CN113603153B - Tungsten doped high nickel cobalt-free precursor and preparation method thereof - Google Patents
Tungsten doped high nickel cobalt-free precursor and preparation method thereof Download PDFInfo
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Abstract
The invention provides a tungsten-doped high-nickel cobalt-free precursor, which is characterized in that the chemical formula of the tungsten-doped high-nickel cobalt-free precursor is Ni a Mn b R 1‑a‑b (OH) 2‑2c (WO 4 ) c The method comprises the steps of carrying out a first treatment on the surface of the Wherein a is more than or equal to 0.9<1.0，0<b<0.1，0<c is less than or equal to 0.1; r is one or more of Mg, ca, al, ti, zr, zn, ba and Sr. Compared with the prior art, the method utilizes the low-cost metal element to replace cobalt element, can ensure the capacity of the high-nickel material and improve the stability of the material, and the high-nickel cobalt-free precursor which is uniformly doped with tungsten and has a stable structure is obtained, so that the problem of secondary ball cracks commonly existing in the high-nickel precursor is solved, the sphericity and the size consistency of secondary particles are good, the primary crystal whisker on the surface is uniform, the porous structure is provided, and the high-nickel cobalt-free positive electrode material obtained after the lithium source is mixed has good circulation stability on the basis of ensuring the capacity.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a tungsten doped high-nickel cobalt-free precursor and a preparation method thereof.
Background
In the existing lithium ion battery anode material, though the high-nickel material has higher energy density, the defects are obvious, the structural stability and the high-temperature stability of the high-nickel material are poor, particles on the surface are easy to change phase, the layered structure is gradually changed into a spinel structure and a rock salt structure, the change process is irreversible, the phase change on the surface can extend into the particles, the particles generate cracks in the charging and discharging process to cause material failure, and particularly when the molar content of nickel is more than 90%, the defects are obvious.
Proper tungsten doping can stably improve the working voltage of the lithium ion battery and ensure the energy density of the battery; the spacing of the layered structure is increased, and the multiplying power performance is improved; and stabilizes the crystal structure of the precursor, thereby enhancing the cycling stability of the cathode material.
At present, a tungsten-doped anode material is synthesized mainly by a high-temperature solid phase method, and a tungsten source is added at the same time when a precursor and a lithium source are sintered. But due to WO 3 The melting point is higher, the existing sintering temperature needs to be greatly improved, and the energy consumption and the equipment requirement are greatly increased. Therefore, the tungsten doping in the precursor synthesis stage can not only improve the stability of the material, but also effectively reduce the cost.
Meanwhile, cobalt in the anode material has the main functions of improving the conductivity and stabilizing the structure of crystals, but is high in price and greatly influenced by market due to the lack of natural resources of cobalt, so that the cobalt is not beneficial to long-term large-scale use. Therefore, mg, ca, al, ti, zr, zn, ba, sr, la, nd, eu, nb, pr, yb, lu, sn, mo and other elements can be adopted to replace the cobalt element to play a role in the positive electrode material.
Therefore, in the precursor synthesis stage, one or more elements are searched for to replace cobalt element, and the cobalt element can be uniformly doped with tungsten element, so that the stability of the high-nickel anode material is important to improve.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a tungsten uniformly doped high nickel cobalt-free precursor with good sphericity and size consistency, uniform surface primary whisker and porous structure and a preparation method thereof, and the precursor material has good cycle stability after being sintered into a positive electrode material.
The invention provides a tungsten doped high-nickel cobalt-free precursor, wherein the chemical formula of the tungsten doped high-nickel cobalt-free precursor is Ni a Mn b R 1-a-b (OH) 2-2c (WO 4 ) c ；
Wherein a is more than or equal to 0.9 and less than or equal to 1.0, b is more than or equal to 0.1, c is more than or equal to 0 and less than or equal to 0.1;
r is one or more of Mg, ca, al, ti, zr, zn, ba and Sr.
The invention also provides a preparation method of the tungsten doped high-nickel cobalt-free precursor, which comprises the following steps:
s1) in a protective atmosphere, mixing nickel salt, manganese salt, R salt, tungstate, a complexing agent and a precipitator in water for reaction to obtain tungsten doped high-nickel cobalt-free precursor mixed slurry;
and S2) aging the mixed slurry of the tungsten-doped high-nickel cobalt-free precursor to obtain the tungsten-doped high-nickel cobalt-free precursor.
Preferably, in the step S1), the concentration of the complexing agent is kept to be 0.1-2 mol/L in the mixing reaction process; the pH value of the reaction solution is kept to be 9-13 in the mixing reaction process.
