CN107579218B - Method for directly preparing nickel-cobalt-aluminum ternary positive electrode material precursor from acid leaching solution of laterite-nickel ore - Google Patents
Method for directly preparing nickel-cobalt-aluminum ternary positive electrode material precursor from acid leaching solution of laterite-nickel ore Download PDFInfo
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Abstract
The invention provides a method for directly preparing a nickel-cobalt-aluminum ternary cathode material precursor from an acid leaching solution of laterite-nickel ore. The method comprises the following steps: A. removing impurities and separating impurities, B, preparing a mixed solution. C. Preparing sodium metaaluminate solution, D, preparing alkaline solution as precipitant, E, precipitation reaction and ageing. The method for preparing the nickel-cobalt-aluminum ternary cathode material precursor directly prepares the product by taking the acid leaching solution of the laterite-nickel ore as the raw material, and has short production flow and low production cost. The ternary precursor material prepared by the method provided by the invention has the advantages of uniform particle size distribution, good stability, high specific capacity, high activity and higher tap density.
Description
Technical Field
The invention relates to a preparation method of a precursor of a lithium battery anode material, in particular to a method for directly preparing a precursor of a nickel-cobalt-aluminum ternary anode material from an acid leaching solution of laterite-nickel ore.
Background
The lithium ion secondary battery has been greatly and heteroscedasticity in the fields of traffic facilities, military equipment, digital products and the like by virtue of the advantages of high average working voltage, large energy density, long cycle life, small self-discharge, no memory effect, adaptability to rapid charge and discharge and the like, and has a wider application prospect in the fields of power batteries of electric bicycles, electric automobiles and the like.
The positive electrode material of a lithium ion secondary battery, which is one of the main factors affecting the cost and performance thereof, is conventional LiCoO2The anode material is gradually replaced by a ternary material which is partially Ni and Mn replaced Co due to overhigh cost, and the ternary anode material is LiCoO2/LiNiO2/LiMn2O4In a eutectic system, which has both LiCoO and2、LiNiO2、LiMn2O4the three materials have the advantages of high specific capacity, low cost, stable cycle performance and the like. However, the nickel-cobalt-manganese ternary cathode material of the lithium ion battery in the prior art has the following problems:
(1) the nickel substitution amount is low, so that the actual capacity of the nickel-cobalt-manganese ternary positive electrode material is low;
(2) the nickel-rich nickel-cobalt-manganese ternary material has poor stability and relatively low safety, and the wide application of the nickel-rich nickel-cobalt-manganese ternary material is limited;
(3) the prior ternary materials mostly adopt refined sulfate, nitrate and chloride, and have the problems of long flow from initial raw materials to products, large discharge, high cost, no environmental pollution and no environmental protection.
Nickel cobalt is an important strategic non-ferrous metal. In recent years, the demand of nickel and cobalt in the battery field is rapidly increased, and the contradiction between high consumption and low resource supply is increasingly intensified. The traditional method for treating complex nickel-cobalt resources has the problems of long process flow, low resource utilization rate, high energy consumption, emission amplification, serious environmental pollution and the like. In addition, the cost of the ternary material is still higher in the long run, and the prepared main raw materials are sulfates, nitrates and chlorides of nickel, cobalt, manganese and aluminum.
CN106058244A discloses a method for preparing a precursor of a nickel-cobalt-aluminum positive electrode material, which comprises the following steps: preparing a nickel-cobalt-aluminum mixed salt solution containing a complexing agent and a strong alkali solution containing ammonia water; synchronously injecting the nickel-cobalt-aluminum mixed salt solution and the strong alkaline solution into a reaction kettle containing a base solution at a constant speed in a parallel flow manner for carrying out a coprecipitation reaction; and after the injection of the nickel-cobalt-aluminum mixed salt solution is finished, stopping adding the strong alkali solution, aging the slurry after the reaction is completed, and performing liquid-solid separation to obtain the nickel-cobalt-aluminum anode material precursor. The method has the disadvantages of long flow, high cost and no environmental pollution because the refined sulfate is used as the raw material.
Nickel is a main electrochemical active element, the source of the nickel is mainly nickel sulfide or sulfuric acid high-pressure process leachate of the laterite-nickel ore, and the leachate simultaneously contains cobalt, manganese and aluminum elements, so that the research on the acid leachate of the laterite-nickel ore is carried out, and the direct use of the acid leachate as a raw material for preparing the ternary battery material is an important research direction in the field.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for directly preparing a nickel-cobalt-aluminum ternary cathode material precursor from an acid leaching solution of laterite-nickel ore. The method for preparing the nickel-cobalt-aluminum ternary cathode material precursor combines materials and metallurgical technology, takes the acid leaching solution of the laterite-nickel ore as a raw material, and has the advantages of short process flow and low cost.
In order to achieve the purpose, the invention adopts the following scheme:
the invention provides a method for directly preparing a nickel-cobalt-aluminum ternary cathode material precursor from an acid leaching solution of laterite-nickel ore, which comprises the following steps:
A. removing impurities and separating impurities
① taking acid leaching solution of lateritic nickel ore as raw material, adding a first alkaline substance, keeping the pH value of the solution less than 7, carrying out solid-liquid separation to obtain filter cake, dissolving the filter cake with acid solution, and carrying out solid-liquid separation to obtain filtrate;
② adding oxidant and second alkaline substance into the filtrate obtained in step ① to make the pH value of the solution more than 7, and separating solid and liquid to obtain filtrate;
③ adding a third alkaline substance into the filtrate obtained in step ② to make the pH value of the solution higher than that in step ②, performing solid-liquid separation to obtain a filter cake, and dissolving the filter cake in an acid solution to obtain a nickel-cobalt-rich solution;
B. preparing mixed solution
Adding soluble cobalt salt into the nickel-cobalt-rich solution obtained in the step A to obtain a mixed solution, wherein the molar ratio of nickel to cobalt in the mixed solution is 4-5.4;
C. preparing sodium metaaluminate solution
D. Preparing alkaline solution as precipitant
E. Precipitation reaction and aging
And (3) adding a mixed solution of water and ammonia water into a reaction kettle as a base solution, starting the reaction kettle for stirring, introducing nitrogen, heating, simultaneously adding the mixed solution obtained in the step (B), the sodium metaaluminate solution obtained in the step (C) and the precipitator obtained in the step (D) into the reaction kettle, controlling the element molar ratio of aluminum to nickel in a reaction system to be 1/40-1/16, and aging after the reaction is finished to obtain the nickel-cobalt-aluminum ternary cathode material precursor.
