CN113461073A - Ternary precursor and preparation method and application thereof - Google Patents
Ternary precursor and preparation method and application thereof Download PDFInfo
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention relates to the technical field of lithium ion battery materials, in particular to a ternary precursor and a preparation method and application thereof. The preparation method of the ternary precursor comprises the following steps: carrying out a first coprecipitation reaction on a mixture containing mixed metal salt, a precipitator, a complexing agent and a reaction base solution under the condition of nitrogen, continuously introducing nitrogen and air to carry out a second coprecipitation reaction after the D50 particle size of the obtained precipitate is 1.5-2.5 microns, and till the D50 particle size of the precipitate is 3.0-4.5 microns; the mixed metal salt is soluble nickel salt, soluble cobalt salt and soluble manganese salt; in the second coprecipitation reaction, the ratio of the flow rate of the air to the flow rate of the nitrogen is 0.1 to 2.0. The method has the advantages of low preparation cost, simple regulation and control process and easy control, and the obtained ternary precursor has higher specific surface area.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a ternary precursor and a preparation method and application thereof.
Background
Due to environmental concerns and concerns about resource shortages, new energy technologies are being vigorously developed in many countries of the world today. The lithium ion battery has been developed into one of the battery products with the widest application range at present by virtue of the characteristics of light weight, high energy density, environmental protection and no memory effect. Most of the electric automobiles use lithium ion batteries as power supplies, which is also the main application field of the lithium ion batteries. And more countries are beginning to announce the exit time point of fuel vehicles, the larger fuel vehicle market will be replaced by electric vehicles. Standing at a new starting point, under the guidance of a carbon neutralization concept, the clean, efficient and reusable lithium ion battery obtains a larger development space and has a wider development market.
The nickel-cobalt-manganese ternary precursor material prepared by the traditional method at present has large primary crystal grains and compact primary crystal grain distribution, so that the specific surface area of the nickel-cobalt-manganese ternary precursor is small, and the difficulty in sintering the rear-end anode material is increased. Most of the sintered positive electrode material inherits the structural characteristics of the precursor material, so that the sintered positive electrode material has coarse and compact primary crystal grains and small specific particle surface area. In the using process, the small specific surface area can reduce the deintercalation and migration rate of lithium ions, and the contact area of particles and electrolyte is smaller, so that the performance requirements of high-power charging and discharging of the power battery are difficult to meet.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a preparation method of a ternary precursor, which is characterized in that air is introduced after the grain diameter of D50 of ternary precursor particles is 1.5-2.5 mu m, and the introduction rate of the air and nitrogen is a fixed ratio, so that the specific surface area of the ternary precursor particles is effectively improved, the preparation cost is low, the regulation and control process is simple and is easy to control.
The invention also aims to provide the ternary precursor prepared by the preparation method of the ternary precursor. It has a high specific surface area.
Another object of the present invention is to provide a lithium ion battery, which is mainly prepared from the ternary precursor as described above.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a preparation method of a ternary precursor comprises the following steps:
carrying out a first coprecipitation reaction on a mixture containing mixed metal salt, a precipitator, a complexing agent and a reaction base solution under the condition of nitrogen, continuously introducing nitrogen and air to carry out a second coprecipitation reaction after the D50 particle size of the obtained precipitate is 1.5-2.5 microns, and till the D50 particle size of the precipitate is 3.0-4.5 microns;
the mixed metal salt is soluble nickel salt, soluble cobalt salt and soluble manganese salt;
in the second coprecipitation reaction, the ratio of the flow rate of the air to the flow rate of the nitrogen is 0.1 to 2.0.
Preferably, the flow rate of the nitrogen for the first coprecipitation reaction and the second coprecipitation reaction is 0.5-5 m3/h。
Preferably, the mixed metal salt, the precipitator and the complexing agent are respectively mixed with the reaction base solution in the form of solution;
preferably, in the mixed metal salt solution, the sum of the concentrations of nickel ions, cobalt ions and manganese ions is 0.5-3.0 mol/L;
preferably, in the mixed metal salt, the molar ratio of nickel, cobalt and manganese is (1-92): (1-4): (1-4);
preferably, in the precipitant solution, the concentration of the precipitant is 5-10 mol/L;
preferably, the precipitating agent comprises sodium hydroxide;
preferably, in the complexing agent solution, the concentration of the complexing agent is 7-14 mol/L;
preferably, the complexing agent comprises NH3·H2O。
Preferably, the reaction bottom liquid mainly consists of water and NH3·H2O and alkali are prepared;
preferably, the pH of the reaction bottom liquid is 9-12;
preferably, the concentration of ammonium radicals in the reaction base solution is 2-8 g/L;
preferably, the addition amount of the reaction bottom liquid is 1/4-2/4 of the volume of the reaction container.
