CN115180659A - Nickel-cobalt-manganese precursor based on shell-core structure, positive electrode material and preparation method of nickel-cobalt-manganese precursor - Google Patents
Nickel-cobalt-manganese precursor based on shell-core structure, positive electrode material and preparation method of nickel-cobalt-manganese precursor Download PDFInfo
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Abstract
The invention provides a nickel-cobalt-manganese precursor based on a shell-core structure, a positive electrode material and a preparation method thereof, wherein the nickel-cobalt-manganese precursor comprises a core and a shell from inside to outside, the outermost part of the nickel-cobalt-manganese precursor also comprises a coating layer, the core is in a compact net shape, and the shell is in a loose radial shape; wherein, the inner core and the shell layer are nickel-cobalt-manganese hydroxide, and the coating layer is nickel-cobalt-manganese hydroxide containing doping elements. The nickel-cobalt-manganese hydroxide is designed into a shell-core structure with a compact core and a loose shell, the shell is doped and coated, the compact part of the core can improve the structural stability of particles, the loose layer of the shell part is favorable for ion diffusion, lithium ions are embedded and de-embedded, and the coating is favorable for reducing charge transfer impedance and improving thermal stability.
Description
Technical Field
The invention belongs to the field of lithium ion battery materials, and particularly relates to a nickel-cobalt-manganese precursor based on a shell-core structure, a positive electrode material and a preparation method of the nickel-cobalt-manganese precursor.
Background
In the lithium ion electrode material, the core-shell structure of the precursor particles has a great influence on the application effect of the material, and researches show that the core-shell structure can increase the specific surface area and increase the reaction sites, so that the ion transmission rate is accelerated, the shell layer can make up for the short plate with low conductivity of the transition metal oxide, and meanwhile, the shell layer has few side reactions with the electrolyte, plays a role of a protective layer and can effectively improve the structural stability of the electrode material.
The shell-core structure has stability, and generally cannot give consideration to other performances, on the basis of the unique characteristics of the shell-core structure, how to further improve other performances of the precursor and maximally retain the original performances of the shell-core structure is provided, and the prior art proposes a doping mode for modification. The current doping is mainly based on gradient change from an inner core to a shell layer, and the precursor is doped by mostly adopting elements such as Mg, al, zr, ti, W, F and the like, but the whole internal porosity of precursor particles can be changed by the doping in the way, so that the original stability of the shell-core structure is reduced, and the application of the shell-core structure is not suitable.
Disclosure of Invention
Aiming at the technical problems, the invention provides a nickel-cobalt-manganese precursor based on a shell-core structure, which is more suitable for preparing an electrode material, and provides a preparation method of the nickel-cobalt-manganese precursor based on the same technical concept.
The invention is realized by the following technical scheme:
the first aspect of the invention provides a nickel-cobalt-manganese precursor based on a shell-core structure, the nickel-cobalt-manganese precursor comprises a core and a shell from inside to outside, the outermost part of the nickel-cobalt-manganese precursor also comprises a coating layer, the core is in a compact net shape, and the shell is in a loose radial shape; wherein, the inner core and the shell layer are nickel-cobalt-manganese hydroxide, and the coating layer is nickel-cobalt-manganese hydroxide containing doping elements.
The shell-core structure is compact, the shell layer is loose, the compact part of the core is beneficial to improving the structural stability of the particles, the loose layer of the shell layer part is beneficial to ion diffusion and the insertion and extraction of lithium ions, so that the rate capability of the final electrode material is improved. The nickel-cobalt-manganese hydroxide with the shell-core structure is doped and coated to form a coating layer, so that for the performance defect of the electrode material prepared from the nickel-cobalt-manganese hydroxide, the doping elements are selected from transition metals, compounds thereof and other elements with excellent physical and chemical properties, the problems of poor cycle performance and low thermal stability of the electrode material prepared from the nickel-cobalt-manganese precursor can be solved, and the cycle performance and the thermal stability of the electrode material of the lithium battery can be improved.
According to the nickel-cobalt-manganese precursor based on the shell-core structure, the chemical formula of the nickel-cobalt-manganese precursor is as follows:
t[Ni x1 Co y1 Mn (1-x1-y1) (OH) 2 ]·(1-t)[Ni x2 Co y2 Mn (1-x2-y2-z) A z (OH) 2 ]；
the chemical formula of the core and the shell is Ni x1 Co y1 Mn (1-x1-y1) (OH) 2 The chemical formula of the coating layer is Ni x2 Co y2 Mn (1-x2-y2-z) A z (OH) 2 ；
Wherein x1 is more than or equal to 0.5 and less than 1,0 and less than or equal to y1 and less than or equal to 0.5,0.5 and more than x2 and less than or equal to 1,0 and more than y2 and less than or equal to 0.4,0 and more than or equal to z 0.1,0 and less than t 1, and 1-x1-y1 is more than 0,1-x2-y2-z is more than 0,A as doping elements. According to the nickel-cobalt-manganese precursor based on the shell-core structure, the doping element A is at least one or a compound of Ti, mg, zn, cu, al, ga, in, F, la, cr, si, sn and W.
According to the nickel-cobalt-manganese precursor based on the shell-core structure, the doping element A is a W element.