As a preferable technical scheme of the invention, the acid leachate of the laterite-nickel ore in the step A is a hydrochloric acid leachate of the laterite-nickel ore.
Preferably, the first basic substance in step ① is any one or combination of at least two of magnesium oxide, magnesium carbonate, magnesium hydroxide, sodium carbonate, sodium hydroxide, potassium carbonate or potassium hydroxide, typically but not limited to, a combination of magnesium oxide and magnesium carbonate, a combination of magnesium oxide and magnesium hydroxide, a combination of magnesium carbonate and magnesium hydroxide, a combination of sodium hydroxide and potassium carbonate, a combination of magnesium oxide, magnesium carbonate and magnesium hydroxide, a combination of sodium hydroxide, potassium carbonate and potassium hydroxide, and the like, preferably any one or combination of at least two of magnesium oxide, magnesium carbonate or magnesium hydroxide.
Preferably, the first basic material of step ① is in the form of a slurry having a solids content of 1 wt% to 3 wt%, such as 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, or 3 wt%, and the like, but is not limited to the recited values, and other unrecited values within the recited range are equally applicable.
Preferably, the oxidizing agent of step ② is an aqueous solution of hydrogen peroxide.
Preferably, the aqueous hydrogen peroxide solution has a mass fraction of 6 wt% to 15 wt%, such as 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt% or 15 wt%, but not limited to the recited values, and other unrecited values within the range of values are also applicable.
Preferably, the second basic substance in step ② includes, but is not limited to, any one or a combination of at least two of sodium hydroxide, potassium hydroxide, sodium oxide or potassium oxide, typically but not limited to, a combination of sodium hydroxide and potassium hydroxide, a combination of potassium hydroxide and sodium oxide, a combination of sodium oxide and potassium oxide, a combination of sodium hydroxide, potassium hydroxide and sodium oxide, a combination of potassium hydroxide, sodium oxide and potassium oxide, etc.
Preferably, the acid solution of step ② includes any one or a combination of at least two of hydrochloric acid, nitric acid, or sulfuric acid, typically but not limited to, a combination of nitric acid and sulfuric acid, a combination of nitric acid and hydrochloric acid, a combination of hydrochloric acid and sulfuric acid, and a combination of nitric acid, sulfuric acid, and hydrochloric acid.
Preferably, the acid solution of step ② has a mass fraction of 5 wt% to 10 wt%, such as 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt%, but not limited to the recited values, and other values not recited are also applicable within the recited values, the acid solution of step ② has the above-mentioned preferred ranges to facilitate the formation of Ni (OH) in the filter cake of this step2、Co(OH)2And Mg (OH)2Dissolving but retaining MnO2The precipitated state of (c).
Preferably, the third alkaline material of step ③ includes, but is not limited to, any one or a combination of at least two of sodium hydroxide, potassium hydroxide, sodium carbonate or sodium bicarbonate, typically but not limited to, a combination of sodium hydroxide and potassium hydroxide, a combination of potassium hydroxide and sodium carbonate, a combination of sodium carbonate and sodium bicarbonate, a combination of sodium hydroxide, potassium hydroxide and sodium carbonate, a combination of potassium hydroxide, sodium carbonate and sodium bicarbonate, etc.
In the step A, a first alkaline substance is used for removing Fe3+The reaction equation is as follows:
Fe3++3H2O——Fe(OH)3+3H+
in the step A, the oxidizing agent and the second basic substance may be Mn2+And Mg2+A precipitate is formed, which has the reaction equation:
Mn2++H2O2+2OH-——MnO2+2H2O
Mg2++2OH-——Mg(OH)2
in the step A, a third alkaline substance is used to allow Ni to react2+And Co2+A precipitate formed.
Preferably, the pH of step ① is 3.8-4.2, such as, but not limited to, 3.8, 3.9, 4.0, 4.1, or 4.2, and the like, and is not limited to, the recited values, as well as other values within the recited ranges, the pH of step ② is 9-10, such as, but not limited to, 9, 9.2, 9.4, 9.6, 9.8, or 10, and the like, and is also applicable to other values within the recited ranges, the pH of step ③ is 10.1-11.5, such as, but not limited to, 10.1, 10.3, 10.5, 10.7, 10.9, 11.1, 11.3, or 11.5, and the like, and the other values within the recited ranges are also applicable, the pH of step ① is 3.8-4.2, and is favorable for Fe3+Precipitation of (2) to remove impurities, outside of which Fe is produced3+The impurity removal is incomplete, and the pH value of ② is 9-10, so that Mn can be removed2+、Ni2+And Co2+And a small amount of Mg2+A precipitate is formed, the pH value of ③ is 10.1-11.5, which can ensure Ni2+And Co2+Completely precipitated with the remaining Mg2+Difficult to precipitate, and obtaining a filter cake substantially free of other substances by solid-liquid separation after the filtrationCobalt and nickel as metallic impurities.
In step ③, the filter cake may be sampled for nickel cobalt content.
Preferably, the acid solution of step ③ is any one of nitric acid, sulfuric acid, or hydrochloric acid, or a combination of at least two of them, typically but not limited to, a combination of nitric acid and sulfuric acid, a combination of nitric acid and hydrochloric acid, a combination of hydrochloric acid and sulfuric acid, and a combination of nitric acid, sulfuric acid, and hydrochloric acid.
Preferably, the acid solution of step ③ has a mass fraction of 8 wt% to 15 wt%, such as 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, or 15 wt%, but not limited to the recited values, and other values not recited within the range are equally applicable.
In a preferred embodiment of the present invention, the soluble cobalt salt in step B is added in an amount such that the sum of the nickel and cobalt concentrations in the mixed solution obtained in step B is 1.5mol/L to 3mol/L, for example, 1.5mol/L, 1.8mol/L, 2mol/L, 2.3mol/L, 2.5mol/L, 2.7mol/L, 2.9mol/L, or 3mol/L, but the amount is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable. The sum of the nickel and cobalt concentrations in the mixed solution can affect the subsequent precipitation reaction, and if the concentration is too low, the sphericity of the precursor of the nickel-cobalt-aluminum ternary positive electrode material finally generated is low, and the particles are too small; if the concentration is too high, the precursor of the nickel-cobalt-aluminum ternary cathode material finally prepared is agglomerated.
In the step C, the method for preparing the sodium metaaluminate adopts the method in the prior art.