Preferably, in the first coprecipitation reaction and the second coprecipitation reaction, the temperature of a reaction system is 30-75 ℃;
preferably, in the first coprecipitation reaction and the second coprecipitation reaction, the pH of a reaction system is 9-12;
preferably, in the first coprecipitation reaction and the second coprecipitation reaction, the concentration of ammonium radicals in a reaction system is 2-8 g/L;
preferably, in the first coprecipitation reaction and the second coprecipitation reaction, the stirring speed of the reaction system is 100-400 r/min.
Preferably, the first co-precipitation reaction specifically comprises the steps of:
adding the mixed metal salt, the precipitator and the complexing agent into the reaction base solution under the condition of continuously introducing nitrogen for reaction, standing after the reaction, and removing part of the upper-layer reaction solution; and adding the mixed metal salt, the precipitator and the complexing agent into the residual reaction solution for reaction under the condition of continuously introducing nitrogen.
Preferably, the standing time is 1-6 h;
preferably, the time for continuously introducing nitrogen into the residual reaction liquid is 50-65 min;
preferably, the mixed metal salt, the precipitant and the complexing agent are added into the residual reaction solution to react under the condition of stirring, wherein the stirring time is 25-35 min;
preferably, the volume of the residual reaction liquid is 1/3-2/3 of the volume of the reaction container.
Preferably, after the D50 particle size of the precipitate is 3.0-4.5 μm, aging and solid-liquid separation are carried out, and the solid after solid-liquid separation is washed, dried, screened and demagnetized;
preferably, the aging time is 5-7 h;
preferably, the washing comprises: washing until the pH value of washing water is 7-7.5;
preferably, the drying temperature is 100-140 ℃.
The ternary precursor is prepared by the preparation method of the ternary precursor;
preferably, the specific surface area of the ternary precursor is 14-24 m2/g。
The lithium ion battery electrode material is mainly prepared from the ternary precursor.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the preparation method of the ternary precursor, air is introduced after the D50 particle size of the ternary precursor particles grows to be 1.5-2.5 microns, and the introduction rate of the air and nitrogen is set to be a fixed ratio, so that the ternary precursor particles with higher specific surface area are obtained; the preparation cost is low, the regulation and control process is simple and easy to control.
(2) The ternary precursor obtained by the invention has higher specific surface area. The lithium ion battery can be used for preparing a lithium ion battery, and can better meet the performance requirements of high power and charge and discharge of a power battery.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
According to one aspect of the invention, the invention relates to a method for preparing a ternary precursor, comprising the following steps:
carrying out a first coprecipitation reaction on a mixture containing mixed metal salt, a precipitator, a complexing agent and a reaction base solution under the condition of nitrogen, continuously introducing nitrogen and air to carry out a second coprecipitation reaction after the D50 particle size of the obtained precipitate is 1.5-2.5 microns, and till the D50 particle size of the precipitate is 3.0-4.5 microns;
the mixed metal salt is soluble nickel salt, soluble cobalt salt and soluble manganese salt;
in the second coprecipitation reaction, the ratio of the flow rate of the air to the flow rate of the nitrogen is 0.1 to 2.0.
According to the invention, air is introduced after the D50 particle size of the ternary precursor fine particles grows to be 1.5-2.5 microns, and the introduction rate of the air and the nitrogen is a fixed ratio, so that the specific surface area of the ternary precursor particles is effectively increased. The preparation cost is low, the regulation and control process is simple and easy to control.
In one embodiment, the D50 particle size of the precipitate obtained from the first co-precipitation reaction is 1.5-2.5 μm, and may be selected from 1.5 μm, 1.6 μm, 1.7 μm, 1.8 μm, 1.9 μm, 2 μm, 2.1 μm, 2.2 μm, 2.3 μm, 2.4 μm, or 2.5 μm.