Preferably, the step S1) specifically includes:
a) The nickel salt, the manganese salt and the R salt are added in the form of mixed salt solution; the tungstate, the complexing agent and the precipitator are added in the form of aqueous solution;
mixing a complexing agent aqueous solution, a precipitator aqueous solution and water to obtain a reaction base solution;
b) In a protective atmosphere, adding the mixed salt solution and the tungstate solution into the reaction base solution for reaction, and simultaneously adding the complexing agent aqueous solution and the precipitator aqueous solution to control the pH value of the reaction solution and the concentration of the complexing agent, thereby obtaining the tungsten doped high-nickel cobalt-free precursor mixed slurry.
Preferably, the concentration of the complexing agent aqueous solution is 5-13 mol/L; the concentration of the aqueous solution of the precipitant is 5-15 mol/L; the total concentration of metal ions in the mixed salt solution is 0.5-2 mol/L; the concentration of tungsten element in the tungstate solution is 0.01-0.5 mol/L.
Preferably, the flow rate of the mixed salt solution in the step B) is 20-200 mL/min; the flow rate of adding tungstate solution is 5-40 mL/min; the flow rate of the complexing agent aqueous solution is 1-20 mL/min; the flow rate of the aqueous solution of the precipitant is 10-60 mL/min.
Preferably, the temperature of the reaction in the step B) is 40-80 ℃; the reaction is carried out under the condition of stirring; the stirring speed is 600-1200 rpm; the aging temperature is 40-80 ℃; the aging time is 30-90 min.
Preferably, in the step S2), after aging, washing with water, filtering, drying and sieving, the tungsten doped high nickel cobalt free precursor is obtained; the water temperature of the washing is 40-80 ℃; the screen mesh of the screen is 200-400 mesh.
Preferably, the nickel salt is selected from one or more of sulfate, halide and nitrate of nickel; the manganese salt is selected from one or more of sulfate, halide and nitrate of manganese; the R salt is selected from one or more of sulfate, halide and nitrate of R; the tungstate is selected from one or more of sodium tungstate, potassium tungstate, ammonium metatungstate and ammonium phosphotungstate; the complexing agent is selected from one or more of ammonia water, ammonium bicarbonate, disodium ethylenediamine tetraacetate, glycine and triethanolamine; the precipitant is one or more selected from lithium hydroxide, sodium hydroxide, potassium hydroxide and sodium carbonate.
The invention also provides a positive electrode material prepared from the tungsten doped high-nickel cobalt-free precursor and a lithium source.
The invention provides a tungsten doped high-nickel cobalt-free precursor, wherein the chemical formula of the tungsten doped high-nickel cobalt-free precursor is Ni a Mn b R 1-a-b (OH) 2-2c (WO 4 ) c The method comprises the steps of carrying out a first treatment on the surface of the Wherein a is more than or equal to 0.9<1.0，0<b<0.1，0<c is less than or equal to 0.1; r is one or more of Mg, ca, al, ti, zr, zn, ba and Sr. Compared with the prior art, the method utilizes the low-cost metal element to replace cobalt element, can ensure the capacity of the high-nickel material, improves the stability of the material and reduces the cost of raw materials, and the method obtains the high-nickel cobalt-free precursor which is uniformly doped with tungsten and has a stable structure, so that the problem of secondary sphere cracks commonly existing in the high-nickel precursor is solved, the sphericity and the size consistency of secondary particles are good, the primary whisker on the surface is uniform, the porous structure is provided, and the high-nickel cobalt-free positive electrode material obtained after the lithium source is mixed has good circulation stability on the basis of ensuring the capacity.
Drawings
FIG. 1 is a schematic diagram of a reaction vessel and a liquid feeding mode adopted in the embodiment 1 of the present invention;
FIG. 2 is a scanning electron microscope image of the tungsten doped high nickel cobalt free precursor obtained in example 1 of the present invention;
FIG. 3 is a cross-sectional Scanning Electron Microscope (SEM) of the tungsten doped high nickel cobalt-free precursor obtained in example 1 of the present invention;
FIG. 4 is a cross-sectional EDS-mapping diagram of a tungsten doped high nickel cobalt free precursor obtained in example 1 of the present invention;
fig. 5 is a graph showing the full charge-discharge cycle performance of the positive electrode materials prepared from the tungsten doped high nickel cobalt-free precursor obtained in examples 1 to 3 of the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a tungsten doped high-nickel cobalt-free precursor, wherein the chemical formula of the tungsten doped high-nickel cobalt-free precursor is Ni a Mn b R 1-a-b (OH) 2-2c (WO 4 ) c ；
Wherein a is more than or equal to 0.9 and less than or equal to 1.0, preferably a is more than or equal to 0.9 and less than or equal to 0.99, more preferably a is more than or equal to 0.9 and less than or equal to 0.98, still more preferably a is more than or equal to 0.92 and less than or equal to 0.98, and most preferably a is more than or equal to 0.94 and less than or equal to 0.98;0< b <0.1, preferably 0.01.ltoreq.b <0.1;0<c is less than or equal to 0.1; in the examples provided herein, specifically a is 0.96 and b is 0.02.
