CN116199274A - Porous hollow ternary precursor and preparation method thereof - Google Patents
Porous hollow ternary precursor and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of lithium ion battery anode materials, in particular to a porous hollow ternary precursor and a preparation method thereof. The method comprises the following steps: 1) Introducing the nickel-cobalt-manganese ternary mixed solution, inorganic aluminum alkali solution, complexing agent and precipitant into a reaction kettle for codeposition to prepare a nickel-cobalt-manganese-aluminum quaternary core structure; 2) Stopping introducing inorganic aluminum alkali solution after the particle size of the inner core reaches the target particle size, and continuing codeposition to prepare a nickel-cobalt-manganese ternary shell structure; 3) And after the integral particle size reaches the target particle size, placing the reacted material into a strong alkali solution for stirring to dissolve out aluminum hydroxide in the inner core to form a porous hollow structure, and washing, separating and drying to obtain the porous hollow ternary precursor. The method can accurately control the growth size of the inner core through the reaction time, thereby accurately controlling the size of the finished porous hollow structure, and the prepared precursor has excellent multiplying power performance and cycle stability, does not need to add extra equipment, is simple and convenient to operate, and is suitable for industrial industrialization.
Description
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to a porous hollow ternary precursor prepared by a dissolution method and a preparation method thereof.
Background
The current industrialization of the lithium ion battery anode materials mainly comprises lithium manganate, lithium cobaltate, lithium iron phosphate and ternary anode materials. The ternary positive electrode material has the advantages of high energy density, long cycle life, safety, environmental protection and the like, and is widely applied to the fields of power, digital codes, energy storage and the like. The ternary positive electrode material is formed by mixing and sintering a ternary precursor (nickel cobalt manganese hydroxide/nickel cobalt aluminum hydroxide) and lithium salt (lithium hydroxide/lithium carbonate), the performance of the ternary precursor is little influenced in the sintering process, and the morphology, the particle size and the like of the ternary positive electrode material have inheritance to the ternary precursor, so that the 70% performance of the ternary positive electrode material is determined by the advantages and disadvantages of the ternary precursor.
How to ensure the specific capacity of the ternary positive electrode material and simultaneously have excellent multiplying power performance and cycle stability is a research hot spot of the ternary positive electrode material. In particular, along with the rapid development of the rapid charging technology, higher requirements are put on the structural stability of the ternary positive electrode material, and the volume change of the ternary positive electrode material produced under long-time large-current cyclic charge and discharge and side reaction generated between the ternary positive electrode material and electrolyte can cause the damage of the material structure, so that the cyclic capacity of the ternary positive electrode material is rapidly attenuated. If a loose porous hollow structure is formed in the ternary positive electrode material, the structural damage caused by the volume change and side reaction of the material can be effectively relieved, meanwhile, the hollow internal structure can shorten the lithium ion transmission path of the ternary positive electrode material in the process of charging and discharging, accelerate the ion migration rate and simultaneously effectively reduce the electrochemical polarization. Thus, it is highly desirable to prepare a ternary precursor having a porous hollow structure.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a porous hollow ternary precursor and a preparation method thereof. In the preparation process of the ternary precursor, a porous hollow structure is formed in the ternary precursor by adopting a dissolution method, so that the microstructure stability of the material is enhanced, and the electrochemical performance of the material is improved. The invention aims at providing a porous hollow ternary precursor. The invention provides a preparation method of a porous hollow ternary precursor.
The invention adopts the technical proposal for solving the problems that:
the invention provides a preparation method of a porous hollow ternary precursor, which comprises the following steps:
(1) Preparing ternary mixed metal salt solution by adopting nickel, cobalt and manganese inorganic salts; preparing an inorganic aluminum alkali solution; preparing a precipitant aqueous solution; preparing a complexing agent aqueous solution;
(2) Filling pure water into the reaction kettle and the concentrator, circulating, introducing protective gas, introducing complexing agent aqueous solution and precipitant aqueous solution to regulate the concentration of the complexing agent and the first pH value, and controlling the reaction temperature;
simultaneously introducing a ternary mixed metal salt solution, an inorganic aluminum alkali solution, a complexing agent aqueous solution and a precipitator aqueous solution into a reaction kettle under the condition of a first stirring rotating speed, and controlling the reaction pH to be regulated to a second pH in a stepwise manner;
stopping introducing inorganic aluminum alkali solution after the particle size of the reactant reaches the target particle size of the inner core, regulating the reaction pH to a third pH, regulating the rotating speed to a second stirring rotating speed, continuing codeposition to prepare a nickel-cobalt-manganese ternary shell structure, and stopping the reaction after the integral particle size reaches the target particle size;
(3) Standing the reacted material, removing supernatant, adding a strong alkali solution, and stirring to dissolve out aluminum hydroxide in the inner core to form a porous hollow structure; and (5) post-treating to obtain the porous hollow ternary precursor.