In one embodiment, the second coprecipitation reaction is carried out until the D50 particle size of the precipitate is 3.0-4.5 μm, and may be 3.0 μm, 3.1 μm, 3.2 μm, 3.3 μm, 3.4 μm, 3.5 μm, 3.6 μm, 3.7 μm, 3.8 μm, 3.9 μm, 4.0 μm, 4.1 μm, 4.2 μm, 4.3 μm, 4.4 μm or 4.5 μm.
In one embodiment, in the second coprecipitation reaction, the ratio of the flow rate of air to the flow rate of nitrogen is 0.1 to 2.0, and may be selected from 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1,
1.8:1, 1.9:1 or 2: 1.
The soluble nickel salt includes nickel sulfate.
The soluble cobalt salt comprises cobalt sulfate.
The soluble manganese salt comprises manganese sulfate.
Preferably, the flow rate of the nitrogen for the first coprecipitation reaction and the second coprecipitation reaction is 0.5-5 m3/h。
In one embodiment, the flow rates of the nitrogen gas in the first coprecipitation reaction and the second coprecipitation reaction are both 0.5-5 m3H, 0.6m can also be selected3/h、0.8m3/h、1m3/h、1.2m3/h、1.5m3/h、1.7m3/h、2m3/h、2.2m3/h、2.5m3/h、2.7m3/h、3m3/h、3.2m3/h、3.5m3/h、3.7m3/h、4m3/h、4.2m3/h、4.5m3/h、4.7m3/h、4.9m3H or 5m3/h。
Preferably, the mixed metal salt, the precipitant and the complexing agent are respectively mixed with the reaction base solution in the form of solution.
Preferably, the sum of the concentrations of the nickel ions, the cobalt ions and the manganese ions in the mixed metal salt solution is 0.5-3.0 mol/L.
In one embodiment, the sum of the concentrations of nickel ions, cobalt ions and manganese ions in the mixed metal salt solution is 0.5-3.0 mol/L, and optionally 0.8mol/L, 1mol/L, 1.2mol/L, 1.5mol/L, 1.7mol/L, 2mol/L, 2.3mol/L, 2.5mol/L, 2.7mol/L or 3 mol/L.
Preferably, in the mixed metal salt, the ratio of nickel: cobalt: the molar ratio of manganese is (1-92): (1-4): (1-4).
In one embodiment, in the mixed metal salt, the ratio of nickel: cobalt: the molar ratio of manganese may also be selected from 1:1:1, 5:1:1, 10:1:1, 15:2:2, 20:2:1, 30:1:2, 40:1:2.5, 50:2:2.5, 60:3:2, 70:2:3, 80:3:3, 90:3.5:4 or 92:4: 4.
Preferably, the concentration of the precipitant in the precipitant solution is 5-10 mol/L.
In one embodiment, the concentration of the precipitant in the precipitant solution can also be selected from 6mol/L, 7mol/L, 8mol/L, or 9 mol/L.
Preferably, the precipitating agent comprises a soluble base.
Preferably, the soluble base comprises sodium hydroxide.
Preferably, in the complexing agent solution, the concentration of the complexing agent is 7-14 mol/L.
In one embodiment, the concentration of the complexing agent in the complexing agent solution can also be selected from 7mol/L, 8mol/L, 9mol/L, 10mol/L, 11mol/L, 12mol/L or 13 mol/L.
Preferably, the complexing agent comprises NH3·H2O。
Preferably, the reaction bottom liquid mainly consists of water and NH3·H2O and alkali.
Preferably, the pH of the reaction bottom liquid is 9-12.
In one embodiment, the reaction bottom liquid has a pH of 9 to 12, and may be selected from 10 or 11.
Preferably, the concentration of ammonium radicals in the reaction base solution is 2-8 g/L.
In one embodiment, the concentration of ammonium groups in the reaction base solution can also be selected from 2g/L, 3g/L, 4g/L, 5g/L, 6g/L, 7g/L or 8 g/L.
Preferably, the addition amount of the reaction bottom liquid is 1/4-2/4 of the volume of the reaction container.
Preferably, in the first coprecipitation reaction and the second coprecipitation reaction, the temperature of the reaction system is 30-75 ℃.
In one embodiment, in the first coprecipitation reaction and the second coprecipitation reaction, the temperature of the reaction system may be further selected from 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃ or 75 ℃, respectively.
Preferably, in the first coprecipitation reaction and the second coprecipitation reaction, the pH of the reaction system is 9-12.