As a preferable technical scheme of the invention, ammonia water is added into the sodium metaaluminate solution in the step C.
Preferably, the ammonia water has a molar concentration of 1mol/L to 3mol/L, such as 1mol/L, 1.2mol/L, 1.4mol/L, 1.5mol/L, 1.8mol/L, 2mol/L, 2.3mol/L, 2.5mol/L, 2.7mol/L, 2.9mol/L, or 3mol/L, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the ammonia is added in an amount to maintain step ENH in the reaction system4 +In a desired amount to give a concentration of 0.1mol/L to 1mol/L, e.g. NH4 +The concentration of (B) is a desired amount such as 0.1mol/L, 0.2mol/L, 0.4mol/L, 0.6mol/L, 0.8mol/L or 1mol/L, but not limited to the values listed, and other values not listed in the numerical range are also applicable.
The addition of ammonia water in the step C can avoid the continuous addition of ammonia water in the subsequent precipitation reaction process to keep NH4 +In the concentration process, an ammonia water input device is not needed to be additionally arranged in a reaction kettle of the precipitation reaction, so that the cost is reduced.
In a preferred embodiment of the present invention, in the alkaline solution in step D, the alkaline is any one or a combination of at least two of sodium hydroxide, potassium hydroxide, sodium oxide, and potassium oxide, and typical but non-limiting combinations include: a combination of sodium hydroxide and potassium hydroxide, a combination of potassium hydroxide and sodium oxide, a combination of sodium oxide and potassium oxide, a combination of sodium hydroxide, potassium hydroxide and sodium oxide, a combination of potassium hydroxide, sodium oxide and potassium oxide, and the like, with sodium hydroxide being preferred.
Preferably, the concentration of the alkali solution in step D is 2mol/L to 4mol/L, such as 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L or 4mol/L, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
In the step D, the preparation amount of the precipitant preferably satisfies both the proportioning requirement of the nickel-cobalt-aluminum ternary cathode material precursor and the requirement of controlling the pH value of the reaction system in the step E.
In a preferred embodiment of the present invention, the mass fraction of the aqueous ammonia is 0.2 to 0.8 wt%, for example, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7 or 0.8 wt% based on 100 wt% of the total mass of the base solution, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
Preferably, the addition amount of the base solution in the step E is 1/4-1/3 of the volume of the reaction kettle.
Preferably, the stirring speed in step E is 600rpm to 800rpm, such as 600rpm, 650rpm, 700rpm, 750rpm, 800rpm, etc., but is not limited to the recited values, and other values not recited in the range of values are also applicable. The appearance of the obtained nickel-cobalt-aluminum ternary positive electrode material precursor is influenced by overhigh rotating speed, so that the sphericity is reduced; if the rotation speed is too low, the dispersion condition of the newly generated crystals in the reaction is poor, the crystals are easy to agglomerate, and the nickel-cobalt-aluminum ternary cathode material precursor with good dispersion is difficult to obtain.
Preferably, the nitrogen gas flow rate in step E is 0.1L/min to 0.5L/min, such as 0.1L/min, 0.2L/min, 0.3L/min, 0.4L/min, or 0.5L/min, but not limited to the recited values, and other values not recited in the range of values are also applicable.
In a preferred embodiment of the present invention, the heating temperature in step E is 40 to 60 ℃, for example, 40 ℃, 45 ℃, 50 ℃, 55 ℃ or 60 ℃, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable. Due to the fact that the temperature is too high, the reaction is too fast and difficult to control, and particles of a precursor of the nickel-cobalt-aluminum ternary positive electrode material are not uniform; too low a temperature will cause the reaction to be too slow, again not conducive to uniform particles.
Preferably, in step E, the addition rate of the mixed solution in step B and the sodium metaaluminate solution in step C is the same, and is 0.1L/min-10L/min, such as 0.1L/min, 0.5L/min, 1L/min, 3L/min, 5L/min, 7L/min, 9L/min or 10L/min, but not limited to the values listed, and other values not listed in the range of the values are also applicable.
Preferably, in step E, the precipitant in step D is added in an amount to make the reaction system pH 10.5-11.5, such as 10.5, 10.7, 10.9, 11, 11.1, 11.3 or 11.5, but not limited to the recited values, and other values not recited in the range of the values are also applicable. The pH value can influence the appearance of the prepared nickel-cobalt-aluminum ternary positive electrode material precursor, and the precursor is easy to agglomerate due to too high pH value, so that a spherical product with good dispersion is not formed; too low a pH leads to large precipitated particles and insufficient precipitation.
Preferably, in the step E, the mixed solution in the step B, the sodium metaaluminate solution in the step C and the precipitating agent in the step D are added dropwise.
Preferably, in step E, the aging time is 20h to 40h, such as 20h, 25h, 30h, 35h or 40h, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
In step E, the reaction equation for forming the nickel-cobalt-aluminum ternary cathode material precursor is as follows:
0.8Ni2++(0.2-x)Co2++x[Al(OH)4]-——Ni0.8Co0.2-xAlx(OH)2(wherein x is 0.01 to 0.05)
And as a preferable technical scheme of the invention, the method further comprises the steps of carrying out solid-liquid separation, washing and drying on the nickel-cobalt-aluminum ternary cathode material precursor obtained in the step E.
In a preferred embodiment of the present invention, the washing is water washing.
Preferably, the number of washes is 3 to 5, such as 3, 4 or 5.
