CN113651367B - Preparation method of nickel-cobalt-manganese ternary precursor material - Google Patents
Preparation method of nickel-cobalt-manganese ternary precursor material Download PDFInfo
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Abstract
The invention relates to a nickel-cobalt-manganese ternary precursor material and a preparation method thereof. The preparation method comprises the following steps: under inert atmosphere, mixing a nickel-cobalt-manganese ternary metal salt solution with a precipitator solution, ammonia water and a base solution, and reacting to obtain a solution containing ternary metal crystal grains; mixing a nickel-cobalt-manganese ternary metal salt solution, ammonia water, a precipitator solution and the solution containing the ternary metal crystal grains to grow the crystal grains, adjusting the pH, the ammonium ion concentration and the temperature of the solution at least twice in the growing process, adjusting the solid content at least twice to control the total reaction time, aging after the crystal grains grow to the required grain size range, and performing solid-liquid separation to obtain the nickel-cobalt-manganese ternary precursor material. According to the invention, the temperature, the pH value and the ammonium ion concentration are adjusted for multiple times in the growth stage, so that the specific surface area can be obviously increased, and the formation of internal pores is avoided.
Description
Technical Field
The invention relates to the technical field of precursor material preparation, in particular to a nickel-cobalt-manganese ternary precursor material and a preparation method thereof, and more particularly relates to a nickel-cobalt-manganese ternary precursor material and a preparation method thereof, a lithium ion battery anode material and a lithium ion battery.
Background
The nickel-cobalt-manganese ternary precursor is popular among various large precursor manufacturers due to the advantages of high capacity, long service life, low price and the like. In the prior art, the preparation process of the ternary precursor is basically divided into two stages: a nucleation phase and a growth phase. The nucleation stage is mainly to produce grains, and different nucleation processes provide different amounts and qualities of grains for growth and prepare for growth. The growth stage refers to the process of precursor particles from crystal grains to target particle size, and precursors with different tap densities, specific surface areas and morphologies can be prepared by adopting different growth processes. The growth stages of the prior art often employ relatively stable pH, temperature and ammonium ion concentrations.
However, the preparation of the precursor with large specific surface area by using the preparation process can cause the precursor particles to form a rough surface when the particle size is not reached, and the rough surface can not be backfilled in the growth process and can be left in the precursor along with the increase of the particle size, so that pores are generated in the precursor with large specific surface area and particles. Meanwhile, the generated pores easily cause cracking of the positive electrode particles in the charge and discharge processes.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of a nickel-cobalt-manganese ternary precursor material, which can not only adjust the growth rate of precursor particles, adjust the morphology of the precursor material and increase the specific surface area, but also avoid the formation of internal pores of the precursor material by adjusting the temperature, the pH and the ammonium ion concentration for multiple times according to the grain size in the growth stage. The problem of adopt relatively stable pH, temperature and ammonium ion concentration to lead to produce more gas pockets in the precursor material among the prior art is solved.
The second purpose of the invention is to provide the nickel-cobalt-manganese ternary precursor material which has a special structure with high internal compactness, few air holes and large specific surface area.
The third purpose of the invention is to provide a lithium ion battery anode material, which has few internal air holes and can avoid the cracking of the anode material in the charging and discharging process; and the specific surface area is large, which is beneficial to improving the rate capability of the battery.
The fourth purpose of the present invention is to provide a lithium ion battery, which includes a lithium ion battery anode material with a compact interior, and can prevent the anode material from cracking during charging and discharging, prolong the service life of the lithium ion battery, increase the specific surface area, accelerate the charging and discharging speed, and improve the rate capability of the battery.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a preparation method of a nickel-cobalt-manganese ternary precursor material, which comprises the following steps:
(1) Mixing a nickel-cobalt-manganese ternary metal salt solution with a precipitator solution, ammonia water and a base solution in an inert atmosphere, and reacting to obtain a solution containing ternary metal crystal grains;
(2) Mixing a nickel-cobalt-manganese ternary metal salt solution, ammonia water, a precipitator solution and the solution containing the ternary metal crystal grains obtained in the step (1) in an inert atmosphere to grow the crystal grains, adjusting the pH, the ammonium ion concentration and the temperature of the solution at least twice in the growing process, adjusting the solid content at least twice to control the total reaction time, aging after the crystal grains grow to the required grain size range, and performing solid-liquid separation to obtain the nickel-cobalt-manganese ternary precursor material;
in the step (2), the temperature adjusting method specifically includes: when the grain size increases by 1 mu m, the temperature rises by 1 to 20 ℃, preferably 2 to 15 ℃; it is also possible to select 3 deg.C, 4 deg.C, 5 deg.C, 6 deg.C, 7 deg.C, 8 deg.C, 9 deg.C, 10 deg.C, 11 deg.C, 12 deg.C, 13 deg.C or 14 deg.C.
The method for adjusting the pH specifically comprises the following steps: when the grain size increases by 1 mu m, the pH value decreases by 0.01 to 2, preferably 0.02 to 1; 0.05, 0.1, 0.2, 0.3, 0.5, 0.65, 0.8 or 0.9 may also be selected.
The method for adjusting the concentration of the ammonium ions specifically comprises the following steps: when the grain size increases by 1 mu m, the mass concentration of ammonium ions is reduced by 0.01-2 g/L, preferably 0.02-1 g/L, and 0.05g/L, 0.1g/L, 0.2g/L, 0.3g/L, 0.5g/L, 0.8g/L or 0.9g/L can be selected.