R is one or more of Mg, ca, al, ti, zr, zn, ba and Sr.
The invention uses cheap metal element to replace cobalt element, which can improve the stability of the material and reduce the cost of raw materials while ensuring the capacity of the high nickel material, and the invention obtains the high nickel cobalt-free precursor with uniform tungsten doping and stable structure, thereby not only improving the problem of secondary ball cracking commonly existing in the high nickel precursor, but also having good sphericity and size consistency of secondary particles, uniform surface primary whisker and porous structure.
The invention also provides a preparation method of the tungsten doped high-nickel cobalt-free precursor, which comprises the following steps: s1) in a protective atmosphere, mixing nickel salt, manganese salt, R salt, tungstate, a complexing agent and a precipitator in water for reaction to obtain tungsten doped high-nickel cobalt-free precursor mixed slurry; and S2) aging the mixed slurry of the tungsten-doped high-nickel cobalt-free precursor to obtain the tungsten-doped high-nickel cobalt-free precursor.
The source of all the raw materials is not particularly limited, and the raw materials are commercially available.
In the present invention, the nickel salt is a soluble salt of nickel, preferably one or more of sulfate, halide and nitrate of nickel, more preferably one or more of nickel sulfate, nickel chloride and nickel nitrate; the manganese salt is a soluble salt of manganese, preferably one or more of sulfate, halide and nitrate of manganese, more preferably one or more of manganese sulfate, manganese chloride and manganese nitrate; the R salt is a soluble salt of R, preferably one or more of sulfate, halide and nitrate of R, more preferably one or more of sulfate, chloride and nitrate of R; the tungstate is preferably one or more of sodium tungstate, potassium tungstate, ammonium metatungstate and ammonium phosphotungstate; the complexing agent is preferably one or more of ammonia water, ammonium bicarbonate, disodium ethylenediamine tetraacetate, glycine and triethanolamine; the precipitant is preferably one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide and sodium carbonate.
In a protective atmosphere, nickel salt, manganese salt, R salt, tungstate, complexing agent and precipitant are mixed and reacted in water; in the present invention, the above raw materials are all preferably added in the form of an aqueous solution, more preferably specifically: a) The nickel salt, the manganese salt and the R salt are added in the form of mixed salt solution; the tungstate, the complexing agent and the precipitator are added in the form of aqueous solution; mixing a complexing agent aqueous solution, a precipitator aqueous solution and water to obtain a reaction base solution; b) In a protective atmosphere, adding the mixed salt solution and the tungstate solution into the reaction base solution for reaction, and simultaneously adding the complexing agent aqueous solution and the precipitator aqueous solution to control the pH value of the reaction solution and the concentration of the complexing agent, thereby obtaining the tungsten doped high-nickel cobalt-free precursor mixed slurry.
Wherein the total concentration of metal ions in the mixed salt solution is preferably 0.5-2 mol/L, more preferably 1-2 mol/L, and still more preferably 1.5mol/L; the molar ratio of nickel element, manganese element and R element group in the mixed salt solution is a: b: (1-a-b); the concentration of tungsten element in the tungstate solution is preferably 0.01 to 0.5mol/L, more preferably 0.05 to 0.3mol/L, still more preferably 0.1 to 0.2mol/L, and most preferably 0.15mol/L; the concentration of the complexing agent aqueous solution is preferably 5 to 13mol/L, more preferably 6 to 12mol/L, still more preferably 8 to 10mol/L, and most preferably 9mol/L; the concentration of the aqueous precipitant solution is preferably 5 to 15mol/L, more preferably 5 to 13mol/L, still more preferably 5 to 10mol/L.
Mixing a complexing agent aqueous solution, a precipitator aqueous solution and water to obtain a reaction base solution; the pH value of the reaction base solution is preferably 9 to 13, more preferably 10 to 13, still more preferably 11 to 13, and most preferably 11.6 to 12; in the embodiment provided by the invention, the pH value of the reaction base solution is specifically 12, 11.8 or 11.6; the concentration of the complexing agent in the reaction base solution is preferably 0.1 to 2mol/L, more preferably 0.1 to 1.5mol/L, still more preferably 0.1 to 1mol/L, still more preferably 0.2 to 0.8mol/L, and most preferably 0.3 to 0.6mol/L.
