CN116040696A - Preparation method of ternary positive electrode material based on liquid phase coprecipitation technology - Google Patents

Preparation method of ternary positive electrode material based on liquid phase coprecipitation technology Download PDF

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CN116040696A
CN116040696A CN202310031497.2A CN202310031497A CN116040696A CN 116040696 A CN116040696 A CN 116040696A CN 202310031497 A CN202310031497 A CN 202310031497A CN 116040696 A CN116040696 A CN 116040696A
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positive electrode
electrode material
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ternary positive
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冯文茹
刘创
周茜
郑江峰
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Guangdong Jiana Energy Technology Co Ltd
Qingyuan Jiazhi New Materials Research Institute Co Ltd
Jiangxi Jiana Energy Technology Co Ltd
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Qingyuan Jiazhi New Materials Research Institute Co Ltd
Jiangxi Jiana Energy Technology Co Ltd
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    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • 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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    • H01M4/00—Electrodes
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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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    • C01P2006/40—Electric properties
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
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Abstract

The invention provides a preparation method of a ternary positive electrode material based on a liquid phase coprecipitation technology, which comprises the following steps: s1, NCM solution, naOH solution, ammonia water solution and C 6 H 11 O 7 Mixing Na solution and LiOH solution together, controlling pH value to be above 10, heating for reaction, and granulating; s2, after granulation is finished, continuously adding NCM solution, naOH solution, ammonia water solution and C 6 H 11 O 7 Na solution and LiOH solution, growing crystal grains; after 4-10 hours of reaction, adding sodium hexametaphosphate solution; stopping feeding when the grains grow to the grain size of 4-6 mu m; s3, standing and aging the slurry obtained in the step S2, adding oxalic acid solution for washing, and then drying and tabletting to obtain a target product. In the preparation process, lithium is added into the ternary solution of nickel, cobalt and manganeseAnd the element is doped stably by adding a complexing agent, so that the precipitation speed difference of each metal ion in a reaction system is reduced. The invention also provides the high-nickel ternary positive electrode material prepared by the method, and lithium elements are uniformly distributed in ternary positive electrode material particles.

Description

Preparation method of ternary positive electrode material based on liquid phase coprecipitation technology
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a preparation method of a ternary positive electrode material based on a liquid phase coprecipitation technology, and a high nickel ternary positive electrode material prepared by adopting the preparation method.
Background
The lithium ion battery is widely applied to the fields of electric automobiles, smart grids and large-scale energy storage due to the characteristics of high energy density, light weight, no memory effect, good multiplying power performance and long cycle life. However, with the rapid development of the above fields, higher requirements are put on various performance indexes such as energy density, power density and the like of the lithium ion battery.
The energy density of the lithium ion battery mainly depends on the energy density of the positive electrode material, so that the development of a novel positive electrode material with good stability, high specific capacity and good rate capability is a key point that the lithium ion battery can be widely applied.
The ternary layered Nickel Cobalt Manganese (NCM) anode material has the advantages of high voltage, high capacity, long cycle life, good safety performance, no memory effect and small self discharge, and is a common anode material for lithium ion batteries. However, in the ternary positive electrode material, since Ni 2+ Radius of (2)
Figure BDA0004037763060000011
With Li + Radius->
Figure BDA0004037763060000012
Near, ni is liable to occur 2+ Occupying Li + The positive ions are mixed and discharged to lead Li to + Diffusion channels are reduced, which is detrimental to the extraction and intercalation of lithium ions. In addition, the ternary positive electrode material is an agglomerate particle body composed of a plurality of primary grains, and when the material is used for manufacturing a battery pole piece, if the pressure is too high, secondary particles are broken, primary particles in the agglomerate body are more contacted with electrolyte, and the capacity of the electrolyte is accelerated to be attenuated. The ternary positive electrode material with high nickel aggregate has large specific surface area and can increase the contact with electrolyte. Therefore, the particle size distribution and the microscopic morphology of the nickel-cobalt-manganese ternary precursor play a decisive role in the performance of the ternary cathode material.