Because the tungsten base and the alloy thereof have good mechanical and thermal properties, such as high melting point, high thermal conductivity, high hardness, small thermal expansion coefficient, good high-temperature strength, good ductility, good impact toughness and good ray absorption capacity, the cycle performance and the thermal stability of the electrode material of the lithium battery can be improved by partially wrapping the tungsten base. The nickel-cobalt-manganese precursor inner core is designed to be dense net-shaped, the shell layer is designed to be loose and radial, the W element is coated on the surface of the shell layer to form a tungsten coating layer, the structural stability of particles can be improved due to the arrangement of the shell-core structure, the doping element is coated on the surface or interface of the material, the structural stability and safety of the material are further improved, and the W element can be separated out on the surface of a composite crystal grain, so that the shell surface thermal resistance is reduced, the shell-core combination is strengthened, the performances of the material, such as density, wear resistance, high-temperature strength and the like, are further improved, and the cycle performance of the electrode material is improved.
According to the nickel-cobalt-manganese precursor based on the shell-core structure, the doping elements account for 0.01-3% of the total mass of the nickel-cobalt-manganese precursor coating layer, and preferably account for 1.2%.
According to the nickel-cobalt-manganese precursor based on the shell-core structure, the porosity of the core of the nickel-cobalt-manganese precursor is 2% -5%, and the porosity of the shell is 10% -15%, and the chemical performance of the precursor can be improved by setting the density of the core and the density of the shell to be different.
According to the nickel-cobalt-manganese precursor based on the shell-core structure, the average particle size of the nickel-cobalt-manganese precursor is 3-5 μm, the thickness of the inner core is 2-3 μm, the thickness of the shell layer is 1-2 μm, and the thickness of the coating layer is 0.3-1 μm.
According to the nickel-cobalt-manganese precursor based on the shell-core structure, the volume of the core is 30-50% of the total volume of the nickel-cobalt-manganese precursor, the volume of the shell layer is 50-70% of the total volume of the nickel-cobalt-manganese precursor, and the volume of the coating layer is 10-20% of the total volume of the nickel-cobalt-manganese precursor.
According to the nickel-cobalt-manganese precursor based on the shell-core structure, the specific surface area of the nickel-cobalt-manganese precursor is 16m 2 /g～20m 2 The tap density is 1.6g/ml to 1.7g/ml.
According to the nickel-cobalt-manganese precursor based on the shell-core structure, in the shell-core structure of the nickel-cobalt-manganese precursor, the inner core part is in a dense net shape, the structural strength is high, and the stability of the sintered electrode material is improved; the porosity of the shell layer part is high, and the shell layer part presents a loose radial shape, so that lithium ion diffusion in the later sintering lithiation process is facilitated, and the rate capability of the electrode material is improved.
The second aspect of the invention provides a preparation method of a nickel-cobalt-manganese precursor based on a shell-core structure, which comprises the following steps:
(1) Preparing a metal salt solution with the total molar concentration of 1-4 mol/L as a first solution, preparing an alkali solution with the molar concentration of 5-15 mol/L, preparing a complexing agent with the molar concentration of 10-15 mol/L, and putting pure water, the alkali solution and the complexing agent into a first reaction kettle to be uniformly mixed and stirred to be used as a first base solution;
(2) Simultaneously introducing the first solution, an alkali solution and a complexing agent into a first reaction kettle at the speed of 0.0015L/min-0.18L/min, stirring at a first stirring speed to carry out a first co-precipitation reaction, introducing an inert gas for protection in the reaction process, discharging and extracting a mother solution through a concentration device for solidification, controlling a first pH value of the reaction in the reaction process of the first co-precipitation reaction to obtain a slurry with a median particle size of 2-3 mu m, and centrifugally spin-drying to obtain a nickel-cobalt-manganese precursor core;
(3) Preparing a metal salt solution with the total molar concentration of 0.5-2 mol/L as a second solution, preparing a tungsten salt solution with the concentration of 0.005-0.02 mol/L, mixing and stirring pure water, an alkali solution and a complexing agent of 10-15 mol/L uniformly to obtain a second base solution, putting the second base solution into a second reaction kettle, and adding the nickel-cobalt-manganese precursor core prepared in the step (2) as a seed crystal into the second base solution of the second reaction kettle to stir uniformly;
(4) On the basis of the step (3), setting a first stage and a second stage in the reaction process, in the first stage of shell layer growth, simultaneously introducing a second solution, an alkali solution and a complexing agent into a second reaction kettle at the speed of 0.0015L/min-0.18L/min, stirring at a second stirring speed to perform a second coprecipitation reaction, introducing inert gas for protection in the reaction process, discharging a mother solution through concentration equipment for solid extraction, keeping a second pH value of the reaction, and starting the second stage of growth after the precursor core grows to 2.7-4 mu m through the first stage; in the second stage, on the basis of the first stage, the tungsten salt solution, the second solution, the alkali solution and the complexing agent are simultaneously introduced into a second reaction kettle at the speed of 0.0015L/min to 0.18L/min to continuously grow, and the solution is continuously concentrated and solid-extracted to grow into a slurry precipitate with the median particle size of 3 to 5 mu m;
(5) And centrifuging, drying, sieving and demagnetizing the slurry precipitate to obtain the nickel-cobalt-manganese precursor with the tungsten coating and shell-core structure.
Preferably, the reaction temperature and the first pH value of the first coprecipitation reaction are controlled in step (2), and the reaction temperature and the second pH value of the second coprecipitation reaction are controlled in step (4); wherein the reaction temperature of the first coprecipitation reaction is 50-65 ℃, the first pH value is 10-12, the reaction temperature of the second coprecipitation reaction is 50-65 ℃, and the second pH value is 9-11.
Preferably, the pH control method of the first co-precipitation reaction comprises: maintaining the first pH after the first period of reaction time, the pH was lowered by 0.1 every second period of time and finally the pH was maintained within the first pH range.