The preparation method of the nickel-cobalt-manganese ternary precursor material provided by the invention has two independent processes of granulation and growth, and adjusts the growth rate of precursor particles, adjusts the morphology of the precursor material and increases the specific surface area on one hand by adjusting the temperature, the pH and the ammonium ion concentration for multiple times according to the grain size in the growth stage; on the other hand, the formation of internal air holes caused by untimely backfilling in the growth process of the precursor is avoided.
According to the invention, through adjusting the process parameters such as temperature, pH and ammonium ion concentration for multiple times, the internal and external structures of the precursor material are different, the precursor material has a layered sense, the internal structure is more compact, the external structure is more loose, and the precursor with a gradual change type structure is obtained.
Preferably, the gas used for the inert atmosphere comprises one of nitrogen, argon and helium.
Preferably, the nickel-cobalt-manganese ternary metal salt solution comprises a nickel source, a cobalt source and a manganese source.
Preferably, the nickel source comprises at least one of nickel sulfate, nickel chloride, nickel nitrate and nickel acetate.
Preferably, the cobalt source comprises at least one of cobalt sulfate, cobalt chloride, cobalt nitrate and cobalt acetate.
Preferably, the source of manganese comprises at least one of manganese sulfate, manganese chloride, manganese nitrate and manganese acetate.
Preferably, four, five, six, seven, eight, nine or ten times are also selected by adjusting the pH, ammonium ion concentration and temperature of the solution at least three times during the growth.
The process of growing the crystal grains is a growth phase, and the growth phase comprises an initial phase and an intermediate phase. The at least two adjustments of the pH, ammonium ion concentration and temperature of the solution specifically include: raising the temperature, lowering the pH, and reducing the NH in the initial stage and the intermediate stage, respectively 4 + And (4) concentration.
Preferably, in the initial stage of the growth stage, the temperature is increased to increase the temperature of the solution system by 5 to 60 ℃ compared with the nucleation stage (i.e. the process of generating the ternary metal crystal grains), the concentration of ammonium ions is reduced to reduce the ammonium ions by 0.1 to 14g/L compared with the nucleation stage, and the pH is reduced to reduce the pH of the solution system by 0.05 to 4.0.
Preferably, the growth time range is controlled to be 6-60 h, more preferably 10-50 h by controlling the solid content, and 12h, 14h, 17h, 20h, 25h, 30h, 35h, 40h, 45h or 48h can be selected.
The invention further improves the specific surface area of the precursor material by adjusting the solid content and controlling the reaction time.
The process of generating the ternary metal grains refers to a nucleation stage, also referred to as a granulation stage.
Preferably, the base solution comprises ammonium ions and hydroxide ions.
Preferably, the mass concentration of ammonium ions in the base solution is 0.5-20 g/L, and 2g/L, 4g/L, 6g/L, 7g/L, 8g/L, 9g/L, 10g/L, 11g/L, 12g/L, 13g/L, 14g/L, 15g/L, 16g/L, 17g/L, 18g/L or 19g/L can also be selected; the pH of the base solution is 7.5-14, and can also be selected from 7.9, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13 or 13.5.
Preferably, the temperature of the base solution is 30-60 ℃, and can also select 32 ℃, 34 ℃, 36 ℃, 38 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃ or 58 ℃.
Preferably, in the steps (1) and (2), the temperature of the solution system is 30-90 ℃, and 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 68 ℃, 75 ℃, 80 ℃ or 85 ℃ can be selected; more preferably 35 to 75 ℃.
Preferably, in steps (1) and (2), the pH of the solution system is 7.5 to 14, more preferably 8 to 13.5; alternatively 8.5, 9.5, 10, 10.5, 11, 11.5, 12, 12.5 or 13.
Preferably, in the steps (1) and (2), the mass concentration of ammonium ions in the solution system is 0.01-20 g/L, and 0.05g/L, 0.1g/L, 0.5g/L, 1g/L, 2g/L, 3g/L, 4g/L, 6g/L, 7g/L, 8g/L, 9g/L, 12g/L, 13g/L, 14g/L, 16g/L, 17g/L or 19g/L can also be selected; more preferably 1 to 15g/L.
Preferably, in steps (1) and (2), the solution system is continuously stirred at a speed of 250 to 750rpm, more preferably at a speed of 300 to 500rpm.
Preferably, the total reaction time is from 3 to 72 hours, more preferably from 10 to 60 hours; 12h, 14h, 16h, 19h, 23h, 28h, 35h, 40h, 45h, 50h, 52h or 57h can also be selected.
Preferably, in the steps (1) and (2), the total molar concentration of the metal ions in the nickel-cobalt-manganese ternary metal salt solution is 0.1 to 3mol/L, and 0.5mol/L, 1.5mol/L or 2.5mol/L can be selected, and more preferably 1 to 2.5mol/L.
Preferably, in the steps (1) and (2), the molar concentration of ammonium ions in the ammonia water is 0.01-13 mol/L, and 0.5mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L, 11mol/L or 12mol/L can also be selected, and more preferably 0.1-10 mol/L.
Preferably, in the steps (1) and (2), the total molar concentration of all metal ions in the precipitant solution is 0.1-18 mol/L, and 1mol/L, 2.5mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L, 11mol/L, 12mol/L, 13mol/L, 14mol/L, 15mol/L, 16mol/L, 17mol/L or 17.5mol/L can also be selected, and more preferably 2-15 mol/L.