Preferably, the temperature of the drying is 90 ℃ to 120 ℃, such as 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the drying time is 12h to 24h, for example, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h or 24h, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a further preferred technical solution of the method of the present invention, the method comprises the steps of:
A. removing impurities and separating impurities
①, taking a lateritic nickel ore hydrochloric acid leaching solution as a raw material, adding an alkaline substance, controlling the pH value to be 3.8-4.2, and carrying out solid-liquid separation to obtain a filtrate;
②, adding hydrogen peroxide solution into the filtrate obtained in the step ①, controlling the pH value to be 9-10 by using sodium hydroxide, carrying out solid-liquid separation to obtain a filter cake, dissolving the filter cake by using 5-10 wt% of acid solution, and carrying out solid-liquid separation to obtain a filtrate;
③, adding sodium hydroxide into the filtrate obtained in the step ②, adjusting the pH value of the solution to 10.1-11.5, carrying out solid-liquid separation to obtain a filter cake, and dissolving the filter cake with an acid solution to obtain a nickel-cobalt-rich solution;
B. preparing mixed solution
Adding soluble cobalt salt into the nickel-cobalt-rich solution obtained in the step A to obtain a mixed solution, wherein the molar ratio of nickel to cobalt in the mixed solution is 4-5.4, and the sum of the nickel and cobalt concentrations is 1.5-3 mol/L;
C. preparing sodium metaaluminate solution
Preparing a sodium metaaluminate solution, and adding ammonia water with the molar concentration of 1-3 mol/L into the sodium metaaluminate solution;
D. preparing alkaline solution as precipitant
Preparing a sodium hydroxide solution with the concentration of 2-4 mol/L as a precipitator;
E. precipitation reaction and aging
Adding a mixed solution of 1/4-1/3 of reaction kettle volume water and ammonia water into a reaction kettle as a base solution, wherein NH is contained in the base solution3·H2The mass fraction of O is 0.2 to 0.8 percent; starting the reaction kettle for stirring, and controlling the stirring speed to be 600-800 rpm; introducing nitrogen with the flow rate of 0.1L/min-0.5L/min; heating to 40-60 ℃, adding the mixed solution obtained in the step B, the sodium metaaluminate solution obtained in the step C and the precipitant obtained in the step D into a reaction kettle at the same time, wherein the adding speeds of the mixed solution obtained in the step B and the sodium metaaluminate solution obtained in the step C are the same and are both 0.1-10L/min, the molar ratio of aluminum to nickel in a reaction system is ensured to be 1/40-1/16, the adding amount of the precipitant obtained in the step D is such that the pH value of the reaction system is 10.5-11.5, and after the reaction is finished, aging for 20-40 hours to obtain the precursor of the nickel-cobalt-aluminum ternary cathode material;
wherein, in the step A, the basic substance in the step ① is one or at least two of magnesium oxide, magnesium carbonate or magnesium hydroxideThe method comprises the following steps of mixing, wherein the solid content of slurry is 1-3 wt%, the mass fraction of hydrogen peroxide in step ② is 6-15 wt%, the acid in step ② comprises any one or combination of at least two of hydrochloric acid, nitric acid or sulfuric acid, the acid solution in step ③ is any one or combination of at least two of nitric acid, sulfuric acid or hydrochloric acid, the mass fraction of the acid solution is 8-15 wt%, and the adding amount of ammonia water in step C is to maintain NH in the reaction system in step E4 +The concentration is 0.1mol/L to 1 mol/L.
Compared with the prior art, the invention has the following beneficial effects:
the method for preparing the nickel-cobalt-aluminum ternary cathode material precursor directly prepares the product by taking the acid leaching solution of the laterite-nickel ore as the raw material, and has short production flow and low production cost; the method provided by the invention is characterized in that the nickel-cobalt-aluminum ternary precursor material Ni is prepared by the steps of removing impurities from the acid leaching solution of the laterite-nickel ore step by step, preparing mixed salt and meta-aluminate and the like by adopting a homogeneous phase complex coprecipitation method under the protection of nitrogen0.8Co0.2-xAlx(OH)2(wherein x is 0.01-0.05) the product has the advantages of uniform particle size distribution, good stability, high specific capacity, high activity and high tap density (up to 2.33 g/cm)3The product has low impurity content, wherein the mass fraction of the impurity Fe can be reduced to 7ppm, the mass fraction of the impurity Na can be reduced to 51ppm, the mass fraction of the impurity Mg can be reduced to 87ppm, and the mass fraction of the impurity Mn can be reduced to 124 ppm.
Drawings
Fig. 1 is a process flow chart of a method for directly preparing a nickel-cobalt-aluminum ternary cathode material precursor from a lateritic nickel ore hydrochloric acid leach solution, which is provided by embodiment 1 of the invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
The specific embodiment of the invention partially provides a method for preparing a nickel-cobalt-aluminum ternary cathode material precursor by taking acid leaching solution of laterite-nickel ore as a raw material, which comprises the following steps:
A. removing impurities and separating impurities
① taking acid leachate of the lateritic nickel ore as a raw material, adding a first alkaline substance, keeping the pH value of the solution less than 7, and carrying out solid-liquid separation to obtain filtrate;
② adding an oxidant and a second alkaline substance into the filtrate obtained in the step ① to enable the pH value of the solution to be larger than 7, carrying out solid-liquid separation to obtain a filter cake, adding 5-10 wt% of dilute acid into the filter cake to dissolve the filter cake, and carrying out solid-liquid separation to obtain a filtrate;
③ adding a third alkaline substance into the filtrate obtained in step ② to make the pH value of the solution higher than that in step ②, performing solid-liquid separation to obtain a filter cake, and dissolving the filter cake in an acid solution to obtain a nickel-cobalt-rich solution;
B. preparing mixed solution
Adding soluble cobalt salt into the nickel-cobalt-rich solution obtained in the step A to obtain a mixed solution, wherein the molar ratio of nickel to cobalt in the mixed solution is 4-5.4;
C. preparing sodium metaaluminate solution
D. Preparing alkaline solution as precipitant
E. Precipitation reaction and aging
And (3) adding a mixed solution of water and ammonia water into a reaction kettle as a base solution, starting the reaction kettle for stirring, introducing nitrogen, heating, simultaneously adding the mixed solution obtained in the step (B), the sodium metaaluminate solution obtained in the step (C) and the precipitant obtained in the step (D) into the reaction kettle, controlling the element molar ratio of aluminum to nickel in a reaction system to be 1/40-1/16, and aging after the reaction is finished to obtain the nickel-cobalt-aluminum ternary cathode material precursor.
The volume of the diluted acid added in the step A is calculated as follows:
analysis of the crude cake (dry basis), the mass fraction w of nickel hydroxide1The mass fraction of the cobalt hydroxide is w2Assuming that the mass of the filter cake is m kg (dry basis, weighing and metering), and the total concentration of three elements required to be prepared is 2mol/L, the volume of the added diluted acid is as follows:
V＝m*w1/92.7/0.8/2-m/1000
V1equal to V + m/1000, V1Is the volume of the nickel-cobalt-rich solution.