In one embodiment, in the first coprecipitation reaction and the second coprecipitation reaction, the pH of the reaction system may also be selected from 9, 10, 11, or 12, respectively.
Preferably, in the first coprecipitation reaction and the second coprecipitation reaction, the concentration of ammonium groups in a reaction system is 2-8 g/L.
In one embodiment, in the first coprecipitation reaction and the second coprecipitation reaction, the ammonium concentration of the reaction system can be selected from 2g/L, 3g/L, 4g/L, 5g/L, 6g/L, 7g/L or 8 g/L.
Preferably, in the first coprecipitation reaction and the second coprecipitation reaction, the stirring speed of the reaction system is 100-400 r/min.
In one embodiment, in the first coprecipitation reaction and the second coprecipitation reaction, the stirring speed of the reaction system can also be selected from 100r/min, 120r/min, 150r/min, 170r/min, 200r/min, 220r/min, 250r/min, 270r/min, 300r/min, 320r/min, 350r/min, 370r/min and 400 r/min.
Preferably, the first co-precipitation reaction specifically comprises the steps of:
adding the mixed metal salt, the precipitator and the complexing agent into the reaction base solution under the condition of continuously introducing nitrogen for reaction, standing after the reaction, and removing part of the upper-layer reaction solution; and adding the mixed metal salt, the precipitator and the complexing agent into the residual reaction solution for reaction under the condition of continuously introducing inert gas.
Preferably, the standing time is 1-6 h.
In one embodiment, the standing time can also be selected from 1h, 2h, 3h, 4h, 5h or 6 h.
Preferably, the time for continuously introducing the inert gas into the residual reaction liquid is 50-65 min.
In one embodiment, the time for continuously introducing the nitrogen into the remaining mixed system can be selected from 51min, 52min, 53min, 54min, 55min, 56min, 57min, 58min, 59min, 60min, 61min, 62min, 63min or 64 min.
Preferably, the mixed metal salt, the precipitant and the complexing agent are added into the residual reaction solution to react under the condition of stirring, and the stirring time is 25-35 min. It can also be selected from 26min, 27min, 28min, 29min, 30min, 31min, 32min, 33min or 34 min.
Preferably, the volume of the residual reaction liquid is 1/3-2/3 of the volume of the reaction container.
Preferably, after the D50 particle size of the precipitate is 3.0-4.5 μm, aging and solid-liquid separation are carried out, and the solid after solid-liquid separation is washed, dried, screened and demagnetized.
Preferably, the aging time is 5-7 h. 5.5h, 6h or 6.5h can also be selected.
Preferably, the washing comprises: washing until the pH value of the washing water is 7-7.5. 7.1h, 7.2h, 7.3h or 7.4h can also be selected.
Preferably, the drying temperature is 100-140 ℃. It is also possible to select 110 deg.C, 115 deg.C, 120 deg.C, 125 deg.C, 130 deg.C or 135 deg.C.
In a preferred embodiment, the preparation method of the ternary precursor comprises the following steps:
the preparation method of the ternary precursor comprises the following steps:
(a) preparing a nickel-cobalt-manganese soluble mixed salt solution, wherein the sum of the concentrations of nickel ions, cobalt ions and manganese ions is 0.5-3.0 mol/L, and the weight ratio of nickel: cobalt: the molar ratio of manganese is (1-92): (1-4): (1-4); preparation of NH3·H2The concentration of the O solution is 7-14 mol/L; preparing a sodium hydroxide solution with the concentration of 5-10 mol/L;
(b) pure water, an ammonia water solution and an alkali liquor are introduced into a reaction kettle to prepare a reaction base solution, wherein the pH of the reaction base solution is 9-12, the ammonium concentration is 2-8 g/L, and the addition amount of the reaction base solution is 1/4-2/4 of the volume of the reaction kettle;
(c) heating the reaction kettle, starting stirring, introducing nitrogen, wherein the temperature of the reaction kettle is 30-75 ℃, the stirring speed is 100-400 r/min, and the nitrogen introduction speed is 0.5-5 m3H; then, introducing the prepared nickel-cobalt-manganese soluble mixed salt solution, ammonia water solution and sodium hydroxide solution by using a precise metering pump to perform coprecipitation reaction; during the coprecipitation reaction process, the reaction conditions are maintainedThe ammonium concentration is 2-8 g/L, the pH value is 9-12, the stirring speed is 100-400 r/min, and the temperature of the reaction kettle is 30-75 ℃;
(d) continuously stirring, keeping the temperature of the reaction kettle stable, and continuously introducing mixed salt solution, ammonia water solution and alkali liquor; stopping stirring and closing nitrogen when the liquid level in the reaction kettle is over the baffle, standing for 1-6 hours, and then pumping out supernatant liquid by using a pneumatic pump, wherein the volume of the residual reaction liquid is 1/3-2/3 of the volume of the reaction kettle;