Preferably, in steps (1) and (2), the precipitant comprises at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
Preferably, the aging specifically comprises: mixing the mixed solution with alkali, adjusting the pH value to 8-13, and aging for 2-24 h. Wherein, the pH can also be 8.5, 9, 9.5, 10, 10.5, 11 or 12.5; the aging time can also be 3h, 4h, 5h, 6h, 8h, 10h, 12h, 14h, 17h, 19h, 20h, 21h or 23h.
Preferably, the aging specifically comprises: mixing the mixed solution with alkali, adjusting the pH value to 9-12, and aging for 5-20 h.
Preferably, the aging refers to a process of standing and storing the solution for a period of time under certain conditions, specifically, heating and preserving the temperature of the feed liquid reaching the particle size, maintaining the final reaction temperature, and stirring at a small amplitude, mainly continuously reacting the residual trace amount of free Ni, co and Mn metal ions in the mother liquid to grow on the surface of the ternary precursor spherulite, so that on one hand, the material loss is reduced, and on the other hand, the structure of the precursor particles is stabilized and the performance of the precursor is improved.
Preferably, the base comprises at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
Preferably, the solid-liquid separation comprises centrifugation and sedimentation filtration.
Preferably, after the solid-liquid separation, a drying dehydration step is further included.
Preferably, the drying and dehydrating manner includes high-temperature drying and low-temperature drying.
Preferably, the feeding flow rate of the nickel-cobalt-manganese ternary salt solution is determined according to the volume of the reaction kettle in the whole reaction process including the nucleation stage and the growth stage, and is 0.02 to 2000L/h in some specific embodiments of the invention. Initial feed rate of ammonia water through metal ion M 2+ And NH 4 + The molar ratio of the ternary metal ion to the ammonia water is in the range of 1. Initial feed rate of precipitant solution through metal ion M 2+ With OH - (or CO) 3 2- ) Designed molar ratio of ternary metal ion to OH - In the range of 2.0.
The invention also provides a nickel-cobalt-manganese ternary precursor material prepared by the preparation method.
The nickel-cobalt-manganese ternary precursor material provided by the invention has the advantages of layering sense, high internal compactness, few air holes and large specific surface area.
Preferably, the specific surface area of the nickel-cobalt-manganese ternary precursor material is 8-300 g/cm 3 The granularity is 8-20 mu m.
The nickel-cobalt-manganese ternary precursor material is large in particle size and has a large specific surface.
The invention also provides a lithium ion battery anode material which is prepared by adopting the nickel-cobalt-manganese ternary precursor material prepared by the preparation method or the nickel-cobalt-manganese ternary precursor material and lithium salt.
The lithium ion battery anode material provided by the invention has few internal pores, can avoid cracking in the charging and discharging process, has a large specific surface area, and is beneficial to improving the rate capability of the battery.
The invention also provides a lithium ion battery which comprises the anode prepared from the lithium ion battery anode material.
In the charging and discharging processes of the battery, the anode particles are not easy to crack, so that the service life of the lithium ion battery can be prolonged; moreover, the battery has high charging and discharging speed and high rate capability.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the preparation method of the nickel-cobalt-manganese ternary precursor material, the temperature, the pH value and the ammonium ion concentration are adjusted for multiple times according to the grain size in the growth stage, so that on one hand, the formation of internal air holes is avoided by adjusting the appearance of the precursor material; on the other hand, the specific surface area of the precursor material is increased by adjusting the growth rate of the precursor particles.
(2) The preparation method of the nickel-cobalt-manganese ternary precursor material further improves the specific surface area of the precursor material by adjusting the solid content and controlling the reaction time.
(3) The nickel-cobalt-manganese ternary precursor material provided by the invention has the advantages of layering effect, high internal compactness, few air holes and large specific surface area.
(4) The lithium ion battery anode material provided by the invention has few internal air holes, can avoid cracking in the charging and discharging process, has a large specific surface area, and is beneficial to improving the rate capability of the battery.
(5) The lithium ion battery provided by the invention comprises the lithium ion battery anode material with compact interior, so that the anode material can be prevented from cracking in the charging and discharging process, the service life of the lithium ion battery is prolonged, the charging and discharging speed is high, and the multiplying power performance of the battery is high.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a scanning electron microscope image of a nickel-cobalt-manganese ternary precursor material provided in embodiment 1 of the present invention;
fig. 2 is a scanning electron microscope image of the nickel-cobalt-manganese ternary precursor material provided in comparative example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following detailed description, but those skilled in the art will understand that the following described examples are some, not all, of the examples of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the following examples and comparative examples of the present invention, inert gas was uniformly and directly introduced into the reaction vessel in the nucleation stage and in the growth stage; and when the feeding reaches the full kettle, standing the mixture in the reaction kettle for precipitation, then pumping out the supernatant, continuously injecting the nickel-cobalt-manganese ternary salt solution, ammonia water and the precipitating agent into the reaction kettle containing the precipitate, and repeating the operation until the reaction is finished when the reaction kettle is full next time.
The particle size of the precursor material is obtained by testing a British Marvin Mastersize2000 laser particle size analyzer; the specific surface area was measured by a Peard specific surface area meter SSA 3500.