In a protective atmosphere, adding the mixed salt solution and the tungstate solution into a reaction base solution for reaction; the protective atmosphere is preferably nitrogen; in the present invention, it is preferable to continuously introduce a protective atmosphere during the reaction; the flow rate of the protective atmosphere is preferably 0.1-0.8 m 3 Preferably 0.1 to 0.6m 3 And/h, more preferably 0.2 to 0.5m 3 Preferably 0.3 to 0.5m 3 /h; the flow rate of the mixed salt solution is preferably 20-200 mL/min, more preferably 20-150 mL/min, still more preferably 30-100 mL/min, still more preferably 40-80 mL/min, and most preferably 50mL/min; the flow rate of the tungstate solution is preferably 5-40 mL/min, more preferably 5-30 mL/min, still more preferably 5-20 mL/min, and most preferably 5-10 mL/min; the temperature of the reaction is preferably 40-80 ℃, more preferably 50-70 ℃, and still more preferably 55-65 ℃; the reaction is preferably carried out under stirring; the stirring speed is preferably 600-1200 rpm, more preferably 800-1200 rpm; in the examples provided herein, the rotational speed of the agitation is specifically 1000rpm.
Adding complexing agent aqueous solution and precipitant aqueous solution to control pH value of reaction solution and concentration of complexing agent while reacting; the flow rate of the complexing agent aqueous solution is preferably 1-20 mL/min; the flow rate of the aqueous solution of the precipitant is preferably 10-60 mL/min; the complexing agent aqueous solution and the precipitant aqueous solution are added in such an amount that the pH of the reaction solution is preferably 9 to 13, more preferably 10 to 13, still more preferably 10.5 to 13, most preferably 10.7 to 12; in the embodiment provided by the invention, the complexing agent aqueous solution and the precipitant aqueous solution are added in an amount which specifically enables the pH value of the reaction solution to be 11.4, 10.9 or 10.7; the concentration of the complexing agent in the reaction solution is preferably 0.1 to 2mol/L, more preferably 0.1 to 1.5mol/L, still more preferably 0.3 to 1mol/L, and most preferably 0.3 to 0.5mol/L; in the examples provided by the present invention, the concentration of the complexing agent in the reaction solution is specifically set to 0.3 to 0.5mol/L or 0.8 to 1.0mol/L.
In the present invention, the above reaction is preferably carried out in a reaction vessel; the volume of water used in preparing the reaction base solution is preferably 70-80% of the effective volume of the reaction kettle; all raw materials are added into a reaction kettle through a liquid inlet pipe; according to the invention, by controlling the arrangement of the outlet positions of the liquid inlet pipes of the raw materials, the high-nickel cobalt-free precursor which is uniformly doped with tungsten and has a stable crystal structure is synthesized, the problem of secondary sphere cracking commonly existing in the high-nickel precursor is solved, the sphericity and the size consistency of secondary particles are good, and the primary whisker on the surface is uniform and has a porous structure; in the invention, preferably, a complexing agent aqueous solution, a precipitator aqueous solution and a liquid inlet pipe of a tungstate aqueous solution are arranged on one side of a reaction kettle, and a liquid inlet pipe of a mixed salt solution is arranged on the opposite side; the outlets of the liquid inlet pipes of the precipitant aqueous solution, the complexing agent aqueous solution and the mixed salt solution are positioned near the secondary stirring paddle of the reaction kettle, namely below the liquid level of the reaction liquid; the outlet of the tungstate aqueous solution inlet pipe is positioned above the liquid level of the reaction solution, as shown in figure 1.
In the invention, the reaction is preferably carried out for 65-70 h, and the feeding is stopped when the granularity D50 of the product in the reaction liquid reaches about 6 mu m, so as to obtain the tungsten doped high-nickel cobalt-free precursor mixed slurry.
Aging the tungsten doped high-nickel cobalt-free precursor mixed slurry; the aging temperature is preferably 40-80 ℃, more preferably 50-70 ℃, and still more preferably 55-60 ℃; the aging is preferably carried out under stirring; the stirring speed is preferably 600-1200 rpm, more preferably 800-1200 rpm; in the embodiment provided by the invention, the stirring speed is specifically 1000rpm; the aging time is preferably 30 to 90 minutes, more preferably 40 to 80 minutes, still more preferably 50 to 70 minutes, and most preferably 60 minutes.
Preferably washing with water, filtering, drying and sieving after aging; the water temperature of the washing is preferably 40-80 ℃, more preferably 50-70 ℃, and still more preferably 60-65 ℃; the drying temperature is preferably 90-150 ℃, more preferably 100-140 ℃, and still more preferably 120-130 ℃; the drying time is preferably 10 to 20 hours, more preferably 12 to 18 hours, still more preferably 15 to 16 hours; the screen is preferably a 200-400 mesh screen.
After sieving, iron is also preferably removed to obtain a tungsten doped high nickel cobalt free precursor.