(e) continuously adding 0.5-5 m2Introducing nitrogen at a speed of 1h for 1h, starting stirring for 30min, introducing a nickel-cobalt-manganese mixed salt solution, an ammonia water solution and a sodium hydroxide solution by using a precision metering pump, and keeping the temperature, the pH value and the ammonium concentration stable in the whole process;
(f) after the median diameter (D50) of the particles is 1.5-2.5 mu m, continuously introducing air into the reaction kettle by using 1-5 pipelines, wherein the distance between the bottom of the pipelines and the bottom of the reaction kettle is 20-70 cm, the ratio of the flow rate of the air to the flow rate of nitrogen is 0.1-2.0, the ammonium concentration is kept at 2-8 g/L, the pH value is 9-12, the stirring speed is 100-400 r/min, the temperature of the reaction kettle is 30-75 ℃, and the reaction liquid is transferred into an aging kettle to be aged for 5-7 hours until the median diameter (D50) of the particles reaches the target value of 3.0-4.5 mu m;
(g) performing solid-liquid separation on the aged substance to obtain a solid, washing the solid with 0.1-1.5 mol/L alkali liquor, continuously washing with deionized water until the pH value of washing water is 7-7.5, and dehydrating to obtain a wet material; and drying the wet material at a high temperature of 100-140 ℃, and then screening by using a screen and a demagnetizing device to obtain the ternary precursor with high specific surface fine particles.
According to another aspect of the invention, the invention also relates to the ternary precursor prepared by the preparation method of the ternary precursor.
Preferably, the specific surface area of the ternary precursor is 14-24 m2/g。
The lithium ion battery electrode material is mainly prepared from the ternary precursor.
The invention will be further explained with reference to specific examples.
Example 1
The preparation method of the ternary precursor comprises the following steps:
(a) preparing a nickel-cobalt-manganese soluble mixed salt solution, wherein the sum of the concentrations of nickel ions, cobalt ions and manganese ions is 2mol/L, and the weight ratio of nickel: cobalt: the molar ratio of manganese is 5:2: 3; preparation of NH3·H2O solution with the concentration of 7 mol/L; preparing a sodium hydroxide solution with the concentration of 10 mol/L;
(b) introducing pure water, an ammonia water solution and an alkali liquor into a reaction kettle to prepare a reaction bottom liquid, wherein the pH of the reaction bottom liquid is 11, the ammonium concentration is 6g/L, and the addition amount of the reaction bottom liquid is 1/3 of the volume of the reaction kettle;
(c) heating the reaction kettle, starting stirring, introducing nitrogen, wherein the temperature of the reaction kettle is 50 ℃, the stirring speed is 400r/min, and the nitrogen introduction speed is 2m3H; then, introducing the prepared nickel-cobalt-manganese soluble mixed salt solution, ammonia water solution and sodium hydroxide solution by using a precise metering pump to perform coprecipitation reaction; in the coprecipitation reaction process, the ammonium concentration is kept to be 4g/L, the pH value is kept to be 12, the stirring speed is 400r/min, and the temperature of a reaction kettle is 50 ℃;
(d) continuously stirring, keeping the temperature of the reaction kettle stable, and continuously introducing mixed salt solution, ammonia water solution and alkali liquor; stopping stirring and closing nitrogen when the liquid level in the reaction kettle is over the baffle, standing for 5 hours, and then pumping out supernatant by using a pneumatic pump, wherein the volume of the residual reaction liquid is 1/2 of the volume of the reaction kettle;
(e) continue with 2m2Introducing nitrogen at a speed of 1h for 1h, starting stirring for 30min, introducing a nickel-cobalt-manganese mixed salt solution, an ammonia water solution and a sodium hydroxide solution by using a precision metering pump, and keeping the temperature, the pH value and the ammonium concentration stable in the whole process;
(f) after the median diameter (D50) of the particles is 1.9 mu m, continuously introducing air into the reaction kettle by using 1-5 pipelines, keeping the ammonium concentration at 4g/L, the pH value at 12, the stirring speed at 400r/min and the reaction kettle temperature at 50 ℃ until the median diameter (D50) of the particles reaches a target value of 3.5 mu m, and aging the reaction liquid for 6 hours, wherein the distance from the bottom of the pipeline to the bottom of the reaction kettle is 20-70 cm, and the ratio of the air flow rate to the nitrogen flow rate is 1: 5;
(g) performing solid-liquid separation on the aged product to obtain a solid, washing the solid with 1mol/L alkali liquor, continuously washing with deionized water until the pH value of washing water is 7, and dehydrating to obtain a wet material; and drying the wet material at a high temperature of 130 ℃, and then screening the dried wet material by using a screen and a demagnetizing device to obtain the ternary precursor with high specific surface area and fine particles.