Preferably, the nickel, cobalt and manganese inorganic salt in the step (1) is one or more of corresponding sulfate, nitrate and chloride salts; more preferably, the nickel inorganic salt is one or more of nickel sulfate, nickel nitrate and nickel chloride, the cobalt inorganic salt is one or more of cobalt sulfate, cobalt nitrate and cobalt chloride, and the manganese inorganic salt is one or more of manganese sulfate, manganese nitrate and manganese chloride.
Preferably, the total concentration of the metals (nickel cobalt manganese) in the ternary mixed metal salt solution in the step (1) is 80-120 g/L.
Preferably, the proportion of nickel, cobalt and manganese in the ternary mixed metal salt solution in the step (1) accords with Ni x Co y Mn (1-x-y) (OH) 2 Wherein 0 is<x<1，0<y<1。
Preferably, the inorganic aluminum in the inorganic aluminum alkali solution in the step (1) is one or more of sodium metaaluminate and aluminum sulfate; more preferably, the concentration of aluminum in the inorganic aluminum alkali solution in the step (1) is 20-80 g/L, the alkali is sodium hydroxide, and the pH value is 13.00-13.50.
Preferably, the precipitant in the step (1) is one or more of sodium hydroxide and potassium hydroxide. More preferably, the concentration of the aqueous solution of the precipitant in the step (1) is 120 to 440g/L.
Preferably, the complexing agent in the step (1) is one or more of ammonia water and ethylenediamine tetraacetic acid. More preferably, the concentration of the complexing agent aqueous solution in the step (1) is 85-200 g/L.
Preferably, the volume of the reaction kettle in the step (2) is 1-10 m 3 The method comprises the steps of carrying out a first treatment on the surface of the More preferably, the volume of the thickener in the step (2) is 0.1-3 m 3 。
Preferably, the protective gas in the step (2) is one or more of nitrogen or helium.
Preferably, the reaction temperature in the step (2) is 50-70 ℃;
preferably, the concentration of the reaction complexing agent in the step (2) is 2.0-6.5 g/L;
preferably, the first pH of the reaction in the step (2) is 11.80-12.10;
preferably, the first stirring rotation speed in the step (2) is 200-260 rpm;
preferably, the pumping flow rate of the ternary mixed metal salt solution in the step (2) is 30-600L/h;
preferably, the pumping flow rate of the inorganic aluminum alkali solution in the step (2) is 15-400L/h;
preferably, the second pH in the step (2) is 10.50-11.00;
preferably, the step (2) is to reduce the pH by 0.02 per hour;
preferably, the core target particle size in the step (2) is 2.0-5.0 μm;
preferably, the third pH in the step (2) is 10.80-11.20;
preferably, the second stirring rotation speed in the step (2) is 110-160 rpm;
preferably, the overall particle diameter in the step (2) reaches a target particle diameter of 3.0 to 15.0 μm and is not smaller than the target particle diameter of the core.
Preferably, the standing time in the step (3) is 2-4 hours.
Preferably, the strong base added in the step (3) is at least one of sodium hydroxide and potassium hydroxide; more preferably, the mass concentration of the strong alkali sodium hydroxide solution is 32%, and the adding volume is 0.5-5 m 3 The method comprises the steps of carrying out a first treatment on the surface of the More preferably, the stirring time in the step (3) is 10 to 24 hours.
Preferably, the post-treatment comprises the steps of washing and centrifuging the dissolved material, drying, mixing, screening and removing iron to obtain a porous hollow ternary precursor;
more preferably, the water washing temperature is 60-85 ℃;
more preferably, the drying temperature is 100 to 150 ℃.