The calculation of the step B plus soluble cobalt salt is as follows:
the volume of the nickel-cobalt-rich solution in the step A is V1Then, the molar weight of the added soluble cobalt salt is as follows:
ncobalt＝2V1*(0.2-x)-m*w2/92.9 wherein x is 0.01-0.05
In the process of preparing the sodium metaaluminate solution in the step C, the molar weight of the soluble aluminum salt and the sodium hydroxide is calculated as follows:
the volume of the nickel-cobalt-rich solution in the step A is V1Then, the molar amount of the added soluble aluminum salt is:
naluminium＝2V1X is 0.01 to 0.05
nNaOH＝y*nAluminium＝10V1X is 0.01 to 0.05, and y is 2.5 to 5
In the step D, the preparation amount of the precipitator adopting sodium hydroxide is calculated as follows:
VNaOH＝V1*2*2/CNaOH
wherein: vNaOHVolume of sodium hydroxide, V1Volume of nickel-cobalt-rich solution, CNaOHThe molar concentration of the sodium hydroxide is prepared for the requirement.
The following are typical but non-limiting examples of the invention:
example 1
The embodiment provides a method for preparing a nickel-cobalt-aluminum ternary cathode material precursor by taking an acid leaching solution of laterite-nickel ore as a raw material, which comprises the following specific steps:
A. impurity removal and impurity separation: take 150m3The laterite nickel ore hydrochloric acid leaching solution has the following element contents:
① adding 330kg of magnesium oxide slurry with the mass fraction of 1% dropwise, controlling the pH to be 3.8, carrying out solid-liquid separation to remove iron, and taking filtrate;
② adding 5 wt.% NaOH and 8 wt.% hydrogen peroxide 212kg into the pickle liquor, controlling pH to 9.0, separating solid and liquid to obtain filter cake, adding 5 wt.% dilute sulfuric acid 20m3Performing solid-liquid separation to remove Mn and Mg, and taking filtrate;
③ adding 5 wt% NaOH solution into the filtrate, controlling pH to 10.5, filtering to obtain filter cake (dry basis): 778.3kg, 94.3 wt% nickel hydroxide and 5.7 wt% cobalt hydroxide, adding dilute sulfuric acid (10 wt.%) and adjusting volume to 4.17m3The volume of the obtained nickel-rich cobalt solution is 4.95m3。
The content of each element of the nickel-cobalt-rich solution is as follows:
B. preparing a mixed solution: 1.3kmol of cobalt sulfate heptahydrate is added into the nickel-cobalt-rich solution, and the mass is as follows: 365.4kg of the raw materials are mixed and stirred for 0.5h (h is h) to obtain a mixed solution, wherein the molar ratio of nickel to cobalt in the mixed solution is 4.4;
C. preparing an aluminum metaaluminate solution: 0.198kmol of aluminum sulfate octadecahydrate (131.95kg) was weighed, 0.99kmol of sodium hydroxide (39.6kg) was weighed, and the sodium hydroxide was dissolved in 1m3Adding aluminum sulfate octadecahydrate into water under stirring, continuously stirring for 0.5h, and adding the mixed solution into the water to obtain a solution with the thickness of 4m32mol/L ammonia water, and continuously stirring for 0.5h to obtain a mixed solution of metaaluminate and the ammonia water;
D. preparing a precipitator: preparing sodium hydroxide solution with concentration of 4mol/L, 5.1m3；
E. Precipitation reaction and aging: firstly, 4000L of mixed solution of pure water and ammonia water, NH, is added into a reaction kettle3·H2The mass fraction of O is 0.2 percent; starting the reaction kettle for stirring, and controlling the stirring speed at 600 rpm; introducing nitrogen with the flow rate of 0.1L/min; heating to 40 ℃, adjusting the bottom liquid of the reaction kettle to 10.5 by using a sodium hydroxide solution, and then adding the mixed solution obtained in the step B and the sodium metaaluminate obtained in the step C and ammoniaDropwise adding the mixed solution of water and the precipitant obtained in the step D into the reaction kettle at the same time, keeping the adding rate of the mixed solution obtained in the step B and the sodium metaaluminate obtained in the step C consistent, keeping the speed at 5L/min, controlling the element molar ratio of aluminum to nickel in the reaction system to be 1/40, controlling the pH value of the reaction kettle to be 10.50 +/-0.05 by the precipitant obtained in the step D, and aging for 20 hours after dropwise adding is finished to obtain Ni0.8Co0.18Al0.02(OH)2A precursor material;
F. separation and washing: carrying out solid-liquid separation on the precursor suspension containing the nickel-cobalt-aluminum ternary positive electrode material obtained in the step E, and repeatedly washing for 3 times by using pure water;
G. and D, drying, namely putting the precipitate obtained in the step F into an oven for drying at the drying temperature of 100 ℃ for 20 hours to obtain dried Ni0.8Co0.18Al0.02(OH)2A precursor material.
Fig. 1 is a process flow chart of a method for directly preparing a nickel-cobalt-aluminum ternary cathode material precursor from a lateritic nickel ore hydrochloric acid leaching solution provided by this embodiment.
The product of this example has a normal particle size distribution, D50 of 11.27 μm, and a tap density of 2.21g/cm3。
Other technical indexes of the product of the embodiment are shown in table 1.