Preferably, the stirring rate of the first coprecipitation reaction and the second coprecipitation reaction is 200-800 r/min, and the second stirring rate of the second coprecipitation reaction is less than the first stirring rate of the first coprecipitation reaction; in the step (2), the first solution, the alkali solution and the complexing agent are simultaneously fed into the first reaction kettle at different rates; in the step (4), the rates of introducing the second solution, the alkali solution and the complexing agent into the second reaction kettle at the same time are different; in the step (2), the rate of discharging the mother liquor by the concentrator is consistent with the total feeding flow rate, so that the liquid level in the first reaction kettle is stable and no overflow groove is formed; and (5) keeping the discharge rate of the compressor and the total feeding rate consistent in the step (4).
Preferably, the solute of the metal salt solution in the preparation method is at least one of nickel salt, cobalt salt and manganese salt, wherein the nickel salt comprises any one of nickel sulfate, nickel nitrate and nickel acetate, the cobalt salt comprises any one of cobalt sulfate, cobalt nitrate and cobalt acetate, and the manganese salt comprises any one of manganese sulfate, manganese nitrate and manganese acetate; the tungsten salt solution comprises any one of sodium tungstate solution, zinc tungstate solution and ammonium tungstate solution, the alkali solution comprises any one of sodium hydroxide solution, potassium hydroxide solution and lithium hydroxide solution, the inert gas comprises any one of helium, neon and nitrogen, and the complexing agent comprises ammonia water.
Preferably, the volume ratio of the added pure water to the reaction kettle is 0.5-0.8, the volume ratio of the alkali solution to the pure water is 0.0001-0.005, and the volume ratio of the complexing agent to the pure water is 0.01-0.03.
Preferably, the complexing agent does not participate in the reaction and plays a role of complexing metal ions, the alkali solution reacts with the complex, the feeding rate ratio of the first solution to the alkali solution is controlled to be 1-7.5 in the step (2), and the feeding rate ratio of the second solution to the alkali solution is controlled to be 1-7.5 in the step (4) and is used for balancing the pH value in the reaction system; and (4) taking the nickel-cobalt-manganese precursor core synthesized in the step (2) as a seed crystal to be supplied to the step (4) for multiple use.
Preferably, the preparation time of the core part in the step (2) is in the range of 50 to 70% of the total time of the precursor particle growth process, the growth time of the shell layer in the first stage in the step (4) is in the range of 15 to 25% of the total time of the precursor particle growth process, and the coating time of the second stage is in the range of 5 to 15% of the total time of the precursor particle growth process.
The third aspect of the invention also provides a positive electrode material, which is prepared by sintering the nickel-cobalt-manganese precursor and the lithium source in an oxygen-containing atmosphere.
The invention has the following beneficial effects:
1. the shell-core structure is set to be a dense net shape of the core, the shell is loose and radial, the coating layer is designed outside the shell, the dense part of the core is favorable for improving the structural stability of particles, the loose layer of the shell is favorable for ion diffusion and lithium ion deintercalation, so that the rate capability of the final electrode material is improved, and the coating layer is favorable for reducing charge transfer impedance and improving thermal stability.
2. The tungsten-coated nickel-cobalt-manganese precursor of the shell-core structure is adopted to prepare the electrode, so that the charge transfer impedance is effectively reduced, the cycle performance and the thermal stability of the electrode material can be further improved on the basis of keeping the original stability of the shell-core structure, and the overall cycle performance of the battery is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a schematic structural diagram of a shell-core structure of a tungsten-clad nickel-cobalt-manganese precursor material provided in an embodiment of the present invention;
FIG. 2 is a diagram of the distribution of elements provided in examples of the present invention and comparative examples;
FIG. 3 is a scanning electron microscope image and a scanning electron microscope cross-sectional view thereof provided in embodiment 1 of the present invention;
FIG. 4 is a scanning electron microscope image and a scanning electron microscope cross-sectional view thereof provided in embodiment 2 of the present invention;
FIG. 5 is a scanning electron microscope image and a scanning electron microscope cross-sectional view thereof provided in embodiment 3 of the present invention;
FIG. 6 is a scanning electron micrograph and a scanning electron micrograph thereof provided in comparative example 1 of the present invention.
FIG. 7 is a scanning electron micrograph and a scanning electron micrograph thereof provided in comparative example 2 of the present invention.
Fig. 8 is an electrical property test chart exemplarily provided in the examples of the present invention and the comparative example.
In the above drawings, the content of each reference numeral is as follows:
100. a kernel; 200. a shell layer; 300. a coating layer; d1, the grain size of a nickel-cobalt-manganese precursor material core; d2, the particle size of a nickel-cobalt-manganese precursor material shell layer; d3, the particle size of the nickel-cobalt-manganese precursor material coating layer.
Detailed Description
In order to make the above and other features and advantages of the present invention more apparent, the present invention is further described below with reference to the accompanying drawings. It is understood that the specific embodiments described herein are for purposes of illustration only and are not intended to be limiting.
[ SUMMARY OF THE INVENTION ]
The invention provides a nickel-cobalt-manganese precursor based on a shell-core structure, which comprises a core, a shell and a coating layer from inside to outside, wherein the core and the shell comprise primary particles of nickel-cobalt-manganese hydroxide, the coating layer comprises nickel-cobalt-manganese hydroxide containing a doping element, and the doping element is tungsten; wherein, the core of the nickel-cobalt-manganese precursor is in a compact net shape, and the shell layer is in a loose radial shape.