Preferably, the size of the porous hollow structure in the ternary precursor body obtained by the preparation method is 2-5 nm; more preferably, the particle size of the ternary precursor bulk particle is 3.0-15.0 μm and the particle size distribution is 0.3-0.8; more preferably, the tap density of the ternary precursor is 1.0-2.1 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the More preferably, the ternary precursor BET is 5 to 15m 2 /g。
The invention also provides a porous hollow ternary precursor prepared by any one of the preparation methods, wherein the size of the porous hollow structure in the precursor is 2-5 nm, the particle size is 3.0-15.0 mu m, the particle size distribution is 0.3-0.8, and the tap density is 1.0-2.1 g/cm 3 BET of 5 to 15m 2 /g。
The preparation method comprises the steps of introducing a nickel-cobalt-manganese ternary mixed solution, an inorganic aluminum alkali solution, a complexing agent and a precipitant into a reaction kettle for codeposition to prepare a nickel-cobalt-manganese-aluminum quaternary core structure, stopping introducing the inorganic aluminum alkali solution for codeposition to prepare a nickel-cobalt-manganese ternary shell structure after the core particle size reaches a target particle size, then placing reacted materials into a strong alkali solution for stirring after the whole particle size reaches the target particle size to enable aluminum hydroxide in the core to dissolve out to form a porous hollow structure, and washing, separating and drying to obtain the porous hollow ternary precursor. According to the invention, the porosity of the internal porous hollow structure can be precisely controlled by adjusting the content of the aluminum in the inner core, and the prepared precursor has excellent rate capability and cycle stability.
Compared with the prior art, the invention has the following beneficial effects:
according to the technical scheme, the cobalt nickel manganese aluminum core is prepared by utilizing the characteristic of aluminum amphoteric metal and adopting deviated acid radicals or aluminum ions as an aluminum source through a codeposition reaction and nickel cobalt manganese metal ions under the weak alkaline condition, aluminum hydroxide is uniformly distributed in the core, and meanwhile, the grain size of the core can be accurately controlled. And stopping introducing the aluminum source after the required size is reached, and performing codeposition to prepare the cobalt nickel hydroxide manganese ternary shell structure. After the codeposition is finished, the prepared particles are stirred in a strong alkaline environment to dissolve and remove aluminum hydroxide in the inner core, and a porous hollow structure is formed inside the particles;
according to the technical scheme, the growth size of the inner core can be precisely controlled through the reaction time, so that the size of the finished porous hollow structure can be precisely controlled. The ratio of the inner core aluminum hydroxide is precisely controlled through the pumping rate of the aluminum source, so that the porosity of the finished porous hollow structure is precisely controlled.
Compared with the existing conventional ternary precursor preparation technology, the porous hollow ternary precursor prepared by the technical scheme of the invention can realize industrialization without adding extra equipment, and has wide industrial application prospect.
Drawings
FIGS. 1-1 and 1-2 are scanning electron microscope images of porous hollow ternary precursor prepared by the dissolution method of example 1;
FIGS. 2-1 and 2-2 are scanning electron microscope images of porous hollow ternary precursor prepared by the dissolution method of example 2;
FIG. 3-1 and FIG. 3-2 are scanning electron microscope images of porous hollow ternary precursors prepared by the dissolution method of example 3;
FIGS. 4-1 and 4-2 are scanning electron microscope images of porous hollow ternary precursors prepared by the dissolution method of comparative example 1.
Detailed Description
The technical scheme of the invention is further specifically described below through specific embodiments and with reference to the accompanying drawings. It should be understood that the following embodiments are only some embodiments, but not all embodiments, of the present invention, and it should be noted that those skilled in the art may make insubstantial changes to all embodiments without departing from the spirit of the invention, and still fall within the scope of the invention.