Example 2
The preparation method of the ternary precursor comprises the following steps:
(a) preparing a nickel-cobalt-manganese soluble mixed salt solution, wherein the sum of the concentrations of nickel ions, cobalt ions and manganese ions is 2mol/L, and the weight ratio of nickel: cobalt: the molar ratio of manganese is 5:2: 3; preparation of NH3·H2O solution with the concentration of 7 mol/L; preparing a sodium hydroxide solution with the concentration of 10 mol/L;
(b) introducing pure water, an ammonia water solution and an alkali liquor into a reaction kettle to prepare a reaction bottom liquid, wherein the pH of the reaction bottom liquid is 11.8, the ammonium radical concentration is 6g/L, and the addition amount of the reaction bottom liquid is 1/3 of the volume of the reaction kettle;
(c) heating the reaction kettle, starting stirring, introducing nitrogen, wherein the temperature of the reaction kettle is 50 ℃, the stirring speed is 400r/min, and the nitrogen introduction speed is 3m3H; then, introducing the prepared nickel-cobalt-manganese soluble mixed salt solution, ammonia water solution and sodium hydroxide solution by using a precise metering pump to perform coprecipitation reaction; in the coprecipitation reaction process, the ammonium concentration is kept at 6g/L, the pH value is kept at 11.8, the stirring speed is 400r/min, and the temperature of a reaction kettle is 50 ℃;
(d) continuously stirring, keeping the temperature of the reaction kettle stable, and continuously introducing mixed salt solution, ammonia water solution and alkali liquor; stopping stirring and closing nitrogen when the liquid level in the reaction kettle is over the baffle, standing for 3 hours, and then pumping out supernatant liquid by using a pneumatic pump, wherein the volume of the residual reaction liquid is 1/2 of the volume of the reaction kettle;
(e) continue at 3m2Introducing nitrogen at a speed of 1h for 1h, starting stirring for 30min, introducing a nickel-cobalt-manganese mixed salt solution, an ammonia water solution and a sodium hydroxide solution by using a precision metering pump, and keeping the temperature, the pH value and the ammonium concentration stable in the whole process;
(f) after the median diameter (D50) of the particles is 1.9 mu m, continuously introducing air into the reaction kettle by using 1-5 pipelines, wherein the distance between the bottom of each pipeline and the bottom of the reaction kettle is 20-70 cm, and the ratio of the flow rate of the air to the flow rate of the nitrogen is 1:2, keeping the ammonium concentration at 6g/L, the pH value at 11.8, stirring at the speed of 400r/min and the temperature of the reaction kettle at 30-75 ℃ until the median diameter (D50) of the particles reaches a target value of 3.5 mu m, and transferring the reaction solution into an aging kettle for aging for 6 hours;
(g) performing solid-liquid separation on the aged product to obtain a solid, washing the solid with 1.5mol/L alkali liquor, continuously washing with deionized water until the pH value of washing water is 7.5, and dehydrating to obtain a wet material; and drying the wet material at a high temperature of 130 ℃, and then screening the dried wet material by using a screen and a demagnetizing device to obtain the ternary precursor with high specific surface area and fine particles.