In the nickel cobalt manganese precursor mentioned above, the core and the shell comprise pure phase primary particles of nickel cobalt manganese hydroxide, and the coating comprises nickel cobalt manganese hydroxide containing the doping element tungsten.
Wherein, the primary particles refer to fine single crystal particles, the particles are closely contacted with each other, the gap is small, the secondary spherical particles are uniformly distributed, and the prepared electrode has high compaction density; the surface of the crystal is smooth, the lattice defects are few, and the diffusion and the migration of lithium ions in solid particles are facilitated, so that the electrode prepared from the nickel-cobalt-manganese precursor has excellent rate capability; the shell-core structure is designed to be compact in the inner core and loose in the shell layer, the compact part of the inner core is favorable for improving the structural stability of the particles, the loose layer of the shell layer part is favorable for ion diffusion and lithium ion intercalation and deintercalation, so that the rate capability of the final electrode material is improved.
On the basis, because the tungsten base and the tungsten alloy have good mechanical and thermal properties, such as high melting point, high thermal conductivity, large hardness, small thermal expansion coefficient, good high-temperature strength, good ductility, good impact toughness, good ray absorption capacity and the like, the tungsten element is doped in the nickel-cobalt-manganese precursor shell to form a tungsten coating layer outside the shell, so that the charge transfer impedance can be effectively reduced, and the thermal stability of the nickel-cobalt-manganese electrode material is improved.
Therefore, based on the above general inventive concept, the nickel-cobalt-manganese precursor can be modified on the basis of the unique characteristics of the shell-core structure.
In this general inventive concept, the preparation process comprises the following steps:
(1) Preparing a metal salt solution as a first solution, preparing an alkali solution, preparing a complexing agent, and putting pure water, the alkali solution and the complexing agent into a first reaction kettle to be uniformly mixed and stirred to be used as a first base solution;
(2) Simultaneously introducing a first solution, an alkali solution and a complexing agent into a first reaction kettle at a speed within a target range, stirring at a first stirring speed to perform a first coprecipitation reaction, introducing an inert gas for protection in the reaction process, discharging a mother solution through a concentration device, extracting the solid, controlling a first pH value of the reaction in the reaction process of the first coprecipitation reaction to obtain slurry with a median particle size of a first target particle size, and centrifugally spin-drying to obtain a nickel-cobalt-manganese precursor core;
(3) Preparing a metal salt solution as a second solution, preparing a tungsten salt solution, uniformly mixing and stirring pure water, an alkali solution and a complexing agent to obtain a second base solution, putting the second base solution into a second reaction kettle, and adding a nickel-cobalt-manganese precursor core as a seed crystal into the second base solution of the second reaction kettle to be uniformly stirred;
(4) Setting a first stage and a second stage in the reaction process, simultaneously introducing a second solution, an alkali solution and a complexing agent into a second reaction kettle at a speed within a target range in the first stage of shell layer growth, stirring at a second stirring speed to carry out a second coprecipitation reaction, introducing inert gas for protection in the reaction process, discharging clear liquid through concentration equipment, keeping a second pH value of the reaction, and starting the second stage of growth after the precursor core grows to a second target particle size through the first stage; in the second stage, on the basis of the first stage, the tungsten salt solution, a second solution, an alkali solution and a complexing agent are simultaneously introduced into a second reaction kettle to continuously grow, and the tungsten salt solution, the second solution, the alkali solution and the complexing agent are continuously concentrated and solid-extracted to grow into a slurry precipitate with a median particle size of a third target particle size;
(5) And centrifuging, drying, sieving and demagnetizing the slurry precipitate to obtain the nickel-cobalt-manganese precursor with the tungsten coating and shell-core structure.
The following is illustrated by specific examples:
[ example 1 ]
The embodiment of the invention provides a tungsten-doped nickel-cobalt-manganese precursor material M1, which is in a shell-core structure.
The chemical formula of the core and shell material is Ni 0.65 Co 0.20 Mn 0.15 (OH) 2 ，
The chemical formula of the tungsten cladding material is Ni 0.646 Co 0.199 Mn 0.149 W 0.006 (OH) 2 The structural formula of the tungsten-doped nickel-cobalt-manganese precursor material M1 is as follows:
0.67[Ni 0.65 Co 0.20 Mn 0.15 (OH) 2 ]·0.33[Ni 0.646 Co 0.199 Mn 0.149 W 0.006 (OH) 2 ]
the preparation method comprises the following steps:
(1) Calculating and weighing nickel sulfate crystals to prepare 2mol/L uniform metal salt solution, cobalt sulfate crystals to prepare 2mol/L uniform metal salt solution, and manganese sulfate crystals to prepare 2mol/L uniform metal salt solution; mixing the solutions of nickel, cobalt and manganese into a first solution with the concentration of 2mol/L according to the metal molar ratio of 65/20/15; adding 60L of pure water, 0.38L (10.83 mol/L) of sodium hydroxide solution and 1L (11.24 mol/L) of ammonia water into a 100L first reaction kettle, uniformly stirring at 700r/min, keeping the temperature at 60 ℃, and obtaining a first base solution with the pH value of 12.05 +/-0.05;
(2) And respectively introducing the first solution of metal salt, the solution of sodium hydroxide and ammonia water into a first reaction kettle with a prepared first base solution at the rate of 0.067L/min, 0.024L/min and 0.0016L/min for reaction and precipitation, wherein the introduction amount of each solution is set according to the time required by the reaction, the pH value is kept at 12.05 +/-0.05 3h before the reaction and precipitation starts, the pH value is reduced by 0.1 every 1h after the reaction starts for 1h, the final pH value is kept within the range of 11.40 +/-0.05, mother liquor is discharged through a concentration device for solid extraction, and the nickel-cobalt-manganese precipitate with the particle size D50 of 2.0 mu m is obtained after the reaction for 60 h. Centrifugally drying the nickel-cobalt-manganese precipitate to obtain precursor Ni 0.65 Co 0.20 Mn 0.15 (OH) 2 Keeping 10-20% of the moisture of the centrifuge as seed crystals for the subsequent stepsThe preparation method is used.