Example 1
The granularity provided by the embodiment is 16 +/-0.2 mu m, and the specific surface area is 15-17g/cm 3 The preparation method of the NCM622 nickel cobalt manganese ternary precursor material specifically comprises the following steps:
(a) Preparing a solution and a base solution: preparing a nickel-cobalt-manganese ternary salt solution with the total molar concentration of metal ions of 2.0mol/L by using nickel sulfate, cobalt sulfate and manganese sulfate as raw materials, wherein the molar ratio of nickel element to cobalt element to manganese element is 6; preparing ammonia water with the molar concentration of ammonium ions of 8mol/L and a potassium hydroxide solution with the molar concentration of potassium ions of 11 mol/L;
adding 1000L of pure water into a 2000L reaction kettle, continuously introducing nitrogen into the reaction kettle, and heating the pure water to 50 ℃; then adding ammonia water into the reaction kettle, and adjusting NH 4 + Adding potassium hydroxide solution, and adjusting the pH to 12.5 to obtain a base solution, wherein the mass concentration of the base solution is 14 g/L;
(b) Respectively and simultaneously injecting the nickel-cobalt-manganese ternary salt solution, ammonia water and potassium hydroxide solution into a reaction kettle containing a base solution in a nucleation stage, stirring at the rotating speed of 350rpm, and reacting at 50 ℃ for 30min to obtain crystal grains; during the nucleation reaction, NH is adjusted 4 + The mass concentration of the mixed solution is 14g/L, and the pH value of the mixed solution is adjusted to be 12.5;
the method comprises the following steps of (1) designing the nucleation feeding flow rates of ammonia water and potassium hydroxide solution by setting the molar ratio of metal ions to ammonia water in the nickel-cobalt-manganese ternary salt solution to be 1;
the nucleation stage was completed, i.e., when the feeding time was 30min, the grain size was 4.6 μm, the temperature was 50 ℃, the pH was 12.5, and the concentration of ammonium ions was 14g/L.
(c) Adjusting the temperature, the pH value and the ammonium ion concentration of the mixed solution at the initial stage of growth, specifically adjusting the temperature of the mixed solution to 55 ℃, and respectively and simultaneously injecting a nickel-cobalt-manganese ternary salt solution, ammonia water and a potassium hydroxide solution into a solution containing crystal grainsStirring at a rotating speed of 300rpm in the reaction kettle; and reacting NH 4 + The mass concentration of the mixed solution is adjusted to be 5g/L, the pH of the mixed solution is adjusted to be 12.0, and the grain size is 4.6 mu m;
setting the feeding flow rate of the nickel-cobalt-manganese ternary salt solution to be 100L/h, and designing the initial feeding flow rate of the ammonia water and the potassium hydroxide solution in the growth stage by setting the molar ratio of total metal ions in the nickel-cobalt-manganese ternary salt solution to ammonia monohydrate in the ammonia water to be 2;
in the middle stage of growth, adjusting the temperature, pH and ammonium ion concentration of the mixed solution, specifically, when the grain size increases by 1 μm, the temperature rises by 2 ℃, the pH decreases by 0.18, and the mass concentration of ammonium ions decreases by 0.2g/L; that is, when the grain size reaches 19.6 μm, the temperature is 85 ℃, the pH is 9.3, and the mass concentration of ammonium ions is 2g/L;
in the middle stage of growth, the rotation speed of the stirrer was adjusted, 5 μm down to 280rpm,6 μm down to 240rpm,7 μm down to 200rpm,8 μm down to 120rpm,9 μm down to 100rpm,10 μm down to 90rpm,11 μm down to 80rpm,12 μm down to 70rpm, after which the rotation speed was maintained at 70rpm;
controlling the growth time to be 42h by adjusting the solid content;
and after the growth is finished, adding a potassium hydroxide solution into the reaction kettle, adjusting the pH value of the mixed solution to 10.8, aging for 20h, and then centrifugally drying to obtain the NCM622 nickel cobalt manganese ternary precursor material.
Through detection, the particle size D50 of the NCM622 nickel cobalt manganese ternary precursor material prepared by the embodiment is 16.1 μm, and the specific surface area is 15.8g/cm 3 。
Example 2
The particle size provided by the embodiment is 13 +/-0.2 mu m, and the specific surface area is 120-130g/cm 3 The preparation method of the NCM811 Ni-Co-Mn ternary precursor material specifically comprises the following steps:
(a) Preparing a solution and a base solution: preparing a nickel-cobalt-manganese ternary salt solution with the total molar concentration of metal ions of 1.5mol/L by using nickel sulfate, cobalt sulfate and manganese sulfate as raw materials, wherein the molar ratio of nickel elements to cobalt elements to manganese elements is 8; preparing an ammonia water solution with the molar concentration of ammonium ions of 5.0mol/L and a mixed potassium solution of potassium carbonate and potassium hydroxide with the molar concentration of potassium ions of 8.0mol/L (the molar ratio of the potassium carbonate to the potassium in the potassium hydroxide is 1;
adding 1000L of pure water into a 2000L reaction kettle, continuously introducing nitrogen into the reaction kettle, and heating the pure water to 48 ℃; then adding ammonia water into the reaction kettle, and adjusting NH 4 + Adding a precipitator into the solution with the mass concentration of 3g/L, and adjusting the pH value to 11.5 to obtain a base solution;
(b) Respectively and simultaneously injecting the nickel-cobalt-manganese ternary salt solution, ammonia water and a precipitator into a reaction kettle containing a base solution in a nucleation stage, stirring at the rotating speed of 350rpm, and reacting at 48 ℃ for 20min to obtain crystal grains; during the nucleation reaction, NH is adjusted 4 + The mass concentration of the mixed solution is 3g/L, and the pH value of the mixed solution is adjusted to 11.5;
the method comprises the following steps of (1) designing the feeding flow rate of nucleation of ammonia water and a precipitator by setting the molar ratio of metal ions to ammonia water in a nickel-cobalt-manganese ternary salt solution to be 2;
the nucleation stage is ended, namely when the feeding time is 20min, the grain diameter of the crystal grains is 4.1 mu m, the temperature is 48 ℃, the pH value is 11.5, and the concentration of ammonium ions is 3g/L;
