LiNi x Mn y W z O 2 The mass ratio of @ TMO is 1: 5-15; the drying temperature is 60-120 ℃; and the drying time is 5-10 h.
14. The preparation method of the double-layer coated modified high-nickel cobalt-free single crystal ternary cathode material according to claim 2, wherein in the step (5), the calcining temperature is 250-650 ℃; the calcining time is 2-10 h; the calcining atmosphere is argon or nitrogen.
15. The preparation method of the double-layer coated modified high-nickel cobalt-free single crystal ternary cathode material according to claim 3, wherein in the step (5), the calcining temperature is 250-650 ℃; the calcining time is 2-10 h; the calcining atmosphere is argon or nitrogen.
16. The preparation method of the double-layer coated modified high-nickel cobalt-free single crystal ternary cathode material according to claim 12, wherein in the step (5), the calcining temperature is 250-650 ℃; the calcining time is 2-10 h; the calcining atmosphere is argon or nitrogen.
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