(3) Calculating and weighing nickel sulfate crystals to prepare 1.5mol/L uniform metal salt solution, cobalt sulfate crystals to prepare 1.5mol/L uniform metal salt solution, manganese sulfate crystals to prepare 1.5mol/L uniform metal salt solution, and mixing the solutions of the nickel sulfate crystals, the cobalt sulfate crystals and the manganese sulfate crystals into a second solution with the concentration of 1.5mol/L according to the metal molar ratio of 65/20/15 of the nickel, cobalt and manganese. In addition, independently preparing a sodium tungstate solution with the concentration of 0.0185mol/L, adding 60L of pure water, 0.05L (10.83 mol/L) of sodium hydroxide solution and 0.8L (11.24 mol/L) of ammonia water into a 100L second reaction kettle, uniformly stirring at the constant temperature of 60 ℃ at 620r/min, and obtaining a second base solution with the pH value of 11.20 +/-0.05; taking 13.5Kg of kernel prepared in the first step as a seed crystal to be uniformly stirred with the second base solution;
(4) Respectively introducing a second solution of metal salt, a sodium hydroxide solution and ammonia water into a second reaction kettle in which a second base solution with uniformly stirred seed crystals is added at 0.107L/min, 0.029L/min and 0.0021L/min for reaction and precipitation, wherein the introduction amount of each solution is set according to the time required by the reaction, the pH value is kept at 11.20 +/-0.05 after the reaction starts, the solution is continuously concentrated and solidified, and the feeding is stopped when the solution grows to the median particle size D50 of 2.7 mu m after the reaction is carried out for 20 hours, so that a loose shell layer with a first-stage shell growth is obtained;
continuously introducing the prepared sodium tungstate solution, the second metal salt solution, the sodium hydroxide solution and ammonia water into a second reaction kettle for second-stage W-coated growth at the ratio of 0.053L/min, 0.107L/min, 0.029L/min and 0.0029L/min respectively, wherein the introduction amount of each solution is set according to the time required by the reaction, and the reaction is finished when the solution grows to the median particle size D50 of 3.0 mu m after the reaction is carried out for 10 hours;
the doping amount of the W element in the coating stage is that the mass percentage of the doping element corresponding to the doping element compound accounts for 1.2 percent of the mass percentage of the element in the coating layer, and the average molar ratio of the metal ions in the corresponding coating layer is Ni: co: mn: w = 0.646;
(5) Washing, centrifuging, drying, sieving and demagnetizing the reaction precipitation slurry to obtain the precursor material with the W-coated shell-core structure
0.67[Ni 0.65 Co 0.20 Mn 0.15 (OH) 2 ]·0.33[Ni 0.646 Co 0.199 Mn 0.149 W 0.006 (OH) 2 ]。
[ example 2 ]
The difference of comparative example 1 is that the prepared precursor material has different coating amount of shell layer W.
A precursor material of a tungsten-doped nickel-cobalt-manganese precursor material M2 is of a shell-core structure.
The chemical formula of the core and shell material is Ni 0.65 Co 0.20 Mn 0.15 (OH) 2 ，
The chemical formula of the tungsten cladding material is Ni 0.640 Co 0.197 Mn 0.148 W 0.015 (OH) 2 ，
Has a general structural formula of
0.67[Ni 0.65 Co 0.20 Mn 0.15 (OH) 2 ]·0.33[Ni 0.640 Co 0.197 Mn 0.148 W 0.015 (OH) 2 ]
The preparation method comprises the following steps:
preparing a sodium tungstate solution with the concentration of 0.0231 mol/L;
adding 60L of pure water, 0.05L (10.83 mol/L) of sodium hydroxide solution and 0.8L (11.24 mol/L) of ammonia water into a 100L reaction kettle, uniformly stirring at 620r/min, and keeping the temperature at 60 ℃ to obtain a second base solution with the pH value of 11.20 +/-0.05;
taking 13.5Kg of compact inner core prepared in the step (2) in the example 1 as a seed crystal and uniformly stirring the seed crystal and the base solution;
respectively introducing the second solution of the metal salt, the sodium hydroxide solution and ammonia water into a reaction kettle which is added with the base solution with the seed crystal and uniformly stirred at 0.107L/min, 0.029L/min and 0.0021L/min for reaction and precipitation, wherein the introduction amount of each solution is set according to the time required by the reaction, the pH value is kept at 11.20 +/-0.05 after the reaction is started, the solution is continuously concentrated and solid-extracted, and the feeding is stopped when the solution grows to the median particle size D50 of 2.7 mu m after the reaction is carried out for 20 hours, so as to obtain a loose layer shell layer; continuously introducing the prepared 0.0231mol/L sodium tungstate solution, the second metal salt solution, the sodium hydroxide solution and the ammonia water into the reaction kettle for W-coated growth at the speed of 0.107L/min, 0.029L/min and 0.0038L/min respectively, wherein the introduction amount of each solution is set according to the time required by the reaction, and the reaction is finished when the solution grows for 10 hours until the median particle size D50 is 3.0 mu m;
the doping amount of the W element in the coating stage is that the mass percentage of the doping element corresponding to the doping element compound accounts for 3% of the mass percentage of the element in the coating layer of the precursor, and the average molar ratio of the metal ions in the corresponding coating layer is Ni: co: mn: w = 0.640;
washing, centrifuging, drying, sieving and demagnetizing the reaction precipitation slurry to obtain the precursor material with the W-coated shell-core structure
0.67[Ni 0.65 Co 0.20 Mn 0.15 (OH) 2 ]·0.33[Ni 0.640 Co 0.197 Mn 0.148 W 0.015 (OH) 2 ]。
[ example 3 ]
Compared with example 2, except that the prepared precursor material shell is not coated with W.