The invention provides a porous hollow ternary precursor prepared by a dissolution method and a preparation method thereof, wherein the preparation method comprises the following steps:
the nickel, cobalt and manganese inorganic salt is adopted to prepare the Ni-cobalt-manganese alloy according to the nickel-cobalt-manganese ratio Ni x Co y Mn (1-x-y) (OH) 2 Preparing a ternary metal mixed solution with the total concentration of metal salt of 80-120 g/L; preparing an inorganic aluminum salt with the aluminum concentration of 20-80 g/L, and regulating the pH value of the solution to 13.00-13.50 by using sodium hydroxide to obtain an inorganic aluminum alkali solution; preparing a precipitant aqueous solution with the concentration of 120-440 g/L; preparing complexing agent aqueous solution with the concentration of 85-200 g/L;
the volume is 1-10 m 3 Reaction kettle and volume of 0.1-3 m 3 The concentration machine is filled with pure water and circulated, protective gas is introduced, complexing agent aqueous solution and precipitant aqueous solution are introduced to prepare the concentration of the complexing agent in the system to be 2.0-6.5 g/L and the first pH to be 11.80-12.10, and the reaction temperature is controlled to be 50-70 ℃; pumping the ternary mixed solution of nickel, cobalt and manganese into a reaction kettle at the first stirring speed of 200-260 rpm at the flow rate of 30-600L/h, pumping the inorganic aluminum alkali solution into the reaction kettle at the flow rate of 15-400L/h, simultaneously pumping the aqueous solution of the complexing agent and the aqueous solution of the precipitant into the reaction kettle, controlling the reaction pH to be reduced by 0.02 step per hour to adjust the second pH to 10.50-11.00, stopping pumping the inorganic aluminum alkali solution after the particle size of the reactant reaches the target particle size of 2.0-5.0 mu m,and regulating the reaction pH to be 10.80-11.20, regulating the rotating speed to be 110-160 rpm for continuous codeposition to prepare the nickel-cobalt-manganese ternary shell structure, and stopping the reaction after the integral particle size reaches the target particle size of 3.0-15.0 mu m.
Discharging the reacted material into an ageing kettle, standing for 2-4 h, removing supernatant, and adding sodium hydroxide solution with the concentration of 32% to 0.5-5 m 3 Stirring for 10-24 h to dissolve out the aluminum hydroxide in the inner core to form a porous hollow structure;
washing and centrifuging the dissolved material at 60-85 ℃, drying at 100-150 ℃, mixing, sieving and removing iron to obtain a porous hollow ternary precursor, wherein the size of the porous hollow structure in the precursor is 2-5 nm, the particle size is 3.0-15.0 mu m, the particle size distribution is 0.3-0.8, and the tap density is 1.0-2.1 g/cm 3 BET of 5 to 15m 2 /g。
Example 1
The nickel, cobalt and manganese inorganic salt is adopted to prepare the Ni-cobalt-manganese alloy according to the nickel-cobalt-manganese ratio Ni 0.90 Co 0.05 Mn 0.05 (OH) 2 Preparing a ternary metal mixed solution with the total concentration of metal salt of 90 g/L; preparing sodium hydroxide solution with aluminum concentration of 50g/L and pH value of 13.20 by adopting sodium metaaluminate; preparing a sodium hydroxide aqueous solution with the concentration of 400 g/L; preparing an ammonia water solution with the concentration of 95 g/L;
the volume is 2m 3 Reaction kettle and volume of 0.5m 3 The concentration machine is filled with pure water and circulated, nitrogen is introduced, complexing agent aqueous solution and precipitant aqueous solution are introduced to prepare complexing agent concentration of 4.0g/L and first pH value of 11.90, and the reaction temperature is controlled to be 60 ℃; pumping the nickel-cobalt-manganese ternary mixed solution into a reaction kettle at a first stirring speed of 200rpm at a flow rate of 50L/h, pumping sodium metaaluminate alkali solution into a flow rate of 30L/h, simultaneously pumping a complexing agent aqueous solution and a precipitant aqueous solution into the reaction kettle, controlling the reaction pH to be reduced by 0.02 step per hour to adjust the second pH to 11.00, stopping pumping the sodium metaaluminate solution after the particle size of the reactant reaches the core target particle size of 4.0 mu m, adjusting the reaction pH to 10.90, adjusting the rotation speed to the second stirring speed of 120rpm, and continuously co-depositing to prepare the nickel-cobalt-manganese ternary shell structure, wherein the whole particle size reaches the core target particle sizeThe reaction was stopped after the target particle diameter was 10.5. Mu.m.
Discharging the reacted material into an aging kettle, standing for 2h, removing supernatant, adding sodium hydroxide solution with concentration of 32 m and concentration of 2m 3 Stirring for 20h to dissolve out the aluminum hydroxide in the inner core to form a porous hollow structure;
washing and centrifuging the dissolved material with water at 70 ℃, drying at 120 ℃, mixing, sieving and removing iron to obtain the porous hollow ternary precursor.
The ternary precursor material prepared in the embodiment 1 of the invention is subjected to scanning electron microscope test, and the test results are shown in fig. 1-1 and fig. 1-2, so that the ternary precursor material prepared in the embodiment 1 of the invention has a porous hollow structure with the center of 4.0 micrometers.