At present, the preparation method of the positive electrode material mainly comprises a high-temperature solid phase method, a sol-gel method and a method combining a coprecipitation method and a high-temperature solid phase method. The preparation method has the advantages of simple process flow, high energy consumption, long synthesis period, uneven product particles, irregular crystal forms due to high-temperature sintering, wide particle size distribution range of the product and poor stability.
The prior art discloses a preparation method of radial structure spherical NCM811 ternary anode material, which comprises the following steps: preparing nickel salt, cobalt salt and manganese salt solution, wherein Ni: co: mn in a molar ratio of 8:1:1 as solution 1; preparing a precipitant into a solution 2; preparing a complexing agent into a solution 3; adding complexing agent solution into a reaction kettle as base solution; adding the solutions 1, 2 and 3 into a reaction kettle, introducing inert gas for protection, controlling the total ammonia concentration of a reaction system to be 0.5-1.5 mol/L, controlling the pH to be 11.3-11.7, aging for 5-15 hours at the temperature of 45-55 ℃, washing, suction filtering and drying the reaction product to obtain a precursor; taking the precursor and lithium salt as raw materials, and grinding and mixing uniformly; placing the mixed material into a muffle furnace for sintering under the atmosphere of oxygen; sintering is divided into two processes, and sintering is carried out for 4-8 hours at 400-500 ℃; sintering at 700-780 ℃ for 10-15 h; and cooling to room temperature after sintering is completed to obtain the positive electrode material. The method still easily generates the problems of high energy consumption and irregular crystal forms when high temperature is needed later, and the solid lithium salt and the precursor are unevenly mixed, so that uneven particles are easily caused in a high-temperature sintering stage, and the stability and uniformity of the anode material are affected.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a ternary positive electrode material based on a liquid phase coprecipitation technology, wherein lithium element is added into a nickel-cobalt-manganese ternary solution in the preparation process, and a complexing agent is added to stabilize doping elements, so that the precipitation speed difference of each metal ion in a reaction system is reduced, and the lithium element is uniformly doped in ternary layered nickel-cobalt-manganese (NCM) to realize uniform coprecipitation. The invention also provides the high-nickel ternary positive electrode material prepared by the method, and doped lithium elements in ternary positive electrode material particles are uniformly distributed, so that the transmission efficiency of lithium ions can be effectively increased.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of a ternary positive electrode material based on a liquid phase coprecipitation technology comprises the following steps:
s1, NCM solution, naOH solution, ammonia water solution and C 6 H 11 O 7 Mixing Na solution and LiOH solution together, controlling pH value to be above 10, heating for reaction, and granulating;
s2, after granulation is finished, continuously adding NCM solution, naOH solution, ammonia water solution and C 6 H 11 O 7 Na solution and LiOH solution, growing crystal grains; after 4-10 hours of reaction, adding sodium hexametaphosphate solution; stopping feeding when the grains grow to the grain size of 4-6 mu m;
s3, standing and aging the slurry obtained in the step S2, adding oxalic acid solution for washing, and drying and tabletting after washing is finished to obtain the target ternary positive electrode material.
As a further description of the technical solution of the present invention, in the granulation stage of S1, the following steps are specifically included:
s11, respectively preparing the following concentrationsSolution of degree: 1 to 3mol/L of NCM solution, 3 to 8mol/L of NaOH solution, 3 to 5mol/L of ammonia water solution and 0.1 to 2g/L of C 6 H 11 O 7 Na solution and 0.5-3 g/L LiOH solution;
s12, respectively adding 1-3 mol/L of NCM solution, 3-8 mol/L of NaOH solution, 3-5 mol/L of ammonia water solution and 0.1-2 g/L of C 6 H 11 O 7 Na solution and LiOH solution of 0.5-3 g/L are introduced into the reaction kettle at the flow rates of 5-15 ml/min, 1-10 ml/min, 2-7Hz and 2-7Hz, the pH value in the reaction kettle system is controlled to be 10-12, the reaction temperature is 70-80 ℃, and the granulation is finished after 30-40 min.