A precursor material M3 of nickel-cobalt-manganese is in an internal-tight and external-loose structure. The chemical formula of the nickel-cobalt-manganese precursor material core material is Ni 0.65 Co 0.20 Mn 0.15 (OH) 2 The preparation method comprises the following steps:
adding 60L of pure water, 0.05L (10.83 mol/L) of sodium hydroxide solution and 0.8L (11.24 mol/L) of ammonia water into a 100L reaction kettle, uniformly stirring at 620r/min, keeping the temperature at 60 ℃, and obtaining a second base solution with the pH value of 11.20 +/-0.05;
taking 13.5Kg of dense core prepared in the step (2) of the embodiment 1 as seed crystal to be uniformly stirred with the base solution;
respectively introducing the second solution of the metal salt, the solution of sodium hydroxide and ammonia water into a second reaction kettle, into which a second base solution with seed crystals added and uniformly stirred is added, at 0.107L/min, 0.029L/min and 0.0021L/min for reaction and precipitation, wherein the introduction amount of each solution is set according to the time required by the reaction, the pH value is kept at 11.20 +/-0.05 after the reaction starts, the solution is continuously concentrated and extracted for solidification, and the feeding is stopped when the solution grows to the median particle size D50 of 3.0 mu m after the reaction lasts for 30 hours, so that a loose shell layer is obtained;
washing, centrifuging, drying, sieving and demagnetizing the reaction precipitation slurry to obtain a precursor material Ni with an internal tight and external loose structure 0.65 Co 0.20 Mn 0.15 (OH) 2 。
Comparative example 1
Compared with example 3, except that the prepared precursor material has an overall compact particle structure.
A Ni-Co-Mn precursor material D11 has a compact structure with the chemical formula of Ni 0.65 Co 0.20 Mn 0.15 (OH) 2 The preparation method comprises the following steps:
adding 60L of pure water, 0.38L (10.83 mol/L) of sodium hydroxide solution and 1L (11.24 mol/L) of ammonia water into a 100L reaction kettle, uniformly stirring at 700r/min, keeping the temperature at 60 ℃, and obtaining a base solution with the pH value of 12.05 +/-0.05;
and respectively introducing the first solution of metal salt, the sodium hydroxide solution and ammonia water into a reaction kettle with prepared base solution at a rate of 0.067L/min, 0.024L/min and 0.0016L/min for reaction and precipitation, wherein the introduction amount of each solution is set according to the required reaction time, the pH value is kept at 12.05 +/-0.05 3h before the reaction and precipitation starts, the pH value is reduced by 0.1 every 1h after the reaction starts for 1h, the final pH value is kept within the range of 11.40 +/-0.05, mother liquor is discharged by a concentration device for solid lifting, and the nickel-cobalt-manganese precipitate with the medium particle size D50 of 3.0 mu m is obtained after the reaction is performed for 100 h. Washing, centrifuging, drying, sieving and demagnetizing the reaction precipitation slurry to obtain precursor material Ni with consistent internal and external compact structures 0.65 Co 0.20 Mn 0.15 (OH) 2 。
Comparative example 2
In comparison with example 3, with the following differences: the particle structure is loose as a whole.
A Ni-Co-Mn precursor material D21 has a loose structure with uniform internal and external chemical formulas, and a core material with a chemical formula of Ni 0.65 Co 0.20 Mn 0.15 (OH) 2 The preparation method comprises the following steps: will 50Adding L pure water, 0.29L (10.83 mol/L) sodium hydroxide solution and 1.2L (11.24 mol/L) ammonia water into a 100L reaction kettle, uniformly stirring at 650r/min, and keeping the temperature at 60 ℃ to obtain a base solution with the pH value of 12.05 +/-0.05;
and respectively introducing the second solution of the metal salt, the sodium hydroxide solution and ammonia water into a reaction kettle with prepared base solution at the rate of 0.154L/min, 0.042L/min and 0.0030L/min for reaction and precipitation, wherein the introduction amount of each solution is set according to the time required by the reaction, the pH value is kept at 12.05 +/-0.05 3h before the reaction precipitation starts, the pH value is reduced by 0.1 every 1h after the reaction starts for 1h, the final pH value is kept within the range of 11.40 +/-0.05, mother liquor is discharged by a concentration device for lifting and fixation, and the nickel-cobalt-manganese precipitate with the middle particle size D50 of 3.0 mu m is obtained after the reaction for 40 h. Washing, centrifuging, drying, sieving and demagnetizing the reaction precipitation slurry to obtain precursor material Ni with consistent internal and external compact structures 0.65 Co 0.20 Mn 0.15 (OH) 2 。
FIG. 1 is a schematic diagram of a core-shell structure of a nickel-cobalt-manganese precursor material and a W-coated precursor, wherein the overall structure of precursor particles is divided into three parts: the core is a dense net shape, the porosity is small, the diameter of the core part D1 is 2 mu m, the total diameter D2 of the shell is 2.7 mu m, the shell is loose and porous, the porosity is large, the overall thickness of the shell is about 1 mu m, the outermost part is a tungsten coating layer with the thickness of about 0.3 mu m, and D3 is 3 mu m.