(c) Adjusting the temperature, the pH value and the ammonium ion concentration of the mixed solution at the initial growth stage, specifically, adjusting the temperature of the mixed solution to 58 ℃, respectively and simultaneously injecting a nickel-cobalt-manganese ternary salt solution, ammonia water and a potassium carbonate solution into a reaction kettle containing crystal grains, and stirring at the rotating speed of 300 rpm; and reacting NH 4 + The mass concentration of the mixed solution is adjusted to be 2g/L, the pH of the mixed solution is adjusted to be 10.5, and the grain size is 4.1 mu m;
setting the feeding flow rate of the nickel-cobalt-manganese ternary salt solution to be 100L/h, and setting the molar ratio of total metal ions in the nickel-cobalt-manganese ternary salt solution to ammonia monohydrate in ammonia water to be 2;
in the middle stage of growth, adjusting the temperature, pH and ammonium ion concentration of the mixed solution, specifically, when the grain size increases by 1 μm, the temperature increases by 3.5 ℃, the pH decreases by 0.13, and the mass concentration of ammonium ions decreases by 0.02g/L; namely, when the grain size reaches 12.1 μm, the temperature is 86 ℃, the pH is 9.46, and the mass concentration of ammonium ions is 0.18g/L;
in the middle stage of growth, the rotation speed of the stirrer was adjusted, 5 μm was decreased to 280rpm,6 μm was decreased to 240rpm,7 μm was decreased to 200rpm,8 μm was decreased to 120rpm,9 μm was decreased to 100rpm,10 μm was decreased to 90rpm, after which the rotation speed was maintained at 90rpm;
controlling the growth time to be 20h by adjusting the solid content;
after the growth is finished, adding a potassium carbonate solution into the reaction kettle, adjusting the pH value of the mixed solution to 10.5, aging for 10 hours, and then centrifugally drying to obtain the NCM811 nickel-cobalt-manganese ternary precursor material.
Through detection, the particle size D50 of the NCM811 nickel cobalt manganese hydroxide ternary precursor material prepared by the embodiment is 12.9 μm, and the specific surface area is 123g/cm 3 。
Example 3
The particle size provided by the embodiment is 20 +/-0.2 mu m, and the specific surface area is 240-250 g/cm 3 The preparation method of the NCM523 nickel-cobalt-manganese carbonate ternary precursor material specifically comprises the following steps:
(a) Preparing a solution and a base solution: preparing a nickel-cobalt-manganese ternary salt solution with the total molar concentration of metal ions of 1.5mol/L by using nickel sulfate, cobalt sulfate and manganese sulfate as raw materials, wherein the molar ratio of nickel elements to cobalt elements to manganese elements is 5; preparing ammonia water with the molar concentration of ammonium ions of 0.4mol/L and a sodium carbonate solution with the molar concentration of sodium ions of 1.5 mol/L;
adding 1000L of pure water into a 2000L reaction kettle, continuously introducing nitrogen into the reaction kettle, and heating the pure water to 45 ℃; then to the reaction kettleAdding ammonia water, regulating NH 4 + Adding sodium carbonate solution, and adjusting the pH to 7.9 to obtain a base solution, wherein the mass concentration of the base solution is 0.5 g/L;
(b) Respectively and simultaneously injecting the nickel-cobalt-manganese ternary salt solution, ammonia water and sodium carbonate solution into a reaction kettle containing a base solution in a nucleation stage, stirring at the rotating speed of 350rpm, and reacting at 35 ℃ for 40min to obtain crystal grains; during the nucleation reaction, NH is adjusted 4 + The mass concentration of the mixed solution is 0.5g/L, and the pH value of the mixed solution is adjusted to 7.9;
the method comprises the following steps of (1) designing the initial nucleating feeding flow rates of ammonia water and a sodium carbonate solution by setting the molar ratio of metal ions to ammonia water in a nickel-cobalt-manganese ternary salt solution to be 8;
finishing the nucleation stage, namely when the feeding time is 40min, the grain diameter of the crystal grains is 5.3 mu m, the temperature is 45 ℃, the pH value is 7.9, and the concentration of ammonium ions is 0.2g/L;
(c) Adjusting the temperature, the pH value and the ammonium ion concentration of the mixed solution at the initial stage of growth, specifically, adjusting the temperature of the mixed solution to 60 ℃, respectively and simultaneously injecting a nickel-cobalt-manganese ternary salt solution, ammonia water and a sodium carbonate solution into a reaction kettle containing crystal grains, and stirring at the rotating speed of 300 rpm; and reacting NH 4 + The mass concentration of the mixed solution is adjusted to be 0.3g/L, the pH of the mixed solution is adjusted to be 7.8, and the grain size is 5.3 mu m;
setting the feeding flow rate of the nickel-cobalt-manganese ternary salt solution to be 100L/h, and setting the molar ratio of total metal ions in the nickel-cobalt-manganese ternary salt solution to ammonia monohydrate in ammonia water to be 9, and the molar ratio of the total metal ions in the nickel-cobalt-manganese ternary salt solution to sodium ion to be 1;
in the middle stage of growth, adjusting the temperature, pH and ammonium ion concentration of the mixed solution, specifically, when the grain size increases by 1 μm, the temperature rises by 2 ℃, the pH decreases by 0.02, and the mass concentration of ammonium ions decreases by 0.01g/L; that is, when the grain size reached 19.3 μm, the temperature was 88 ℃, the pH was 7.52, and the mass concentration of ammonium ions was 0.16g/L;
in the middle stage of growth, the rotation speed of the stirrer was adjusted, 6 μm was decreased to 240rpm,7 μm was decreased to 200rpm,8 μm was decreased to 120rpm,9 μm was decreased to 100rpm,10 μm was decreased to 80rpm,11 μm was decreased to 60rpm, and then the rotation speed was maintained at 60rpm;
controlling the growth time to be 10h by adjusting the solid content;
after the growth is finished, adding a sodium carbonate solution into the reaction kettle, adjusting the pH value of the mixed solution to 7.9, aging for 18h, and then centrifugally drying to obtain the NCM523 nickel-cobalt-manganese ternary precursor material.