According to the invention, the soluble metal salt replacing cobalt, the soluble metal salt of nickel and manganese and the soluble tungstate are mixed and respectively added into a reaction kettle, the reaction conditions are controlled, so that the coprecipitation of mixed metal ions and tungsten is realized, and tungstate ions generated by ionization of the tungstate can generate precipitation with the mixed metal ions, so that the coprecipitation of the mixed metal ions and tungsten can be realized under the condition that other precipitants are not added; meanwhile, in the preparation process, a tungsten doped high-nickel cobalt-free precursor can be obtained through controlling reaction conditions and a liquid inlet mode of a complexing agent, a precipitator and metal salt and through the procedures of synthesis, aging, washing, drying, sieving, iron removal and the like, so that a high-nickel cobalt-free precursor with uniform tungsten doping and stable crystal structure is obtained, the problem of secondary sphere cracking commonly existing in the high-nickel precursor is solved, the sphericity and the size consistency of secondary particles are also good, and primary crystal whiskers on the surface are uniform and have a porous structure; furthermore, the preparation method is simple, only needs to be slightly improved on the conventional ternary precursor synthesis reaction equipment, and effectively reduces the production cost.
The invention also provides a positive electrode material prepared from the tungsten doped high-nickel cobalt-free precursor and a lithium source.
In the invention, the preparation method specifically comprises the following steps: and mixing the tungsten doped high-nickel cobalt-free precursor with a lithium source, and performing secondary calcination treatment in an oxygen atmosphere to obtain the anode material. The secondary calcination treatment specifically comprises the following steps: calcining for 20-30 h at 500-900 deg.C, and calcining for 15-25 h at 600-800 deg.C.
In order to further illustrate the present invention, the following examples are provided to describe a tungsten doped high nickel cobalt free precursor and a method for preparing the same in detail.
The reagents used in the examples below are all commercially available.
Example 1
1.1, preparing a solution A with the concentration of an ammonia water complexing agent of 9mol/L by deionized water; and preparing a solution B with the concentration of the sodium hydroxide precipitant of 5mol/L by deionized water.
1.2 preparing solution C with total concentration of three ions of Ni, mn and Mg of 1.5mol/L by deionized water, nickel sulfate, manganese sulfate and magnesium sulfate, wherein Ni: mn: mg molar ratio = 96:2:2; preparation of WO with deionized Water and sodium tungstate 4 Solution D with ion concentration of 0.15 mol/L.
1.3 adding 80L deionized water into a 100L reaction kettle, introducing the solutions A and B to prepare a base solution E with pH of 12.0 and ammonia concentration of 0.3mol/L, controlling the temperature of the base solution to 55 ℃ and stirring at 1000rpm.
1.4 into the reaction kettle at a rate of 0.3m 3 Introducing nitrogen into the flow rate/h, and introducing the solution A, B, C, D into the reaction kettle through a precise constant flow pump according to the liquid inlet mode of FIG. 1, wherein the stable flow rate of the solution C is 50mL/min; solution D had a steady flow of 10mL/min. Controlling the pH value of the reaction process to be 11.4, the ammonia concentration to be 0.3-0.5 mol/L, the temperature to be 55 ℃, and continuously introducing nitrogen in the reaction process.
1.5 maintaining the reaction time for 65-70 h, stopping feeding until the material granularity D50 in the reaction kettle reaches about 6.0 mu m, obtaining mixed slurry F, continuously stirring for 60min, discharging, washing with deionized water at 55 ℃, centrifuging, drying in a blast drying oven at 120 ℃ for 15h until the water reaches the requirement, sieving with a 400-mesh screen, and removing iron to obtain the tungsten doped high-nickel cobalt-free precursor.
Analyzing the tungsten doped high nickel cobalt free precursor obtained in the example 1 by using a scanning electron microscope to obtain a surface scanning electron microscope image of the tungsten doped high nickel cobalt free precursor, wherein the surface scanning electron microscope image is shown in fig. 2; obtaining a cross-section scanning electron microscope image of the sample, as shown in figure 3; the resulting cross-sectional EDS-mapping graph is shown in FIG. 4.
Example 2
2.1, preparing a solution A with the concentration of an ammonia water complexing agent of 7mol/L by deionized water; and preparing a solution B with the concentration of the sodium hydroxide precipitant of 5mol/L by deionized water.
2.2 preparing solution C with total concentration of three ions of Ni, mn and Ti of 1.5mol/L by deionized water, nickel sulfate, manganese sulfate and titanium sulfate, wherein Ni: mn: ti molar ratio = 96:2:2; preparation of WO with deionized Water and Ammonia tungstate 4 Solution D with ion concentration of 0.15 mol/L.
2.3 adding 80L deionized water into a 100L reaction kettle, introducing the solutions A and B to prepare a base solution E with pH of 11.8 and ammonia concentration of 0.3mol/L, controlling the temperature of the base solution to 55 ℃ and stirring at 1000rpm.
2.4 into the reaction kettle at a rate of 0.3m 3 Introducing nitrogen into the flow rate/h, and introducing the solution A, B, C, D into the reaction kettle through a precise constant flow pump according to the liquid inlet mode of FIG. 1, wherein the stable flow rate of the solution C is 50mL/min; solution D had a steady flow of 10mL/min. Controlling the pH value of the reaction process to be 10.9, the ammonia concentration to be 0.3-0.5 mol/L, the temperature to be 65 ℃, and continuously introducing nitrogen in the reaction process.