As can be seen from the element distribution diagram in FIG. 2, the Ni, co and Mn elements are uniformly distributed and concentrated, mainly in the tungsten coating layer, the W element is concentrated and distributed in the outermost layer, and the tungsten coating layer is relatively uniform, and the single-sphere and multi-sphere graphs are compared to see that the Ni, co and Mn elements are distributed similarly, and the overall particle consistency is relatively good.
As can be seen from fig. 3, the M1 nickel cobalt manganese doped tungsten precursor material prepared in example 1 has a dense stacking of primary particles of the core, a small gap between the primary particles, a obviously loose radial shape on the shell portion, a fibrous primary particle on the surface, and many pores.
As can be seen from fig. 4, the overall structure of the M2 ni-co-mn doped tungsten precursor material prepared in example 2 is close to that of M1, the surface primary particle fiber is finer, and the porosity is slightly less than that of M1.
As can be seen from fig. 5, the structure of the M3 ni-co-mn precursor prepared in example 3 is close to that of M1 and M2, the surface primary particle fiber is the thickest compared with the former two, and the pore size is slightly larger than the former two.
As can be seen from fig. 6 to 7, the precursor D11 prepared in comparative example 1 has a relatively uniform internal and external structure, is compact as a whole, and has the lowest surface porosity, and the precursor D21 prepared in comparative example 2 has a loose shape as a whole and has the highest surface porosity.
As shown in fig. 8, when the precursor material synthesized above is subjected to a fastening electrical property test by the same treatment method, the obtained electrochemical properties are as follows, the rate capability and the cycle performance of the W-coated precursor material with the inner-tight and outer-loose shell core structure are excellent, the capacity can be maintained at 99.58% after 1C charging and discharging for 50 cycles, and the cycle performance of the undoped coated precursor material with the consistent inner and outer structures is worse.
The structural data of the precursor materials prepared in the above examples 1 to 3 and comparative examples 1 to 2 are shown in table 1 below.
TABLE 1
The precursor materials prepared in examples 1 to 3 and comparative examples 1 to 2 were subjected to the same treatment method for the test of the charging electrical properties, and the results are shown in table 2.
TABLE 2
As can be seen from tables 1 and 2:
comparing example 1 with example 2, it can be seen that when the tungsten-based doping amount is increased from 0.4% to 1%, the cycle and rate performance is reduced, because the tungsten-based content is too high, segregation occurs during the cladding process, and lamellar small nuclei are formed during the growth of the particles, so that the overall consistency of the particles is influenced to a certain extent, and the performance is reduced.
The comparison between the embodiment 1 and the embodiment 3 shows that when the shell layer is coated with a proper amount of tungsten base, the rate capability is better than that of the shell layer which is not coated with the tungsten base, mainly because the doping element of the shell layer inhibits the growth of primary particles from the aspect of macroscopic structure, the primary particles are refined, the particle pores are increased, the specific surface area is increased, the transmission distance of Li < + > is further shortened, the rate capability of the ternary material is improved, and the W element is coated on the surface from the aspect of microscopic ion dynamics, the charge transfer resistance can be reduced, so that the capacity retention rate and the rate capability of the material are improved.
The rate performance of comparative example 1 is significantly reduced compared to example 3 due to the low ratio and porosity due to its overall dense structure, reduced Li + The transmission channel of (1); compared with example 3, the capacity and the cycle performance of comparative example 2 are reduced, because the overall loose structure of the composite material causes the specific surface area and the porosity to be too high and the tap density to be too low, the crystal form is transformed during the calcination process, the particle strength is poor, the composite material is fragile during the compaction process, the capacity is reduced, and the excessively loose structure also causes the material to be easily broken under the condition of high potential, so that the cycle performance is reduced.
In summary, the nickel-cobalt-manganese precursor based on the shell-core structure, the positive electrode material and the preparation method thereof have the advantages that the internal structure stability is improved by constructing the dense mesh structure in the nickel-cobalt-manganese precursor material, and the Li is increased by synthesizing the radial outer loose layer + The transmission efficiency is improved in the structure of the nickel-cobalt-manganese precursor material; meanwhile, the transition metal tungsten is coated on the surface layer of the nickel-cobalt-manganese precursor material to form a tungsten coating layer, so that the charge transfer resistance is effectively reduced, and the thermal stability is improved; the nickel, the cobalt and the manganese are reasonably coated and matched with each other, so that the cycle performance and the multiplying power of the nickel, the cobalt and the manganese electrode material are effectively improvedAnd the performance of the lithium battery is improved. Meanwhile, the preparation method of the nickel-cobalt-manganese precursor material based on the shell-core structure has the advantages of controllable operation, simple synthesis method, easy realization of process and technology, and commercial application value.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (15)
1. The nickel-cobalt-manganese precursor based on the shell-core structure comprises a core and a shell from inside to outside, and is characterized in that the outermost part of the nickel-cobalt-manganese precursor further comprises a coating layer, the core is in a compact net shape, and the shell is in a loose radial shape;
the inner core and the shell layer are made of nickel-cobalt-manganese hydroxide, and the coating layer is made of nickel-cobalt-manganese hydroxide containing a doping element.