In the precursor granulation stage, liOH solution is combined with NCM solution, naOH solution, ammonia solution and C 6 H 11 O 7 Na solution is introduced into the reaction kettle together, so that compared with a high-temperature sintering solid-phase method, the method can save more energy on one hand and avoid the problem of serious lithium loss in the sintering stage on the other hand.
In the charging process, the concentration of LiOH solution is preferably 0.5-3 g/L, and the flow rate is 2-7Hz, so that lithium ions can be uniformly doped and distributed in the final ternary positive electrode material.
As a further description of the technical scheme of the present invention, in the coprecipitation reaction generation stage of S2, the method specifically includes the following steps:
s21, after granulation is finished, NCM solution with the concentration of 1 to 3mol/L, naOH solution with the concentration of 3 to 8mol/L, ammonia solution with the concentration of 3 to 5mol/L and C with the concentration of 0.1 to 2g/L 6 H 11 O 7 The flow rates of Na solution and LiOH solution with the concentration of 0.5-3 g/L are respectively adjusted to 15-22 ml/min, 5-12 ml/min, 18-23 ml/min, 3-10 Hz and 3-10 Hz, and the reaction is carried out to grow crystal grains;
s22, after 4-10 hours of reaction, adding 0.5-2 mol/L sodium hexametaphosphate solution at a flow rate of 5-10 Hz;
s23, stopping feeding when the grains grow to the grain size of 4-6 mu m.
Compared with the granulation stage, the flow rate (flow rate) of the solution introduced in the coprecipitation reaction generation stage is greatly improved. In this reaction stage, the primary grains grow faster, consuming more solution, and thus increasing the flow rate. After 4-10 hours of reaction, the introduced sodium hexametaphosphate solution can improve the dispersion effect of the solution and the sphericity of the particles.
As a further description of the technical solution of the present invention, in the post-processing stage of S3, the method specifically includes the following steps:
s31, standing and aging the slurry in the reaction kettle, and washing with 1-4 mol/L oxalic acid solution;
s32, after washing, drying the wet material, performing magnetic removal and sieving, and tabletting to obtain the target ternary positive electrode material.
As a further description of the technical scheme of the invention, the NCM solution is a ternary precursor of nickel, cobalt and manganese, and the chemical components of the NCM solution are Ni x Co y Mn (1-x-y-z) Wherein x is more than or equal to 0.80 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.1, z is more than or equal to 0 and less than or equal to 0.1,0<1-x-y-z<0.1。
As a further description of the technical scheme of the invention, the C 6 H 11 O 7 Na is chelating agent, C 6 H 11 O 7 Na (sodium gluconate) is also a structure directing agent, and can be doped lithium element which is uniformly mixed in the ternary positive electrode material.
As a further description of the technical scheme of the invention, the sodium hexametaphosphate is a dispersing agent. Sodium hexametaphosphate as a dispersing agent can improve the dispersing effect of the solution and the sphericity of particles.
Preferably, the preparation method of the ternary positive electrode material based on the liquid phase coprecipitation technology specifically comprises the following steps:
s1, respectively preparing the following concentration solutions: 1.7mol/L NCM solution, 4.0mol/L NaOH solution, 3.5mol/L ammonia solution, 0.15g/L C 6 H 11 O 7 Na solution and 1.3g/L LiOH solution; introducing the mixture into a 100L reaction kettle at flow rates of 6ml/min, 4.5ml/min, 3.7Hz and 2.8Hz respectively, controlling the pH in the reaction kettle system to be 10-12, controlling the reaction temperature to be 75 ℃, and granulating after 30 min;
s2, after granulation is finished, NCM solution, naOH solution, ammonia water solution and C 6 H 11 O 7 The flow rates of the Na solution and the LiOH solution are respectively adjusted to 17.5ml/min, 8.1ml/min, 15ml/min, 4.5Hz and 4.5Hz; after 6 hours of reaction, 1.5mol/L sodium hexametaphosphate solution is introduced at a flow rate of 6 Hz; stopping feeding when the grains grow to a grain size of 5 μm;
s3, standing and aging the slurry in the reaction kettle, and washing with 1mol/L oxalic acid solution; and after washing, drying the wet material, performing magnetic removal and sieving, and tabletting to obtain the target ternary positive electrode material.