Example 3
The preparation method of the ternary precursor comprises the following steps:
(a) preparing a nickel-cobalt-manganese soluble mixed salt solution, wherein the sum of the concentrations of nickel ions, cobalt ions and manganese ions is 2mol/L, and the weight ratio of nickel: cobalt: the molar ratio of manganese is 60: 15: 25; preparation of NH3·H2O solution with the concentration of 7 mol/L; preparing a sodium hydroxide solution with the concentration of 10 mol/L;
(b) introducing pure water, an ammonia water solution and an alkali liquor into a reaction kettle to prepare a reaction bottom liquid, wherein the pH of the reaction bottom liquid is 11.9, the ammonium concentration is 5g/L, and the addition amount of the reaction bottom liquid is 1/3 of the volume of the reaction kettle;
(c) heating the reaction kettle, starting stirring, introducing nitrogen, wherein the temperature of the reaction kettle is 50 ℃, the stirring speed is 400r/min, and the nitrogen introduction speed is 4m3H; then, introducing the prepared nickel-cobalt-manganese soluble mixed salt solution, ammonia water solution and sodium hydroxide solution by using a precise metering pump to perform coprecipitation reaction; in the coprecipitation reaction process, the ammonium concentration is kept to be 5g/L, the pH value is kept to be 11.9, the stirring speed is 300r/min, and the temperature of a reaction kettle is 30-75 ℃;
(d) continuously stirring, keeping the temperature of the reaction kettle stable, and continuously introducing mixed salt solution, ammonia water solution and alkali liquor; stopping stirring and closing nitrogen when the liquid level in the reaction kettle is over the baffle, standing for 4 hours, and then pumping out supernatant liquid by using a pneumatic pump, wherein the volume of the residual reaction liquid is 1/2 of the volume of the reaction kettle;
(e) continue at 4m2Introducing nitrogen at a speed of 1h for 1h, starting stirring for 30min, introducing a nickel-cobalt-manganese mixed salt solution, an ammonia water solution and a sodium hydroxide solution by using a precision metering pump, and keeping the temperature, the pH value and the ammonium concentration stable in the whole process;
(f) after the median diameter (D50) of the particles is 1.9 mu m, continuously introducing air into the reaction kettle by using 1-5 pipelines, keeping the ammonium concentration at 5g/L, the pH value at 11.9, the stirring speed at 300r/min and the reaction kettle temperature at 50 ℃ until the median diameter (D50) of the particles reaches a target value of 3.5 mu m, keeping the ammonium concentration at 5g/L and the pH value at 1.5 by using the pipeline bottom which is 20-70 cm away from the bottom of the reaction kettle, and keeping the ratio of the air flow rate to the nitrogen flow rate at 1: 1;
(g) performing solid-liquid separation on the aged product to obtain a solid, washing the solid with 1mol/L alkali liquor, continuously washing with deionized water until the pH value of washing water is 7, and dehydrating to obtain a wet material; and drying the wet material at the high temperature of 120 ℃, and then screening the dried wet material by using a screen and a demagnetizing device to obtain the ternary precursor with high specific surface area and fine particles.
Comparative example 1
The preparation method of the ternary precursor comprises the following steps of (f) introducing air, and transferring the reaction liquid into an aging kettle for aging for 6 hours after the median diameter (D50) of the particles reaches a target value of 3.5 mu m; the other conditions were the same as in example 3.
Examples of the experiments
Specific surface areas of the ternary precursors obtained in examples and comparative examples are shown in table 1.
TABLE 1 specific surface area of ternary precursors
| Examples and comparative examples | Specific surface area (m) of ternary precursor2/g) |
| Example 1 | 18.9 |
| Example 2 | 17.6 |
| Example 3 | 21.3 |
| Comparative example 1 | 9.7 |
According to the preparation method of the ternary precursor, air is introduced after the D50 particle size of the ternary precursor particles grows to be 1.5-2.5 microns, and the introduction rate of the air and nitrogen is set to be a fixed ratio, so that the ternary precursor particles with higher specific surface area are obtained. In contrast, in comparative example 1, air was not introduced at a specific time point during the preparation process, and the specific surface area of the obtained ternary precursor particles was low.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and 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.
Claims (10)
1. A preparation method of a ternary precursor is characterized by comprising the following steps:
carrying out a first coprecipitation reaction on a mixture containing mixed metal salt, a precipitator, a complexing agent and a reaction base solution under the condition of nitrogen, continuously introducing nitrogen and air to carry out a second coprecipitation reaction after the D50 particle size of the obtained precipitate is 1.5-2.5 microns, and till the D50 particle size of the precipitate is 3.0-4.5 microns;
the mixed metal salt is soluble nickel salt, soluble cobalt salt and soluble manganese salt;
in the second coprecipitation reaction, the ratio of the flow rate of the air to the flow rate of the nitrogen is 0.1 to 2.0.