2. The nickel cobalt manganese precursor of claim 1, of the formula:
t[Ni x1 Co y1 Mn (1-x1-y1) (OH) 2 ]·(1-t)[Ni x2 Co y2 Mn (1-x2-y2-z) A z (OH) 2 ]；
the chemical formula of the inner core and the shell layer is Ni x1 Co y1 Mn (1-x1-y1) (OH) 2 The chemical formula of the coating layer is Ni x2 Co y2 Mn (1-x2-y2-z) A z (OH) 2 ；
Wherein x1 is more than or equal to 0.5 and less than 1,0 and less than or equal to y1 and less than or equal to 0.5,0.5 and more than x2 and less than or equal to 1,0 and more than y2 and less than or equal to 0.4,0 and more than or equal to z 0.1,0 and less than t 1, and 1-x1-y1 is more than 0,1-x2-y2-z is more than 0,A as doping elements.
3. The nickel-cobalt-manganese precursor of claim 1 or 2, wherein the doping element comprises at least one of Ti, mg, zn, cu, al, ga, in, F, la, cr, si, sn, W or a compound thereof.
4. The nickel-cobalt-manganese precursor of claim 1 or 2, wherein the doping element is W.
5. The nickel-cobalt-manganese precursor according to claim 1, wherein the doping element accounts for 0.01-3% of the total mass of the coating layer.
6. The nickel-cobalt-manganese precursor of claim 5, wherein the porosity of the inner core is 2% to 5% and the porosity of the shell layer is 10% to 15%.
7. The nickel-cobalt-manganese precursor according to claim 5, wherein the average particle diameter of the nickel-cobalt-manganese precursor is 3 to 5 μm, the thickness of the inner core is 2 to 3 μm, the thickness of the shell layer is 1 to 2 μm, and the thickness of the coating layer is 0.3 to 1 μm.
8. The nickel-cobalt-manganese precursor according to claim 5, wherein the volume of the inner core is 30-50% of the total volume of the nickel-cobalt-manganese precursor, the volume of the shell layer is 50-70% of the total volume of the nickel-cobalt-manganese precursor, and the volume of the coating layer is 10-20% of the total volume of the nickel-cobalt-manganese precursor.
9. The nickel-cobalt-manganese precursor of claim 5, having a specific surface area of 16m 2 /g～20m 2 The tap density is 1.6 g/mL-1.7 g/mL.
10. A method for preparing a nickel-cobalt-manganese precursor, the nickel-cobalt-manganese precursor comprising the nickel-cobalt-manganese precursor of any one of claims 1 to 9, comprising the steps of:
(1) Preparing a first solution containing metal salt, an alkali solution, a complexing agent and a first base solution;
(2) Carrying out a first coprecipitation reaction on the first solution, the alkali solution, the complexing agent and the first base solution to obtain a nickel-cobalt-manganese precursor core;
(3) Preparing a second solution containing metal salt, a tungsten salt solution and a second base solution, and adding the nickel-cobalt-manganese precursor core into the second base solution;
(4) Carrying out a second coprecipitation reaction on the second solution, the alkali solution, the complexing agent and the second base solution to obtain a target particle size, and adding the tungsten salt solution to continue the reaction to obtain a slurry precipitate;
(5) And centrifuging, drying, sieving and demagnetizing the slurry precipitate to obtain the nickel-cobalt-manganese precursor with the tungsten coating and shell-core structure.
11. The method according to claim 10, wherein the reaction temperature and the first pH of the first coprecipitation reaction are controlled in step (2), and the reaction temperature and the second pH of the second coprecipitation reaction are controlled in step (4);
wherein the reaction temperature of the first coprecipitation reaction is 50-65 ℃, the first pH value is 10-12, the reaction temperature of the second coprecipitation reaction is 50-65 ℃, and the second pH value is 9-11.
12. The method of claim 11, wherein the controlling the pH in the first co-precipitation reaction comprises: maintaining the first pH after the first period of reaction, the pH is lowered by 0.1 every second period of time, and finally the pH is maintained within the first pH range.
13. The method according to any one of claims 10 to 12, wherein the solute of the metal salt solution in the method is at least one of nickel salt, cobalt salt and manganese salt;
wherein the nickel salt comprises any one of nickel sulfate, nickel nitrate and nickel acetate, the cobalt salt comprises any one of cobalt sulfate, cobalt nitrate and cobalt acetate, and the manganese salt comprises any one of manganese sulfate, manganese nitrate and manganese acetate;
the tungsten salt solution comprises any one of sodium tungstate solution, zinc tungstate solution and ammonium tungstate solution, the alkali solution comprises any one of sodium hydroxide solution, potassium hydroxide solution and lithium hydroxide solution, and the complexing agent comprises ammonia water.
14. The production method according to claim 10, wherein the feed rate ratio of the first solution to the alkali solution is controlled to 1 to 7.5 in step (2), and the feed rate ratio of the second solution to the alkali solution is controlled to 1 to 7.5 in step (4) for balancing the pH value in the reaction; and (3) the nickel-cobalt-manganese precursor kernel synthesized in the step (2) is provided for the step (4) to be used for multiple times as a seed crystal.
15. A positive electrode material obtained by sintering a nickel-cobalt-manganese precursor according to any one of claims 1 to 9 or a nickel-cobalt-manganese precursor obtained by the production method according to any one of claims 10 to 14 with a lithium source in an oxygen-containing atmosphere.
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