2.5 maintaining the reaction time for 65-70 h, stopping feeding until the material granularity D50 in the reaction kettle reaches about 6.0 mu m, obtaining mixed slurry F, continuously stirring for 60min, discharging, washing with deionized water at 65 ℃, centrifuging, drying in a blast drying oven at 120 ℃ for 15h until the water reaches the requirement, sieving with a 400-mesh screen, and removing iron to obtain the tungsten doped high-nickel cobalt-free precursor.
Example 3
3.1, preparing a solution A with the concentration of an ammonium bicarbonate complexing agent of 9mol/L by deionized water; solution B with carbonic acid precipitant concentration of 2.5mol/L is prepared by deionized water.
3.2 use deionized waterPreparing a solution C with total concentration of Ni, mn and Al ions of 1.5mol/L by using nickel chloride, manganese chloride and aluminum chloride, wherein Ni: mn: al=96: 2:2; preparation of WO with deionized Water and ammonium tungstate 4 Solution D with ion concentration of 0.15 mol/L.
3.3 adding 80L deionized water into a 100L reaction kettle, introducing the solutions A and B to prepare a base solution E with pH of 11.6 and ammonia concentration of 0.6mol/L, controlling the temperature of the base solution to 65 ℃ and stirring at 1000rpm.
3.4 into the reaction kettle at a rate of 0.3m 3 Introducing nitrogen into the flow rate/h, and introducing the solution A, B, C, D into the reaction kettle through a precise constant flow pump according to the liquid inlet mode of FIG. 1, wherein the stable flow rate of the solution C is 50mL/min; solution D had a steady flow of 10mL/min. Controlling the pH value of the reaction process to be 10.7, the ammonia concentration to be 0.8-1.0 mol/L, the temperature to be 65 ℃, and continuously introducing nitrogen in the reaction process.
3.5 maintaining the reaction time for 65-70 h, stopping feeding until the material granularity D50 in the reaction kettle reaches about 6.0 mu m, obtaining mixed slurry F, continuously stirring for 60min, discharging, washing with deionized water at 55 ℃, centrifuging, drying at 120 ℃ in a blast drying oven for 15h until the water reaches the requirement, sieving with a 400-mesh screen, and removing iron to obtain the tungsten doped high-nickel cobalt-free precursor.
Comparative example 1
1.1, preparing a solution A with the concentration of an ammonia water complexing agent of 9mol/L by deionized water; and preparing a solution B with the concentration of the sodium hydroxide precipitant of 5mol/L by deionized water.
1.2 preparing solution C with total concentration of three ions of Ni, mn and Mg of 1.5mol/L by deionized water, nickel sulfate, manganese sulfate and magnesium sulfate, wherein Ni: mn: mg molar ratio = 96:2:2.
1.3 adding 80L deionized water into a 100L reaction kettle, introducing the solutions A and B to prepare a base solution D with pH of 12.0 and ammonia concentration of 0.3mol/L, controlling the temperature of the base solution to 55 ℃ and stirring at 1000rpm.
1.4 into the reaction kettle at a rate of 0.3m 3 Introducing nitrogen into the flow rate/h, introducing the solution A, B, C into the reaction kettle by a precise constant flow pump according to the liquid inlet mode of FIG. 1, wherein the stable flow rate of the solution C is 50mL/min, and a soluble salt liquid inlet pipe containing W element is not used and is usedAnd (5) sealing treatment. Controlling the pH value of the reaction process to be 11.4, the ammonia concentration to be 0.3-0.5 mol/L, the temperature to be 55 ℃, and continuously introducing nitrogen in the reaction process.
1.5 maintaining the reaction time for 65-70 h, stopping feeding until the material granularity D50 in the reaction kettle reaches about 6.0 mu m, obtaining mixed slurry E, continuously stirring for 60min, discharging, washing with deionized water at 55 ℃, centrifuging, drying at 120 ℃ in a blast drying oven for 15h until the water reaches the requirement, sieving with a 400-mesh screen, and removing iron to obtain the high-nickel cobalt-free precursor.
Comparative example 2
2.1, preparing a solution A with the concentration of an ammonia water complexing agent of 7mol/L by deionized water; and preparing a solution B with the concentration of the sodium hydroxide precipitant of 5mol/L by deionized water.
2.2 preparing solution C with total concentration of three ions of Ni, mn and Ti of 1.5mol/L by deionized water, nickel sulfate, manganese sulfate and titanium sulfate, wherein Ni: mn: ti molar ratio = 96:2:2.