2. The method for preparing a ternary precursor according to claim 1, wherein the flow rates of the nitrogen gas in the first coprecipitation reaction and the second coprecipitation reaction are both 0.5-5 m3/h。
3. The method for preparing a ternary precursor according to claim 1, wherein the mixed metal salt, the precipitating agent and the complexing agent are respectively mixed with the reaction base solution in the form of solutions;
preferably, in the mixed metal salt solution, the sum of the concentrations of nickel ions, cobalt ions and manganese ions is 0.5-3.0 mol/L;
preferably, in the mixed metal salt, the molar ratio of nickel, cobalt and manganese is (1-92): (1-4): (1-4);
preferably, in the precipitant solution, the concentration of the precipitant is 5-10 mol/L;
preferably, the precipitating agent comprises sodium hydroxide;
preferably, in the complexing agent solution, the concentration of the complexing agent is 7-14 mol/L;
preferably, the complexing agent comprises NH3·H2O。
4. The method according to claim 1, wherein the reaction bottom liquid is mainly composed of water and NH3·H2O and alkali are prepared;
preferably, the pH of the reaction bottom liquid is 9-12;
preferably, the concentration of ammonium radicals in the reaction base solution is 2-8 g/L;
preferably, the addition amount of the reaction bottom liquid is 1/4-2/4 of the volume of the reaction container.
5. The preparation method of the ternary precursor according to claim 1, wherein in the first coprecipitation reaction and the second coprecipitation reaction, the temperature of the reaction system is 30-75 ℃;
preferably, in the first coprecipitation reaction and the second coprecipitation reaction, the pH of a reaction system is 9-12;
preferably, in the first coprecipitation reaction and the second coprecipitation reaction, the concentration of ammonium radicals in a reaction system is 2-8 g/L;
preferably, in the first coprecipitation reaction and the second coprecipitation reaction, the stirring speed of the reaction system is 100-400 r/min.
6. The method according to claim 1, wherein the first coprecipitation reaction comprises the following steps:
adding the mixed metal salt, the precipitator and the complexing agent into the reaction base solution under the condition of continuously introducing nitrogen for reaction, standing after the reaction, and removing part of the upper-layer reaction solution; and adding the mixed metal salt, the precipitator and the complexing agent into the residual reaction solution for reaction under the condition of continuously introducing nitrogen.
7. The preparation method of the ternary precursor according to claim 6, wherein the standing time is 1-6 h;
preferably, the time for continuously introducing nitrogen into the residual reaction liquid is 50-65 min;
preferably, the mixed metal salt, the precipitant and the complexing agent are added into the residual reaction solution to react under the condition of stirring, wherein the stirring time is 25-35 min;
preferably, the volume of the residual reaction liquid is 1/3-2/3 of the volume of the reaction container.
8. The method for preparing the ternary precursor according to any one of claims 1 to 7, wherein after the D50 particle size of the precipitate is 3.0 to 4.5 μm, the precipitate is aged and subjected to solid-liquid separation, and the solid after the solid-liquid separation is washed, dried, screened and demagnetized;
preferably, the aging time is 5-7 h;
preferably, the washing comprises: washing until the pH value of washing water is 7-7.5;
preferably, the drying temperature is 100-140 ℃.
9. The ternary precursor prepared by the method for preparing the ternary precursor according to any one of claims 1 to 8;
preferably, the specific surface area of the ternary precursor is 14-24 m2/g。
10. A lithium ion battery electrode material, characterized in that it is mainly prepared from the ternary precursor of claim 9.
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| CN115448382A (en) * | 2022-09-13 | 2022-12-09 | 广东邦普循环科技有限公司 | High-nickel ternary precursor and preparation method and application thereof |
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| CN114394630A (en) * | 2021-12-31 | 2022-04-26 | 宜宾光原锂电材料有限公司 | Preparation method for controlling morphology of ternary precursor material |
| CN115072804A (en) * | 2022-07-08 | 2022-09-20 | 金驰能源材料有限公司 | Method for regulating and controlling XRD diffraction intensity ratio of crystal faces of precursor (101) and precursor (001) |
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| CN115849463A (en) * | 2022-12-19 | 2023-03-28 | 广东佳纳能源科技有限公司 | High-nickel ternary precursor and preparation method thereof |
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