Preferably, the preparation method of the ternary positive electrode material based on the liquid phase coprecipitation technology specifically comprises the following steps:
s1, respectively preparing the following concentration solutions: 1mol/L NCM solution, 3mol/L NaOH solution, 3mol/L ammonia water solution, 0.1g/L C 6 H 11 O 7 Na solution and 0.5g/L LiOH solution; introducing the mixture into a 100L reaction kettle at flow rates of 5ml/min, 1ml/min, 2Hz and 2Hz respectively, controlling the pH in the reaction kettle system to be 10-12, and granulating after 30min at the reaction temperature of 75 ℃;
s2, after granulation is finished, NCM solution, naOH solution, ammonia water solution and C 6 H 11 O 7 The flow rates of the Na solution and the LiOH solution are respectively adjusted to 15ml/min, 5ml/min, 18ml/min, 3Hz and 3Hz; after 4 hours of reaction, introducing 0.5mol/L sodium hexametaphosphate solution at a flow rate of 5Hz; stopping feeding when the grains grow to a grain size of 4.5 μm;
s3, standing and aging the slurry in the reaction kettle, and washing with 1mol/L oxalic acid solution; and after washing, drying the wet material, performing magnetic removal and sieving, and tabletting to obtain the target ternary positive electrode material.
The invention also provides a ternary positive electrode material, which is prepared by adopting the preparation method of the ternary positive electrode material. According to the ternary positive electrode material, doped lithium elements can be uniformly distributed in positive electrode material particles, so that the transmission rate of lithium ions is increased, the internal lattice structure of the positive electrode in a high lithium removal state is stabilized, the specific capacity and the cycling stability of the monocrystal layered positive electrode material in a high charge cut-off voltage state are remarkably improved, and meanwhile side reactions such as oxygen production on the surface of the high-voltage positive electrode can be effectively reduced.
Based on the technical scheme, compared with the prior art, the invention has the following technical effects:
(1) According to the preparation method of the ternary positive electrode material, a liquid phase coprecipitation technology is adopted, lithium element is added into a nickel-cobalt-manganese ternary solution, and a complexing agent is added to stabilize doping elements, so that the precipitation speed difference of each metal ion in a reaction system is reduced, the lithium element is uniformly doped into ternary layered nickel-cobalt-manganese (NCM), and uniform coprecipitation is realized.
(2) According to the ternary positive electrode material obtained by the preparation method of the ternary positive electrode material, the doped lithium elements can be uniformly distributed in the ternary positive electrode material particles, so that the transmission efficiency of lithium ions can be effectively increased, the internal lattice structure of the positive electrode in a high lithium removal state is stabilized, and the specific capacity and the cycling stability of the positive electrode material are improved.
Drawings
Fig. 1 is a flowchart of a preparation method of a ternary positive electrode material of the present invention.
Fig. 2 is an SEM image of the ternary cathode material prepared in example 1 of the present invention.