2.3 adding 80L deionized water into a 100L reaction kettle, introducing the solutions A and B to prepare a base solution D with pH of 11.8 and ammonia concentration of 0.3mol/L, controlling the temperature of the base solution to 55 ℃ and stirring at 1000rpm.
2.4 into the reaction kettle at a rate of 0.3m 3 And introducing nitrogen into the flow rate/h, introducing the solution A, B, C into the reaction kettle through a precise constant flow pump according to the liquid inlet mode of the figure 1, wherein the stable flow rate of the solution C is 50mL/min, and sealing the solution C without using a soluble salt liquid inlet pipe containing W element. Controlling the pH value of the reaction process to be 10.9, the ammonia concentration to be 0.3-0.5 mol/L, the temperature to be 65 ℃, and continuously introducing nitrogen in the reaction process.
2.5 maintaining the reaction time for 65-70 h, stopping feeding until the material granularity D50 in the reaction kettle reaches about 6.0 mu m, obtaining mixed slurry E, continuously stirring for 60min, discharging, washing with deionized water at 65 ℃, centrifuging, drying in a blast drying oven at 120 ℃ for 15h until the water reaches the requirement, sieving with a 400-mesh screen, and removing iron to obtain the high-nickel cobalt-free precursor.
Comparative example 3
3.1, preparing a solution A with the concentration of an ammonium bicarbonate complexing agent of 9mol/L by deionized water; solution B with carbonic acid precipitant concentration of 2.5mol/L is prepared by deionized water.
3.2 preparing solution C with total concentration of three ions of Ni, mn and Al of 1.5mol/L by deionized water, nickel chloride, manganese chloride and aluminum chloride, wherein Ni: mn: al=96: 2:2.
3.3 adding 80L deionized water into a 100L reaction kettle, introducing the solutions A and B to prepare a base solution D with pH of 11.6 and ammonia concentration of 0.6mol/L, controlling the temperature of the base solution to 65 ℃ and stirring at 1000rpm.
3.4 into the reaction kettle at a rate of 0.3m 3 And introducing nitrogen into the flow rate/h, introducing the solution A, B, C into the reaction kettle through a precise constant flow pump according to the liquid inlet mode of the figure 1, wherein the stable flow rate of the solution C is 50mL/min, and sealing the solution C without using a soluble salt liquid inlet pipe containing W element. Controlling the pH value of the reaction process to be 10.7, the ammonia concentration to be 0.8-1.0 mol/L, the temperature to be 65 ℃, and continuously introducing nitrogen in the reaction process.
3.5 maintaining the reaction time for 65-70 h, stopping feeding until the material granularity D50 in the reaction kettle reaches about 6.0 mu m, obtaining mixed slurry F, continuously stirring for 60min, discharging, washing with deionized water at 55 ℃, centrifuging, drying at 120 ℃ in a blast drying oven for 15h until the water reaches the requirement, sieving with a 400-mesh screen, and removing iron to obtain the high-nickel cobalt-free precursor.
The tungsten doped high nickel cobalt free precursor obtained in examples 1 to 3 and the high nickel cobalt free precursor obtained in comparative examples 1 to 3 were respectively mixed with battery grade lithium hydroxide according to lithiation ratio Li (ni+mn+r) =1.05, subjected to secondary calcination treatment in an oxygen atmosphere, subjected to primary calcination at 860 ℃ for 20 hours, and subjected to secondary calcination at 740 ℃ for 15 hours, to obtain a positive electrode material. The first charge and discharge performance is tested by using a CR2032 button cell, and the mass ratio of the positive electrode materials in the button cell is as follows: high nickel cobalt-free positive electrode material, acetylene black, polyvinylidene fluoride (PVDF) =94:3:3, celgard polypropylene diaphragm is adopted, metal lithium sheet is used as a negative electrode, and 1mol/L LiPF electrolyte is adopted 6 +DEC/EC (volume ratio 1:1) mixed solution. The first charge and discharge performance test data of the button cell under the conditions of 25 ℃ and 0.2C are obtained as shown in Table 1.
The full-cell cycle performance is tested by adopting a 053048 soft-package battery, the proportion of the positive electrode material, the material of the diaphragm and the proportion of the electrolyte in the full-cell are the same as those of the button cell, and the negative electrode is modified natural graphite, so that the soft-package battery charge-discharge cycle performance curve diagram under the conditions of 45 ℃ and 3.0-4.2V and 1C is shown in figure 5.
TABLE 1 detection results of semi-electric properties of cathode materials
Examples are Ni: co: mn molar ratio = 96:2:2, preparing a conventional high-nickel ternary precursor without tungsten doping according to the method of the embodiment 1, and mixing a lithium source to obtain the positive electrode material by adopting the same sintering process conditions.
As can be seen from the semi-electric property data of table 1, the positive electrode materials of examples 1 to 3 and comparative examples 1 to 3 and sample were not greatly different in capacity, but the positive electrode materials obtained in examples 1 to 3 were significantly superior to those of comparative examples 1 to 3 and sample in the first charge and discharge efficiency.