Through detection, the particle size D50 of the NCM523 nickel-cobalt-manganese carbonate ternary precursor material prepared in the embodiment is 19.9 μm, and the specific surface area is 246g/cm 3 。
Example 4
The particle size provided by the embodiment is 8 +/-0.2 mu m, and the specific surface area is 26-28g/cm 3 The preparation method of the NCM622 nickel cobalt manganese ternary precursor material specifically comprises the following steps:
(a) Preparing a solution and a base solution: preparing a nickel-cobalt-manganese ternary salt solution with the total molar concentration of metal ions of 3.0mol/L by using nickel chloride, cobalt chloride and manganese chloride as raw materials, wherein the molar ratio of nickel elements to cobalt elements to manganese elements is 6; preparing ammonia water with the molar concentration of ammonium ions of 13.0mol/L and a sodium hydroxide solution with the molar concentration of hydroxide ions of 18 mol/L;
adding 1000L of pure water into a 2000L reaction kettle, continuously introducing nitrogen into the reaction kettle, and heating the pure water to 90 ℃; then adding ammonia water into the reaction kettle, and adjusting NH 4 + Adding sodium hydroxide solution, and adjusting the pH to 14.0 to obtain a base solution, wherein the mass concentration of the base solution is 15g/L;
(b) Respectively and simultaneously injecting the nickel-cobalt-manganese ternary salt solution, ammonia water and sodium hydroxide solution into a reaction kettle containing a base solution in a nucleation stage, stirring at the rotating speed of 350rpm, and reacting at 30 ℃ for 5min to obtain crystal grains; during the nucleation reaction, NH is adjusted 4 + The mass concentration of (A) is 15g/L,adjusting the pH value of the mixed solution to 14.0;
the method comprises the following steps of (1) designing the nucleation feeding flow rates of ammonia water and sodium hydroxide solution by setting the molar ratio of metal ions to ammonia water in a nickel-cobalt-manganese ternary salt solution to be 1;
finishing the nucleation stage, namely when the feeding time is 5min, the grain diameter of the crystal grains is 3.2 mu m, the temperature is 30 ℃, the pH value is 14, and the concentration of ammonium ions is 15g/L;
(c) Adjusting the temperature, the pH value and the ammonium ion concentration of the mixed solution at the initial stage of growth, specifically, adjusting the temperature of the mixed solution to 40 ℃, respectively and simultaneously injecting a nickel-cobalt-manganese ternary salt solution, ammonia water and a sodium hydroxide solution into a reaction kettle containing crystal grains, and stirring at the rotating speed of 300 rpm; and reacting NH 4 + The mass concentration of (2) is adjusted to 8g/L, the pH of the mixed solution is adjusted to 10.0, and the grain size is 3.2 mu m at the moment;
setting the feeding flow rate of the nickel-cobalt-manganese ternary salt solution to be 50L/h, setting the molar ratio of total metal ions in the nickel-cobalt-manganese ternary salt solution to ammonia monohydrate in ammonia water to be 2;
in the middle stage of growth, adjusting the temperature, pH and ammonium ion concentration of the mixed solution, specifically, when the grain size is increased by 1 μm for the first time, the temperature is increased by 20 ℃, the pH is reduced by 0.2, and the mass concentration of ammonium ions is reduced by 2g/L; when the grain size increases by 1 μm, the temperature increases by 5 ℃, the pH decreases by 0.35, and the mass concentration of ammonium ions decreases by 1.5g/L; namely, when the grain size reaches 7.2 μm, the temperature is 75 ℃, the pH is 8.75, and the mass concentration of ammonium ions is 1.5g/L;
in the middle stage of growth, the rotation speed of stirring is adjusted, 5 μm is reduced to 280rpm,6 μm is reduced to 240rpm,7 μm is reduced to 190rpm, and then the rotation speed is maintained at 190rpm;
controlling the growth time to be 26h by adjusting the solid content;
and after the growth is finished, adding a sodium hydroxide solution into the reaction kettle, adjusting the pH value of the mixed solution to 9.5, aging for 24 hours, and then centrifugally drying to obtain the NCM622 nickel cobalt manganese ternary precursor material.