Example 2
The embodiment provides a method for preparing a nickel-cobalt-aluminum ternary cathode material precursor by taking an acid leaching solution of laterite-nickel ore as a raw material, which comprises the following specific steps:
A. impurity removal and impurity separation: get 75m3The laterite nickel ore hydrochloric acid leaching solution has the following element contents:
① slowly adding 248.5kg magnesium carbonate slurry with mass fraction of 2%, controlling pH within 4.0, filtering to remove iron, and collecting filtrate;
② then 5 wt% NaOH and 159kg of 10 wt% hydrogen peroxide were added to the pickle liquor, and the pH was controlled to 9.5, filtering to obtain a filter cake, and adding 10 wt% of dilute nitric acid 10m3Performing solid-liquid separation to remove Mn and Mg, and taking filtrate;
③ adding 5 wt% NaOH solution into the filtrate, controlling pH to 11, filtering to obtain filter cake (dried basis) 583.7kg, containing nickel hydroxide 94.3 wt% and cobalt hydroxide 5.7 wt%, and dilute nitric acid (10 wt.%) 3.13m3The volume of the obtained nickel-rich cobalt solution is 3.71m3. The content of each element of the nickel-cobalt-rich solution is as follows:
B. preparing a mixed solution: adding 0.98kmol of cobalt nitrate hexahydrate into the nickel-cobalt-rich solution, wherein the mass is as follows: 285.2kg, mixing and stirring for 0.5h (h is h) to obtain a mixed solution, wherein the molar ratio of nickel to cobalt in the mixed solution is 4.4;
C. preparing an aluminum metaaluminate solution: 0.149kmol of aluminum nitrate octadecahydrate (55.7kg) was weighed, 0.75kmol of sodium hydroxide (30kg) was weighed, and the sodium hydroxide was dissolved in 0.75m3Adding aluminum sulfate octadecahydrate into water under stirring, continuously stirring for 0.5h, and adding the mixed solution into the water to obtain a solution with the thickness of 3m32mol/L ammonia water, and continuously stirring for 0.5h to obtain a mixed solution of metaaluminate and the ammonia water;
D. preparing a precipitator: preparing 4.0m sodium hydroxide solution with the concentration of 4mol/L3；
E. Precipitation reaction and aging: firstly, 3000L of mixed solution of pure water and ammonia water, NH, is added into a reaction kettle3·H2The mass fraction of O is 0.5 percent; starting the reaction kettle for stirring, and controlling the stirring speed at 700 rpm; introducing nitrogen with the flow rate of 0.3L/min; heating to 50 ℃, adjusting the bottom liquid of the reaction kettle to 11.0 by using a sodium hydroxide solution, then simultaneously dropwise adding the mixed solution obtained in the step B, the mixed solution of sodium metaaluminate and ammonia water obtained in the step C and the precipitating agent obtained in the step D into the reaction kettle, keeping the adding rates of the mixed solution obtained in the step B and the sodium metaaluminate obtained in the step C consistent, wherein the speed is 8L/min, the element molar ratio of aluminum to nickel in the reaction system is 1/40, and controlling the reaction by using the precipitating agent obtained in the step DThe pH value of the kettle is 11.00 +/-0.05, and the kettle is aged for 30 hours after the dropwise addition is finished to obtain Ni0.8Co0.18Al0.02(OH)2A precursor material;
F. separation and washing: carrying out solid-liquid separation on the suspension obtained in the step E, and repeatedly washing the suspension for 3 times by using pure water;
G. and D, drying, namely putting the precipitate obtained in the step F into an oven for drying at the drying temperature of 100 ℃ for 20 hours to obtain dried Ni0.8Co0.18Al0.02(OH)2A precursor material.
The particle size of the product of this example is normally distributed, D50 is 9.89 μm, and the tap density is higher, 2.3g/cm3。
Other technical indexes of the product of the embodiment are shown in table 1.
Example 3
The embodiment provides a method for preparing a nickel-cobalt-aluminum ternary cathode material precursor by taking an acid leaching solution of laterite-nickel ore as a raw material, which comprises the following specific steps:
A. impurity removal and impurity separation: take 50m3The laterite nickel ore hydrochloric acid leaching solution has the following element contents:
① dropwise adding 101.5kg of magnesium hydroxide slurry with the mass fraction of 3%, controlling the pH value within 4.2, filtering to remove iron, and taking filtrate;
② adding 5 wt% NaOH and 15 wt% hydrogen peroxide 89kg into the pickle liquor, controlling pH to 10.0, filtering to obtain filter cake, adding 5 wt% dilute hydrochloric acid 5m3Performing solid-liquid separation to remove Mn and Mg, and taking filtrate;
③ adding 5 wt% NaOH solution into the filtrate, controlling pH at 11.5, filtering to obtain filter cake (dried basis) of 389.2kg, nickel hydroxide content of the filter cake at 94.3 wt%, cobalt hydroxide content of the filter cake at 5.7 wt%, and dilute hydrochloric acid (10 wt%) at 2.09m3The volume of the obtained nickel-rich cobalt solution is 2.48m3. The content of each element in the nickel-cobalt-rich solutionThe following were used:
B. preparing a mixed solution: adding 0.65kmol of cobalt chloride hexahydrate into the nickel-cobalt-rich solution, wherein the mass is as follows: 154.6kg, and the mixture is stirred for 0.5h (h is h) to obtain a mixed solution, wherein the molar ratio of nickel to cobalt in the mixed solution is 4.4;
C. preparing an aluminum metaaluminate solution: 0.099kmol of aluminum chloride hexahydrate (23.89kg) was weighed, 0.5kmol of sodium hydroxide (20kg) was weighed, and the sodium hydroxide was dissolved in 0.5m3Adding aluminum chloride hexahydrate into water under stirring, stirring for 0.5h, and adding the mixed solution to 2m32mol/L ammonia water, and continuously stirring for 0.5h to obtain a mixed solution of metaaluminate and the ammonia water;
D. preparing a precipitator: 2.5m sodium hydroxide solution with the concentration of 4mol/L is prepared3；
E. Precipitation reaction and aging: firstly, 2000L of mixed solution of pure water and ammonia water, NH, is added into a reaction kettle3·H2The mass fraction of O is 0.8%; starting the reaction kettle for stirring, and controlling the stirring speed at 800 rpm; introducing nitrogen with the flow rate of 0.5L/min; heating to 60 ℃, adjusting the pH value of the bottom liquid of the reaction kettle to 11.5 by using a sodium hydroxide solution, then simultaneously dropwise adding the mixed solution obtained in the step B, the mixed solution of sodium metaaluminate and ammonia water obtained in the step C and the precipitating agent obtained in the step D into the reaction kettle, keeping the adding rates of the mixed solution obtained in the step B and the sodium metaaluminate obtained in the step C consistent, keeping the adding speed at 10L/min, controlling the element molar ratio of aluminum to nickel in the reaction system to be 1/40, controlling the pH value of the reaction kettle to be 11.50 +/-0.05 by using the precipitating agent obtained in the step D, aging for 40 hours after the dropwise adding is finished, and obtaining Ni0.8Co0.18Al0.02(OH)2A precursor material;
F. separation and washing: carrying out solid-liquid separation on the suspension obtained in the step E, and washing for 3 times by using pure water;
G. and D, drying, namely putting the precipitate obtained in the step F into an oven for drying at the temperature of 120 ℃ for 20 hours to obtain dried Ni0.8Co0.18Al0.02(OH)2A precursor material.
The particle size of the product of this example is normally distributed, D50 is 7.38 μm, and the tap density is higher, 2.33g/cm3。
Other technical indexes of the product of the embodiment are shown in table 1.
Example 4
The embodiment provides a method for preparing a nickel-cobalt-aluminum ternary cathode material precursor by taking an acid leaching solution of laterite-nickel ore as a raw material, and the specific preparation method is as shown in embodiment 3, except that:
in the step B, the adding amount of cobalt chloride hexahydrate is changed, so that the molar ratio of nickel to cobalt in the mixed solution is 5.3;
in step E, the elemental molar ratio of aluminum to nickel in the reaction system was made 1/16.