The porous hollow ternary precursor D50 prepared in example 1 of the present invention was 10.42. Mu.m.
The porous hollow ternary precursor prepared in example 1 of the present invention had a particle size distribution of 0.38.
The tap density of the porous hollow ternary precursor prepared in the embodiment 1 of the invention is 1.82g/cm 3 。
The porous hollow ternary precursor prepared in example 1 of the present invention has BET of 8.33m 2 /g。
Example 2
The nickel, cobalt and manganese inorganic salt is adopted to prepare the Ni-cobalt-manganese alloy according to the nickel-cobalt-manganese ratio Ni 0.88 Co 0.08 Mn0.04(OH) 2 Preparing a ternary metal mixed solution with the total concentration of metal salt of 120 g/L; preparing sodium hydroxide solution with aluminum concentration of 40g/L and pH value of 13.20 by adopting sodium metaaluminate; preparing a sodium hydroxide aqueous solution with the concentration of 200 g/L; preparing an ammonia water solution with the concentration of 95 g/L;
the volume is 2m 3 Reaction kettle and volume of 0.5m 3 The concentration machine is filled with pure water and circulated, nitrogen is introduced, complexing agent aqueous solution and precipitant aqueous solution are introduced to prepare complexing agent concentration of 3.0g/L and first pH value of 12.00, and reaction temperature is controlled to 65 ℃; pumping the ternary mixed solution of nickel, cobalt and manganese into the solution tank at a first stirring speed of 260rpm at a flow rate of 50L/h, pumping sodium metaaluminate alkali solution into the solution tank at a flow rate of 20L/h, and mixing the aqueous solution of complexing agent and the aqueous solution of precipitant with the solution of complexing agentAnd then the reaction kettle is introduced, the reaction pH is controlled to be reduced by 0.02 step-type per hour to adjust the second pH to 10.90, the introduction of the sodium metaaluminate solution is stopped after the particle size of the reactant reaches the target particle size of the inner core to be 2.0 mu m, the reaction pH is adjusted to be 10.80, the rotation speed is adjusted to be 130rpm for the second rotation stirring speed, the co-deposition is continued to prepare the nickel-cobalt-manganese ternary shell structure, and the reaction is stopped after the integral particle size reaches the target particle size of 10.0 mu m.
Discharging the reacted material into an aging kettle, standing for 2h, removing supernatant, adding sodium hydroxide solution with concentration of 32 m and concentration of 2m 3 Stirring for 20h to dissolve out the aluminum hydroxide in the inner core to form a porous hollow structure;
washing and centrifuging the dissolved material with water at 70 ℃, drying at 120 ℃, mixing, sieving and removing iron to obtain the porous hollow ternary precursor.
The ternary precursor material prepared in the embodiment 2 of the invention is subjected to scanning electron microscope test, and the test results are shown in fig. 2-1 and fig. 2-2, so that the ternary precursor material prepared in the embodiment 2 of the invention has a porous hollow structure with the center of 2.0 micrometers.
The porous hollow ternary precursor D50 prepared in example 2 of the present invention was 9.98. Mu.m.
The porous hollow ternary precursor prepared in example 2 of the present invention had a particle size distribution of 0.38.
The tap density of the porous hollow ternary precursor particles prepared in the embodiment 2 of the invention is 1.95g/cm 3 。
The porous hollow ternary precursor particles prepared in example 2 of the present invention had BET of 6.49m 2 /g。
Example 3
The nickel, cobalt and manganese inorganic salt is adopted to prepare the Ni-cobalt-manganese alloy according to the nickel-cobalt-manganese ratio Ni 0.65 Co 0.15 Mn 0.20 (OH) 2 Preparing a ternary metal mixed solution with the total concentration of metal salt of 90 g/L; preparing sodium hydroxide solution with aluminum concentration of 50g/L and pH value of 13.20 by adopting sodium metaaluminate; preparing a sodium hydroxide aqueous solution with the concentration of 200 g/L; preparing an ammonia water solution with the concentration of 170 g/L;
the volume is 8m 3 Reaction kettle and volume of 2m 3 The concentration machine is filled with pure water and circulatedCirculating, introducing nitrogen, introducing complexing agent aqueous solution and precipitant aqueous solution to prepare complexing agent concentration of 4.5g/L and first pH of 12.30, and controlling reaction temperature to 60 ℃; pumping the nickel-cobalt-manganese ternary mixed solution into a reaction kettle at the conditions of a first stirring rotating speed of 240rpm, pumping the sodium metaaluminate alkali solution into the reaction kettle at the flow rate of 600L/h, pumping the sodium metaaluminate alkali solution into the reaction kettle at the flow rate of 200L/h, controlling the reaction pH to be reduced by 0.02 step per hour to a second pH of 11.00, stopping pumping the sodium metaaluminate solution after the particle size of the reactant reaches the target particle size of 2.0 mu m, regulating the reaction pH to a third pH of 10.70, regulating the rotating speed to the second stirring rotating speed of 160rpm, continuing codeposition to prepare the nickel-cobalt-manganese ternary shell structure, and stopping the reaction after the whole particle size reaches the target particle size of 3.5 mu m.