Through detection, the particle size D50 of the NCM622 nickel cobalt manganese ternary precursor material prepared by the embodiment is 8.1 μm, and the specific surface area is 27.8g/cm 3 。
Example 5
The particle size provided by the example is 15 +/-0.2 mu m, and the specific surface area is 120-130g/cm 3 The preparation method of the NCM811 nickel cobalt manganese ternary precursor material specifically comprises the following steps:
(a) Preparing a solution and a base solution: preparing a nickel-cobalt-manganese ternary salt solution with the total molar concentration of metal ions of 0.1mol/L by using nickel sulfate, cobalt sulfate and manganese sulfate as raw materials, wherein the molar ratio of nickel elements to cobalt elements to manganese elements is (8); preparing a mixed solution of ammonia water with the molar concentration of ammonium ions of 0.01mol/L and sodium carbonate and sodium hydroxide with the molar concentration of hydroxide ions of 0.1mol/L (the molar ratio of the sodium carbonate to the sodium in the sodium hydroxide is 1;
adding 1000L of pure water into a 2000L reaction kettle, continuously introducing nitrogen into the reaction kettle, and heating the pure water to 30 ℃; then adding ammonia water into the reaction kettle, and adjusting NH 4 + Adding a precipitator with the mass concentration of 1g/L, and adjusting the pH value to 8.0 to obtain a base solution;
(b) Respectively and simultaneously injecting the nickel-cobalt-manganese ternary salt solution, ammonia water and a precipitator into a reaction kettle containing a base solution in a nucleation stage, stirring at the rotating speed of 350rpm, and reacting at 30 ℃ for 60min to obtain crystal grains; during the nucleation reaction, NH is adjusted 4 + The mass concentration of the mixed solution is 1g/L, and the pH value of the mixed solution is adjusted to 8.25;
the feeding flow rate of the nickel-cobalt-manganese ternary salt solution is 80L/h, the volume of the reaction kettle is 2000L, and the feeding flow rates of the ammonia water and the precipitator are adjusted by setting the molar ratio of metal ions to the ammonia water in the nickel-cobalt-manganese ternary salt solution to be 4;
the nucleation stage was completed, i.e., when the feeding time was 6min, the grain size was 5.6 μm, the temperature was 30 ℃, the pH was 8.25, and the concentration of ammonium ions was 1g/L.
(c) Adjusting the temperature, the pH value and the ammonium ion concentration of the mixed solution at the initial stage of growth, specifically, adjusting the temperature of the mixed solution to 70 ℃, respectively and simultaneously injecting a nickel-cobalt-manganese ternary salt solution, ammonia water and a potassium carbonate solution into a reaction kettle containing crystal grains, and stirring at the rotating speed of 300 rpm; and reacting NH 4 + The mass concentration of the mixed solution is adjusted to be 0.5g/L, the pH of the mixed solution is adjusted to be 8, and the grain size is 5.6 mu m;
the method comprises the following steps of (1) adjusting the feeding flow rate of a nickel-cobalt-manganese ternary salt solution to be 130L/h, wherein the feeding flow rate of ammonia water and a precipitator solution is adjusted by setting the molar ratio of total metal ions in the nickel-cobalt-manganese ternary salt solution to ammonia monohydrate in the ammonia water to be 10 and the molar ratio of the total metal ions to sodium ions in the nickel-cobalt-manganese ternary salt solution to be 2;
in the middle stage of growth, adjusting the temperature, pH and ammonium ion concentration of the mixed solution, specifically, when the grain size increases by 1 μm, the temperature increases by 5 ℃, the pH decreases by 0.05, and the mass concentration of ammonium ions decreases by 0.05g/L; namely, when the grain size reaches 14.6 μm, the temperature is 75 ℃, the pH is 7.55, and the mass concentration of ammonium ions is 0.05g/L;
in the middle stage of growth, the rotation speed of the stirrer was adjusted, 6 μm was decreased to 240rpm,7 μm was decreased to 200rpm,8 μm was decreased to 120rpm,9 μm was decreased to 100rpm,10 μm was decreased to 90rpm, and thereafter the rotation speed was maintained at 90rpm;
controlling the growth time to be 35h by adjusting the solid content;
after the growth is finished, adding a potassium carbonate solution into the reaction kettle, adjusting the pH value of the mixed solution to 8, aging for 2 hours, and then centrifugally drying to obtain the NCM811 nickel-cobalt-manganese ternary precursor material.
Through detection, the particle size D50 of the NCM811 Ni-Co-Mn ternary precursor material prepared by the embodiment is 15.1 mu m, and the specific surface area is 123g/cm 3 。
Comparative example 1
The particle size provided by the comparative example is 16 +/-0.2 mu m, and the specific surface area is 15-17g/cm 3 The NCM622 nickel cobalt manganese ternary precursor material of (a) was prepared in substantially the same manner as in example 1, except that, in the step (c), the temperature, pH and ammonium ion concentration of the mixed solution were adjusted only at the initial stage of growth, specifically, the reaction temperature was adjusted to 55 ℃, and NH was adjusted 4 + The mass concentration of the mixed solution is adjusted to be 5g/L, and the pH value of the mixed solution is adjusted to be 12; while the temperature, pH and ammonium ion concentration of the mixed solution were not adjusted in the intermediate stage of growth.
Through detection, the particle size D50 of the NCM622 nickel cobalt manganese ternary precursor material prepared by the comparative example is 16.2 mu m, and the specific surface area is 5.3g/cm 3 。
Comparative example 2
The particle size provided by the comparative example is 16 +/-0.2 mu m, and the specific surface area is 15-17g/cm 3 The preparation method of the NCM622 nickel cobalt manganese ternary precursor material is basically the same as that of example 1, except that in the step (c), the solid content is not adjusted, and the growth time is controlled to 138h.