As can be seen from the full charge-discharge cycle performance data of fig. 5, the capacity retention rates of the positive electrode materials obtained in examples 1 to 3 after multiple charge-discharge cycles are significantly better than those of comparative examples 1 to 3 and samples.
Claims (5)
1. The preparation method of the tungsten doped high nickel cobalt-free precursor is characterized by comprising the following steps of:
s1) in a protective atmosphere, mixing nickel salt, manganese salt, R salt, tungstate, a complexing agent and a precipitator in water for reaction to obtain tungsten doped high-nickel cobalt-free precursor mixed slurry;
s2) aging the mixed slurry of the tungsten-doped high-nickel cobalt-free precursor to obtain a tungsten-doped high-nickel cobalt-free precursor;
the chemical formula of the tungsten doped high nickel cobalt-free precursor is Ni a Mn b R 1-a-b （OH） 2-2c （WO 4 ） c ；
Wherein a is more than or equal to 0.96 and less than or equal to 0.98,0.01, b is more than or equal to 0.1, and c is more than or equal to 0 and less than or equal to 0.1;
r is one or more of Mg, ca, al, ti, zr, zn, ba and Sr;
in the step S1), the concentration of the complexing agent is kept to be 0.1-2 mol/L in the mixing reaction process; the pH value of the reaction solution is kept to be 9-13 in the mixing reaction process;
the step S1) specifically comprises the following steps:
a) The nickel salt, the manganese salt and the R salt are added in the form of mixed salt solution; the tungstate, the complexing agent and the precipitator are added in the form of aqueous solution;
mixing a complexing agent aqueous solution, a precipitator aqueous solution and water to obtain a reaction base solution;
b) In a protective atmosphere, adding a mixed salt solution and a tungstate solution into a reaction base solution for reaction, and simultaneously adding a complexing agent aqueous solution and a precipitator aqueous solution to control the pH value of the reaction solution and the concentration of the complexing agent to obtain a tungsten doped high-nickel cobalt-free precursor mixed slurry;
the reaction is carried out in a reaction kettle; the complexing agent aqueous solution, the precipitator aqueous solution and the tungstate aqueous solution are arranged on one side of the reaction kettle, and the mixed salt aqueous solution inlet pipe is arranged on the opposite side; the outlets of the liquid inlet pipes of the precipitant aqueous solution, the complexing agent aqueous solution and the mixed salt solution are positioned below the liquid level of the reaction liquid; the outlet of the tungstate aqueous solution inlet pipe is positioned above the liquid level of the reaction solution;
the concentration of the complexing agent aqueous solution is 5-13 mol/L; the concentration of the aqueous solution of the precipitant is 5-15 mol/L; the total concentration of metal ions in the mixed salt solution is 0.5-2 mol/L; the concentration of tungsten element in the tungstate solution is 0.01-0.5 mol/L; the pH value of the reaction base solution is 9-13;
the temperature of the reaction in the step B) is 40-80 ℃; the reaction is carried out under the condition of stirring; the stirring speed is 600-1200 rpm; the aging temperature is 40-80 ℃; aging for 30-90 min;
the flow rate of the mixed salt solution in the step B) is 20-200 mL/min; the flow rate of adding the tungstate solution is 5-40 mL/min; the flow rate of the complexing agent aqueous solution is 1-20 mL/min; the flow rate of the aqueous solution of the precipitant is 10-60 mL/min.
2. The preparation method according to claim 1, wherein the reaction is stopped when the product particle size D50 in the reaction liquid reaches about 6 μm, and the tungsten doped high nickel cobalt free precursor mixed slurry is obtained.
3. The preparation method according to claim 1, wherein the step S2) is performed with aging, washing with water, filtering, drying, and sieving to obtain a tungsten doped high nickel cobalt free precursor; the water temperature of the washing is 40-80 ℃; the screened screen is a 200-400 mesh screen.
4. The method of claim 1, wherein the nickel salt is selected from one or more of a sulfate, a halide, and a nitrate of nickel; the manganese salt is selected from one or more of sulfate, halide and nitrate of manganese; the R salt is selected from one or more of sulfate, halide and nitrate of R; the tungstate is selected from one or more of sodium tungstate, potassium tungstate, ammonium metatungstate and ammonium phosphotungstate; the complexing agent is selected from one or more of ammonia water, ammonium bicarbonate, disodium ethylenediamine tetraacetate, glycine and triethanolamine; the precipitant is one or more selected from lithium hydroxide, sodium hydroxide, potassium hydroxide and sodium carbonate.
5. The positive electrode material is characterized by being prepared from a tungsten doped high-nickel cobalt-free precursor prepared by any one of the preparation methods 1-4 and a lithium source.
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