Discharging the reacted material into an aging kettle, standing for 4 hours, removing supernatant, adding sodium hydroxide solution with the concentration of 32% and 5m 3 Stirring for 15h to dissolve out the aluminum hydroxide in the inner core to form a porous hollow structure;
washing and centrifuging the dissolved material with water at 70 ℃, drying at 120 ℃, mixing, sieving and removing iron to obtain the porous hollow ternary precursor.
The ternary precursor material prepared in the embodiment 3 of the invention is subjected to scanning electron microscope test, and the test results are shown in fig. 3-1 and 3-2, so that the ternary precursor material prepared in the embodiment 3 of the invention has a porous hollow structure with the center of 2.0 micrometers.
The porous hollow ternary precursor D50 prepared in example 3 of the invention is 3.48 μm;
the porous hollow ternary precursor prepared in example 3 of the invention has a particle size distribution of 0.69 μm
The tap density of the porous hollow ternary precursor prepared in the embodiment 3 of the invention is 1.76g/cm 3 。
The porous hollow ternary precursor prepared in example 3 of the present invention has a BET of 9.86m 2 /g。
Comparative example 1
The nickel, cobalt and manganese inorganic salt is adopted to prepare the Ni-cobalt-manganese alloy according to the nickel-cobalt-manganese ratio Ni 0.84 Co 0.12 Mn 0.04 (OH) 2 Preparing total concentration of metal saltThe density of the ternary metal mixed solution is 90 g/L; preparing sodium hydroxide solution with the concentration of 200 g/L; preparing an ammonia water solution with the concentration of 170 g/L;
the volume is 8m 3 Reaction kettle and volume of 2m 3 The concentration machine is filled with pure water and circulated, nitrogen is introduced, complexing agent aqueous solution and precipitant aqueous solution are introduced to prepare complexing agent concentration of 4.5g/L and first pH value of 12.20, and the reaction temperature is controlled to be 65 ℃; pumping the nickel-cobalt-manganese ternary mixed solution into a reaction kettle at the first stirring rotating speed of 240rpm, simultaneously introducing the complexing agent aqueous solution and the precipitator aqueous solution into the reaction kettle, controlling the reaction pH to be reduced by 0.02 step per hour, adjusting the pH to be the second pH to be 10.85, and stopping the reaction after the particle size reaches the target particle size of 3.8 mu m.
Discharging the reacted material into an aging kettle, standing for 4 hours, removing supernatant, adding sodium hydroxide solution with the concentration of 32% and 0.5m 3 And stirring for 2h;
washing and centrifuging the materials at 70 ℃, drying at 120 ℃, mixing, sieving and removing iron to obtain the porous hollow ternary precursor.
The ternary precursor material prepared in comparative example 3 is subjected to scanning electron microscope test, and the test results are shown in fig. 4-1 and fig. 4-2, so that the ternary precursor material prepared in comparative example 1 has no porous hollow structure in the center.
The porous hollow ternary precursor D50 prepared in comparative example 1 of the present invention is 3.74 μm;
the particle size distribution of the porous hollow ternary precursor prepared in comparative example 1 of the invention is 0.70 mu m
The tap density of the porous hollow ternary precursor prepared in comparative example 1 of the invention is 1.79g/cm 3 。
The porous hollow ternary precursor prepared in comparative example 1 of the present invention has BET of 6.81m 2 /g。
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the invention in any way, but other variations and modifications are possible without exceeding the technical solutions described in the claims.