Detailed Description
In order that the invention may be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments that are illustrated in the appended drawings. The drawings illustrate preferred embodiments of the invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Fig. 1 is a flow chart of a preparation method of a ternary positive electrode material, as shown in fig. 1, and the preparation method of the ternary positive electrode material based on a liquid phase coprecipitation technology comprises the following steps:
s1, granulating stage
The following solutions were prepared separately: 1 to 3mol/L of NCM solution, 3 to 8mol/L of NaOH solution, 3 to 5mol/L of ammonia water solution and 0.1 to 2g/L of C 6 H 11 O 7 Na solution and 0.5-3 g/L LiOH solution;
mixing the above NCM solution, naOH solution, ammonia water solution, and C 6 H 11 O 7 Na solution and LiOH solution are respectively introduced into a reaction kettle at flow rates of 5-15 ml/min, 1-10 ml/min, 2-7Hz and 2-7Hz, the pH value in the reaction kettle system is controlled to be 10-12, the reaction temperature is 70-80 ℃, and granulation is finished after 30-40 min;
s2, a coprecipitation reaction generation stage
After granulation, NCM solution of 1-3 mol/L, naOH solution of 3-8 mol/L, ammonia water solution of 3-5 mol/L and C of 0.1-2 g/L are added 6 H 11 O 7 The flow rates of Na solution and LiOH solution with the concentration of 0.5-3 g/L are respectively adjusted to 15-22 ml/min, 5-12 ml/min, 18-23 ml/min, 3-10 Hz and 3-10 Hz, and the reaction is carried out to grow crystal grains;
after 4 to 10 hours of reaction, adding 0.5 to 2mol/L sodium hexametaphosphate solution at a flow rate of 5 to 10 Hz;
when the grains were grown to a grain size of 4 to 6. Mu.m, the feeding was stopped.
S3, post-treatment stage
Standing and aging the slurry in the reaction kettle, and washing with 1-4 mol/L oxalic acid solution;
and after washing, drying the wet material, and tabletting the dried material after magnetic removal and sieving to obtain the target ternary positive electrode material.
Wherein the NCM solution is a ternary precursor of nickel, cobalt and manganese, and the chemical component of the NCM solution is Ni x Co y Mn (1-x-y-z) Wherein x is more than or equal to 0.80 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.1, z is more than or equal to 0 and less than or equal to 0.1,0<1-x-y-z<0.1。
C 6 H 11 O 7 Na is used as chelating agent and structure directing agent to uniformly mix doped lithium elementIn ternary positive electrode materials.
Sodium hexametaphosphate is used as a dispersing agent, so that the dispersing effect of the solution can be improved, and the sphericity of particles can be improved.
Example 1
The ternary positive electrode material is prepared by the following method, and the preparation method specifically comprises the following steps:
s1, firstly, respectively preparing the following solutions: 1.7mol/L NCM solution, 4.0mol/L NaOH solution, 3.5mol/L ammonia solution, 0.15g/L C 6 H 11 O 7 Na solution and 1.3g/L LiOH solution; then, the mixture is respectively introduced into a 100L reaction kettle at flow rates of 6ml/min, 4.5ml/min, 3.7Hz and 2.8Hz, the pH value in the reaction kettle system is controlled to be 10-12, the reaction temperature is 75 ℃, and the granulation is finished after 30 min.
S2, after granulation is finished, NCM solution, naOH solution, ammonia water solution and C 6 H 11 O 7 The flow rates of the Na solution and the LiOH solution are respectively adjusted to 17.5ml/min, 8.1ml/min, 15ml/min, 4.5Hz and 4.5Hz; after 6 hours of reaction, 1.5mol/L sodium hexametaphosphate solution is introduced at a flow rate of 6 Hz; when the grains were grown to a grain size of 5. Mu.m, the feeding was stopped.
S3, standing and aging the slurry in the reaction kettle, and washing with 1mol/L oxalic acid solution; and after washing, drying the wet material, performing magnetic removal and sieving, and tabletting to obtain the target ternary positive electrode material.
Fig. 1 is an SEM image of the ternary cathode material prepared in this embodiment, as shown in fig. 1, the target ternary cathode material has good sphericity and regular crystal form, so that agglomeration of secondary particles can be reduced.
Example 2
The ternary positive electrode material is prepared by the following method, and the preparation method specifically comprises the following steps:
s1, firstly, respectively preparing the following solutions: 1mol/L NCM solution, 3mol/L NaOH solution, 3mol/L ammonia water solution, 0.1g/L C 6 H 11 O 7 Na solution and 0.5g/L LiOH solution; then, flows of 5ml/min, 1ml/min, 2Hz and 2Hz, respectivelyIntroducing the mixture into a 100L reaction kettle, controlling the pH in the reaction kettle system to be 10-12, reacting at 75 ℃, and granulating after 30 min.