Ni obtained in example0.8Co0.15Al0.05(OH)2The particle size of the product is normally distributed, the D50 is 7.71 mu m, the tap density is higher and is 2.24g/cm3。
Other technical indexes of the product of the embodiment are shown in table 1.
Example 5
The embodiment provides a method for preparing a nickel-cobalt-aluminum ternary cathode material precursor by taking an acid leaching solution of laterite-nickel ore as a raw material, and the specific preparation method is as shown in embodiment 3, except that:
in the step B, the adding amount of cobalt chloride hexahydrate is changed, so that the molar ratio of nickel to cobalt in the mixed solution is 5;
in step E, the elemental molar ratio of aluminum to nickel in the reaction system was made 1/20.
Ni obtained in example0.8Co0.16Al0.04(OH)2The particle size of the product is normally distributed, the D50 is 7.12 mu m, the tap density is higher and is 2.27g/cm3。
Other technical indexes of the product of the embodiment are shown in table 1.
Example 6
The embodiment provides a method for preparing a nickel-cobalt-aluminum ternary cathode material precursor by taking an acid leaching solution of laterite-nickel ore as a raw material, and the specific preparation method is as shown in embodiment 3, except that:
in step A, the pH was controlled to 10.8 at step ②.
Ni obtained in example0.8Co0.18Al0.02(OH)2The product has normally distributed particle size, D50 of 7.83 μm, and high tap density of 2.19g/cm3。
Other technical indexes of the product of the embodiment are shown in table 1.
Comparative example 1
The specific procedure of this comparative example refers to example 3 except that in step A, in step ①, the pH is controlled to 8.
As a result, the final product contains a large amount of impurity iron, so that the magnetic substance exceeds the standard, the performance is seriously reduced, and the product cannot be used.
The technical indexes of the comparative product are shown in Table 1.
TABLE 1 technical indices of the products of the inventive examples and comparative examples (the contents of the substances in the tables are mass fractions)
As can be seen from the above examples 1-6 and the comparative example 1, the method for directly preparing the nickel-cobalt-aluminum ternary precursor material Ni from the acid leaching solution of the laterite-nickel ore provided by the invention prepares the nickel-cobalt-aluminum ternary precursor material Ni by the homogeneous phase complexation coprecipitation method under the protection of nitrogen through the procedures of removing impurities from the acid leaching solution of the laterite-nickel ore step by step, preparing mixed salt and meta-aluminate and the like0.8Co0.2-xAlx(OH)2(wherein x is 0.01-0.05), and the precursor material has the advantages of uniform particle size distribution, good stability, high specific capacity, high activity, high tap density and the like. Comparative example the nickel cobalt aluminum tris having excellent properties could not be obtained because the scheme of the present invention was not usedA meta-precursor material.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (31)
1. A method for directly preparing a nickel-cobalt-aluminum ternary cathode material precursor from an acid leaching solution of laterite-nickel ore is characterized by comprising the following steps:
A. removing impurities and separating impurities
① taking acid leachate of the lateritic nickel ore as a raw material, adding a first alkaline substance, keeping the pH value of the solution less than 7, and carrying out solid-liquid separation to obtain filtrate;
② adding oxidant and second alkaline substance into the filtrate obtained in step ① to make the pH value of the solution be greater than 7, carrying out solid-liquid separation to obtain filter cake, dissolving the filter cake with acid solution, and carrying out solid-liquid separation to obtain filtrate;
③ adding a third alkaline substance into the filtrate obtained in step ② to make the pH value of the solution higher than that in step ②, performing solid-liquid separation to obtain a filter cake, and dissolving the filter cake in an acid solution to obtain a nickel-cobalt-rich solution;
B. preparing mixed solution
Adding soluble cobalt salt into the nickel-cobalt-rich solution obtained in the step A to obtain a mixed solution, wherein the molar ratio of nickel to cobalt in the mixed solution is 4-5.4;
C. preparing sodium metaaluminate solution
D. Preparing alkaline solution as precipitant
E. Precipitation reaction and aging
Adding a mixed solution of water and ammonia water into a reaction kettle as a base solution, starting the reaction kettle for stirring, introducing nitrogen, heating, simultaneously adding the mixed solution obtained in the step B, the sodium metaaluminate solution obtained in the step C and the precipitator obtained in the step D into the reaction kettle, controlling the element molar ratio of aluminum to nickel in a reaction system to be 1/40-1/16, and aging after the reaction is finished to obtain a precursor of the nickel-cobalt-aluminum ternary cathode material;
wherein, in step ①, the first basic substance is any one or a combination of at least two of magnesium oxide, magnesium carbonate or magnesium hydroxide;
step ②, the oxidant is hydrogen peroxide solution;
the second basic substance in step ② is sodium hydroxide;
step ③ wherein the third alkaline substance comprises any one or a combination of at least two of sodium hydroxide, potassium hydroxide, sodium carbonate, or sodium bicarbonate;
in the alkaline solution in the step D, the alkali used is any one or the combination of at least two of sodium hydroxide, potassium hydroxide, sodium oxide or potassium oxide.
2. The method according to the claim 1, characterized in that the acid leachate of lateritic nickel ores of step a is a hydrochloric leachate of lateritic nickel ores.
3. The method of claim 1, wherein said first alkaline material of step ① is in the form of a slurry having a solids content of 1 wt% to 3 wt%.
4. The method according to claim 1, wherein the mass fraction of the aqueous hydrogen peroxide solution is 6 to 15 wt%.
5. The method of claim 1, wherein the acid solution of step ② comprises any one of hydrochloric acid, nitric acid, or sulfuric acid, or a combination of at least two thereof.
6. The method as claimed in claim 1, wherein the mass fraction of the acid solution in step ② is 5 wt% to 10 wt%.
7. The method of claim 1, wherein the third alkaline substance of step ③ is sodium hydroxide.
8. The method of claim 1, wherein the pH of step ① is 3.8-4.2, the pH of step ② is 9-10, and the pH of step ③ is 10.1-11.5.
9. The method of claim 1, wherein the acid solution of step ③ is any one of nitric acid, sulfuric acid, or hydrochloric acid, or a combination of at least two of them.