Claims (10)
1. The preparation method of the porous hollow ternary precursor is characterized by comprising the following steps of:
(1) Preparing ternary mixed metal salt solution by adopting nickel, cobalt and manganese inorganic salts; preparing an inorganic aluminum alkali solution; preparing a precipitant aqueous solution; preparing a complexing agent aqueous solution;
(2) Filling pure water into the reaction kettle and the concentrator, circulating, introducing protective gas, introducing complexing agent aqueous solution and precipitant aqueous solution, regulating the concentration of the complexing agent and the first pH value, and controlling the reaction temperature;
simultaneously introducing a ternary mixed metal salt solution, an inorganic aluminum alkali solution, a complexing agent aqueous solution and a precipitator aqueous solution into a reaction kettle under the condition of a first stirring rotating speed, and controlling the reaction pH to be regulated to a second pH in a stepwise manner;
stopping introducing inorganic aluminum alkali solution after the particle size of the reactant reaches the target particle size of the inner core, regulating the reaction pH to a third pH, regulating the rotating speed to a second stirring rotating speed, continuing codeposition to prepare a nickel-cobalt-manganese ternary shell structure, and stopping the reaction after the integral particle size reaches the target particle size;
(3) Standing the reacted material, removing supernatant, adding strong alkali solution, and stirring to form a porous hollow structure; and (5) post-treating to obtain the porous hollow ternary precursor.
2. The preparation method of the porous hollow ternary precursor according to claim 1, wherein in the step (1), inorganic salts of nickel, cobalt and manganese are one or more of corresponding sulfate, nitrate and chloride, the total concentration of metals in ternary mixed metal salt solution is 80-120 g/L, and the proportion of nickel, cobalt and manganese accords with a formula Ni x Co y Mn (1-x-y) (OH) 2 Wherein 0 is<x<1，0<y<1。
3. The preparation method of the porous hollow ternary precursor according to claim 1, wherein the inorganic aluminum in the inorganic aluminum alkali solution in the step (1) is one or more of sodium metaaluminate and aluminum sulfate; the concentration of aluminum in the inorganic aluminum alkali solution is 20-80 g/L, and the pH value is 13.00-13.50.
4. The preparation method of the porous hollow ternary precursor according to claim 1, wherein the precipitant in the step (1) is one or more of sodium hydroxide and potassium hydroxide, and the concentration is 120-440 g/L.
5. The preparation method of the porous hollow ternary precursor according to claim 1, wherein the complexing agent in the step (1) is one or more of ammonia water and ethylenediamine tetraacetic acid, and the concentration is 85-200 g/L.
6. The method for preparing a porous hollow ternary precursor according to claim 1, wherein the reaction temperature in the step (2) is 50-70 ℃; the concentration of the reaction complexing agent is 2.0-6.5 g/L; the first pH of the reaction is 11.80-12.10.
7. The method for preparing a porous hollow ternary precursor according to claim 1, wherein the first stirring speed in the step (2) is 200-260 rpm; the pumping flow of the ternary mixed metal salt solution is 30-600L/h; the pumping flow rate of the inorganic aluminum alkali solution is 15-400L/h; the second pH is 10.50-11.00; the step-wise decrease was 0.02pH per hour.
8. The method for preparing a porous hollow ternary precursor according to claim 1, wherein the core target particle size in the step (2) is 2.0-5.0 μm; the third pH is 10.80-11.20; the second stirring rotation speed is 110-160 rpm; the overall grain diameter reaches the target grain diameter of 3.0-15.0 mu m.
9. The method for preparing a porous hollow ternary precursor according to claim 1, wherein the strong base added in the step (3) is at least one of sodium hydroxide and potassium hydroxide, and the stirring time is 10-24 hours.
10. A porous hollow ternary precursor prepared by the method of any one of claims 1-9.
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| CN117509756A (en) * | 2023-11-20 | 2024-02-06 | 金驰能源材料有限公司 | Nickel-rich aluminum-doped nickel-cobalt-manganese ternary precursor and preparation method thereof |
| CN117964003A (en) * | 2024-03-28 | 2024-05-03 | 四川新能源汽车创新中心有限公司 | High-nickel ternary precursor material, positive electrode material, preparation method and application |
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| CN117509756A (en) * | 2023-11-20 | 2024-02-06 | 金驰能源材料有限公司 | Nickel-rich aluminum-doped nickel-cobalt-manganese ternary precursor and preparation method thereof |
| CN117964003A (en) * | 2024-03-28 | 2024-05-03 | 四川新能源汽车创新中心有限公司 | High-nickel ternary precursor material, positive electrode material, preparation method and application |
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