Through detection, the particle size D50 of the NCM622 nickel cobalt manganese ternary precursor material prepared in the comparative example is 16.1 mu m, and the specific surface area is 6.1g/cm 3 。
By comparing the specific surface areas of the nickel-cobalt-manganese ternary precursor materials prepared in the embodiment 1 and the comparative examples 1-2, the specific surface area of the precursor material can be remarkably increased by adjusting the temperature, the pH and the ammonium ion concentration for multiple times according to the grain size in the growth stage.
Test example 1
Scanning electron microscope tests are performed on the nickel-cobalt-manganese ternary precursor materials prepared in example 1 and comparative example 1, and the results are shown in fig. 1 and fig. 2 respectively.
As can be seen from a comparison of fig. 1 and 2, the precursor material prepared in example 1 of the present invention by adjusting the temperature, pH and ammonium ion concentration several times according to the grain size during the growth stage has a significantly higher specific surface area than comparative example 1 in which the temperature, pH and ammonium ion concentration are adjusted only once during the growth stage.
While particular embodiments of the present invention have been illustrated and described, it will be appreciated that the above embodiments are only intended to illustrate the technical solution of the present invention and not to limit it; those of ordinary skill in the art will understand that: modifications may be made to the above-described embodiments, or equivalents may be substituted for some or all of the features thereof without departing from the spirit and scope of the present invention; the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention; it is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (21)
1. A preparation method of a nickel-cobalt-manganese ternary precursor material is characterized by comprising the following steps:
(1) Mixing a nickel-cobalt-manganese ternary metal salt solution with a precipitator solution, ammonia water and a base solution in an inert atmosphere, and reacting to obtain a solution containing ternary metal crystal grains;
(2) Mixing a nickel-cobalt-manganese ternary metal salt solution, ammonia water, a precipitator solution and the solution containing the ternary metal crystal grains obtained in the step (1) in an inert atmosphere to grow the crystal grains, adjusting the pH, the ammonium ion concentration and the temperature of the solution at least twice in the growth process, controlling the growth time range to be 6-60 h by controlling the solid content, aging after the crystal grains grow to the required grain size range, and performing solid-liquid separation to obtain the nickel-cobalt-manganese ternary precursor material;
in the step (2), the temperature adjusting method specifically includes: when the grain size increases by 1 μm, the temperature increases by 1-20 ℃;
the method for adjusting the pH specifically comprises the following steps: when the grain size increases by 1 μm, the pH value decreases by 0.01-2;
the method for adjusting the concentration of the ammonium ions specifically comprises the following steps: when the grain size is increased by 1 mu m, the mass concentration of ammonium ions is reduced by 0.01-2 g/L.
2. The method according to claim 1, wherein in the step (2), the temperature adjusting method specifically comprises: when the grain size increases by 1 μm, the temperature increases by 2-15 ℃.
3. The method according to claim 1, wherein in the step (2), the method for adjusting the pH specifically comprises: when the grain size is increased by 1 mu m, the pH value is reduced by 0.02-1.
4. The method according to claim 1, wherein the method for adjusting the ammonium ion concentration in step (2) specifically comprises: when the grain size is increased by 1 mu m, the mass concentration of ammonium ions is reduced by 0.02-1 g/L.
5. The method according to claim 1, wherein in the step (1), the base solution includes ammonium ions and hydroxide ions.
6. The method according to claim 5, wherein the mass concentration of ammonium ions in the base solution is 0.5 to 20g/L, and the pH of the base solution is 7.5 to 14.
7. The production method according to claim 1, wherein the temperature of the solution system in steps (1) and (2) is 30 to 90 ℃.
8. The production method according to claim 1, wherein the temperature of the solution system in steps (1) and (2) is 35 to 75 ℃.
9. The production method according to claim 1, wherein in the steps (1) and (2), the pH of the solution system is 7.5 to 14.
10. The production method according to claim 1, wherein in the steps (1) and (2), the pH of the solution system is 8 to 13.5.
11. The method according to claim 1, wherein the mass concentration of ammonium ions in the solution system in steps (1) and (2) is 0.01 to 20g/L.
12. The method according to claim 1, wherein the mass concentration of ammonium ions in the solution system in steps (1) and (2) is 1 to 15g/L.
13. The preparation method according to claim 1, wherein in the steps (1) and (2), the total molar concentration of metal ions in the nickel-cobalt-manganese ternary metal salt solution is 0.1-3 mol/L.
14. The preparation method according to claim 1, wherein in the steps (1) and (2), the total molar concentration of metal ions in the nickel-cobalt-manganese ternary metal salt solution is 1-2.5 mol/L.
15. The method according to claim 1, wherein the molar concentration of ammonium ions in the ammonia water in the steps (1) and (2) is 0.01 to 13mol/L.
16. The method according to claim 1, wherein the molar concentration of ammonium ions in the ammonia water in the steps (1) and (2) is 0.1 to 10mol/L.
17. The method according to claim 1, wherein in steps (1) and (2), the total molar concentration of all metal ions in the precipitant solution is 0.1 to 18mol/L.
18. The method according to claim 1, wherein in steps (1) and (2), the total molar concentration of all metal ions in the precipitant solution is 2 to 15mol/L.
19. The method according to claim 1, wherein in steps (1) and (2), the precipitant comprises at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.
20. The preparation method according to claim 1, wherein in step (2), the aging specifically comprises: mixing the mixed solution with alkali, adjusting the pH value to 8-13, and aging for 2-24 h.
21. The method of claim 20, wherein the pH is adjusted to 9 to 12 and aged for 5 to 20 hours.
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