10. The method as claimed in claim 1, wherein the mass fraction of the acid solution in step ③ is 8 wt% to 15 wt%.
11. The method of claim 1, wherein the soluble cobalt salt of step B is added in an amount such that the sum of the nickel and cobalt concentrations in the mixed solution obtained in step B is 1.5mol/L to 3 mol/L.
12. The method of claim 1, wherein ammonia is added to said sodium metaaluminate solution in step C.
13. The method of claim 12, wherein the ammonia water has a molar concentration of 1 to 3 mol/L.
14. The method of claim 12, wherein the ammonia is added in an amount to maintain NH in the reaction system of step E4 +The concentration is 0.1mol/L to 1 mol/L.
15. The method of claim 1, wherein in the alkaline solution of step D, the base used is sodium hydroxide.
16. The method of claim 1, wherein the concentration of the alkaline solution in step D is 2mol/L to 4 mol/L.
17. The method according to claim 1, wherein the mass fraction of the aqueous ammonia is 0.2 wt% to 0.8 wt% based on 100 wt% of the total mass of the base solution.
18. The method of claim 1, wherein the amount of the base solution added in step E is 1/4-1/3 of the volume of the reaction kettle.
19. The method of claim 1, wherein the stirring speed in step E is 600rpm to 800 rpm.
20. The method of claim 1, wherein the flow rate of the nitrogen gas in the step E is 0.1L/min to 0.5L/min.
21. The method of claim 1, wherein the heating temperature in step E is 40 ℃ to 60 ℃.
22. The method according to claim 1, wherein in step E, the mixed solution in step B and the sodium metaaluminate solution in step C are added at the same rate of 0.1L/min to 10L/min.
23. The method according to claim 1, wherein in the step E, the precipitant in the step D is added in an amount such that the pH of the reaction system is 10.5 to 11.5.
24. The method as claimed in claim 1, wherein in step E, the mixed solution of step B, the sodium metaaluminate solution of step C and the precipitant of step D are added dropwise.
25. The method according to claim 1, wherein in step E, the aging time is 20-40 h.
26. The method of claim 1, further comprising the steps of performing solid-liquid separation, washing and drying on the nickel-cobalt-aluminum ternary positive electrode material precursor obtained in the step E.
27. The method of claim 26, wherein the washing is with water.
28. The method of claim 26, wherein the number of washes is 3 to 5.
29. The method of claim 26, wherein the temperature of the drying is between 90 ℃ and 120 ℃.
30. The method of claim 26, wherein the drying is maintained for a time period of 12 to 24 hours.
31. Method according to claim 1, characterized in that it comprises the following steps:
A. removing impurities and separating impurities
①, taking a lateritic nickel ore hydrochloric acid leaching solution as a raw material, adding an alkaline substance, controlling the pH value to be 3.8-4.2, and carrying out solid-liquid separation to obtain a filtrate;
②, adding hydrogen peroxide solution into the filtrate obtained in the step ①, controlling the pH value to be 9-10 by using sodium hydroxide, carrying out solid-liquid separation to obtain a filter cake, dissolving the filter cake by using 5-10 wt% of acid solution, and carrying out solid-liquid separation to obtain a filtrate;
③, adding sodium hydroxide into the filtrate obtained in the step ②, adjusting the pH value of the solution to 10.1-11.5, carrying out solid-liquid separation to obtain a filter cake, and dissolving the filter cake with an acid solution to obtain a nickel-cobalt-rich solution;
B. preparing mixed solution
Adding soluble cobalt salt into the nickel-cobalt-rich solution obtained in the step A to obtain a mixed solution, wherein the molar ratio of nickel to cobalt in the mixed solution is 4-5.4, and the sum of the nickel and cobalt concentrations is 1.5-3 mol/L;
C. preparing sodium metaaluminate solution
Preparing a sodium metaaluminate solution, and adding ammonia water with the molar concentration of 1-3 mol/L into the sodium metaaluminate solution;
D. preparing alkaline solution as precipitant
Preparing a sodium hydroxide solution with the concentration of 2-4 mol/L as a precipitator;
E. precipitation reaction and aging
Adding a mixed solution of 1/4-1/3 of reaction kettle volume water and ammonia water into a reaction kettle as a base solution, wherein NH is contained in the base solution3·H2The mass fraction of O is 0.2 to 0.8 percent; starting the reaction kettle for stirring, and controlling the stirring speed to be 600-800 rpm; introducing nitrogen with the flow rate of 0.1L/min-0.5L/min; heating to 40-60 ℃, adding the mixed solution obtained in the step B, the sodium metaaluminate solution obtained in the step C and the precipitant obtained in the step D into a reaction kettle at the same time, wherein the adding speeds of the mixed solution obtained in the step B and the sodium metaaluminate solution obtained in the step C are the same and are both 0.1-10L/min, the molar ratio of aluminum to nickel in a reaction system is ensured to be 1/40-1/16, the adding amount of the precipitant obtained in the step D is such that the pH value of the reaction system is 10.5-11.5, and after the reaction is finished, aging for 20-40 hours to obtain the precursor of the nickel-cobalt-aluminum ternary cathode material;
wherein in the step A, the alkaline substance in the step ① is any one or combination of at least two of magnesium oxide, magnesium carbonate or magnesium hydroxide and is in a slurry form, the solid content of the slurry is 1 wt% -3 wt%, the mass fraction of the hydrogen peroxide in the step ② is 6 wt% -15 wt%, the acid solution in the step ③ is any one or combination of at least two of nitric acid, sulfuric acid or hydrochloric acid, the mass fraction of the acid solution is 8 wt% -15 wt%, and the adding amount of the ammonia water in the step C is the amount of NH in the reaction system maintaining the step E4 +The concentration is 0.1mol/L to 1 mol/L.
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| CN109052492B (en) * | 2018-07-24 | 2020-02-07 | 眉山顺应动力电池材料有限公司 | Method for preparing ternary cathode material from laterite nickel ore nitric acid leaching solution |
| CN108970621B (en) * | 2018-08-08 | 2021-02-26 | 芜湖格丰环保科技研究院有限公司 | Method for preparing water body COD degradation catalyst by using laterite-nickel ore smelting waste residues and application of water body COD degradation catalyst in ozone degradation |
| CN109592720B (en) * | 2018-11-23 | 2021-06-11 | 湖南中伟新能源科技有限公司 | Ternary precursor solution purification method |
| CN111471862B (en) * | 2019-01-24 | 2021-12-07 | 河北中科同创道格赛尔新材料科技有限公司 | Treatment method of laterite-nickel ore pickle liquor |
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