S2, after granulation is finished, NCM solution, naOH solution, ammonia water solution and C 6 H 11 O 7 The flow rates of the Na solution and the LiOH solution are respectively adjusted to 15ml/min, 5ml/min, 18ml/min, 3Hz and 3Hz; after 4 hours of reaction, introducing 0.5mol/L sodium hexametaphosphate solution at a flow rate of 5Hz; when the grains were grown to a grain size of 4.5. Mu.m, the feeding was stopped.
S3, standing and aging the slurry in the reaction kettle, and washing with 1mol/L oxalic acid solution; and after washing, drying the wet material, performing magnetic removal and sieving, and tabletting to obtain the target ternary positive electrode material.
Example 3
The ternary positive electrode material is prepared by the following method, and the preparation method specifically comprises the following steps:
s1, firstly, respectively preparing the following solutions: 3mol/L NCM solution, 8mol/L NaOH solution, 5mol/L ammonia water solution, 2g/L C 6 H 11 O 7 Na solution and 3g/L LiOH solution; then, respectively introducing the mixture into a 100L reaction kettle at flow rates of 15ml/min, 10ml/min, 7Hz and 7Hz, controlling the pH in the reaction kettle system at 10-12, reacting at 75 ℃, and granulating after 30 min.
S2, after granulation is finished, NCM solution, naOH solution, ammonia water solution and C 6 H 11 O 7 The flow rates of the Na solution and the LiOH solution are respectively adjusted to 22ml/min, 12ml/min, 23ml/min, 10Hz and 19Hz; after 10 hours of reaction, 2mol/L sodium hexametaphosphate solution is introduced at a flow rate of 5Hz; when the grains were grown to a grain size of 4.5. Mu.m, the feeding was stopped.
S3, standing and aging the slurry in the reaction kettle, and washing with 1mol/L oxalic acid solution; and after washing, drying the wet material, performing magnetic removal and sieving, and tabletting to obtain the target ternary positive electrode material.
Example 4
The ternary positive electrode material is prepared by the following method, and the preparation method specifically comprises the following steps:
s1, firstly, respectively preparing the following solutions: 1.7mol/L NCM solution, 4.0mol/L NaOH solution, 3.5mol/L ammonia solution, 0.8g/L C 6 H 11 O 7 Na solution, 1.3g/L LiOH solution; then, the mixture is respectively introduced into a 100L reaction kettle at flow rates of 6ml/min, 4.5ml/min, 3.7Hz and 2.8Hz, the pH value in the reaction kettle system is controlled to be 10-12, the reaction temperature is 75 ℃, and the granulation is finished after 30 min.
S2, after granulation is finished, NCM solution, naOH solution, ammonia water solution and C 6 H 11 O 7 The flow rates of the Na solution and the LiOH solution are respectively adjusted to 17.5ml/min, 8.1ml/min, 15ml/min, 4.5Hz and 4.5Hz; after 6 hours of reaction, 1.5mol/L sodium hexametaphosphate solution is introduced at a flow rate of 6 Hz; when the grains were grown to a grain size of 5.5. Mu.m, the feeding was stopped.
S3, standing and aging the slurry in the reaction kettle, and washing with 1mol/L oxalic acid solution; and after washing, drying the wet material, performing magnetic removal and sieving, and tabletting to obtain the target ternary positive electrode material.
Comparative example 1
The ternary positive electrode material is prepared by the following method, and the preparation method specifically comprises the following steps:
s1, firstly, respectively preparing the following solutions: 1mol/L NCM solution, 1.5mol/L NaOH solution and 2.5mol/L ammonia solution; then, the mixture is respectively introduced into a 100L reaction kettle at the flow rates of 3.5ml/min, 6ml/min and 4.5ml/min, the pH value in the reaction kettle system is controlled to be 10-12, the reaction temperature is 75 ℃, and the granulation is finished after 30 min.
S2, after granulation is finished, respectively adjusting the flow rates of the NCM solution, the NaOH solution and the ammonia water solution to 17.5ml/min, 8.1ml/min and 15ml/min; after 6 hours of reaction, 1.5mol/L sodium hexametaphosphate solution is introduced at a flow rate of 6 Hz; when the grains were grown to a grain size of 5.0. Mu.m, the feeding was stopped.
S3, standing and aging the slurry in the reaction kettle, and washing with pure water; and after washing, drying the wet material, performing magnetic removal and sieving, and tabletting to obtain the ternary precursor.
S4, mixing the obtained ternary precursor and solid LiOH according to the proportion of 1:1.05, putting the mixture into a muffle furnace, sintering the mixture from room temperature to 930 ℃, cooling the mixture to room temperature, taking the mixture out, grinding and sieving the mixture, and obtaining the ternary positive electrode material.
The ternary cathode materials prepared in examples 1 to 4 and comparative example 1 were tested, and the test results are shown in table 1.
TABLE 1 Performance test data for ternary cathode materials prepared in example 1-example 4 and comparative example 1
Ternary positive electrode material Product pH First charge and discharge efficiency
Example 1 pH＝7 92.77％
Example 2 pH＝9 89.12％
Example 3 pH＝10 84.65％
Example 4 pH＝8 83.90％
Comparative example 1 pH＝11 82.34％
As can be seen from Table 1, compared with the conventional coprecipitation method and high temperature solid phase method for preparing the ternary cathode material in comparative example 1, the liquid phase coprecipitation reaction method is adopted for preparing the ternary cathode material in examples 1-4, the initial discharge efficiency is higher, and the initial charge and discharge efficiency of the ternary cathode material in example 1 reaches more than 90%.
The foregoing is merely illustrative and explanatory of the invention as it is described in more detail and is not thereby to be construed as limiting the scope of the invention. It should be noted that modifications and improvements can be made by those skilled in the art without departing from the spirit of the invention, and that these obvious alternatives fall within the scope of the invention.

Claims (10)

1. The preparation method of the ternary positive electrode material based on the liquid phase coprecipitation technology is characterized by comprising the following steps of:
s1, NCM solution, naOH solution, ammonia water solution and C 6 H 11 O 7 Mixing Na solution and LiOH solution together, controlling pH value to be above 10, heating for reaction, and granulating;
s2, after granulation is finished, continuously adding NCM solution, naOH solution, ammonia water solution and C 6 H 11 O 7 Na solution and LiOH solution, growing crystal grains; after 4-10 hours of reaction, adding sodium hexametaphosphate solution; stopping feeding when the grains grow to the grain size of 4-6 mu m;
s3, standing and aging the slurry obtained in the step S2, adding oxalic acid solution for washing, and drying and tabletting after washing is finished to obtain the target ternary positive electrode material.
2. The method for preparing a ternary positive electrode material according to claim 1, characterized in that in the granulation phase of S1, it comprises in particular the following steps:
s11, respectively preparing the following concentration solutions: 1 to 3mol/L of NCM solution, 3 to 8mol/L of NaOH solution, 3 to 5mol/L of ammonia water solution and 0.1 to 2g/L of C 6 H 11 O 7 Na solution and 0.5-3 g/L LiOH solution;
s12, respectively adding 1-3 mol/L of NCM solution, 3-8 mol/L of NaOH solution, 3-5 mol/L of ammonia water solution and 0.1-2 g/L of C 6 H 11 O 7 Na solution and LiOH solution of 0.5-3 g/L are introduced into the reaction kettle at the flow rates of 5-15 ml/min, 1-10 ml/min, 2-7Hz and 2-7Hz, the pH value in the reaction kettle system is controlled to be 10-12, the reaction temperature is 70-80 ℃, and the granulation is finished after 30-40 min.
3. The method for preparing a ternary positive electrode material according to claim 1, characterized in that in the phase of co-precipitation reaction formation of S2, it comprises in particular the following steps:
s21, after granulation is finished, NCM solution with the concentration of 1 to 3mol/L, naOH solution with the concentration of 3 to 8mol/L, ammonia solution with the concentration of 3 to 5mol/L and C with the concentration of 0.1 to 2g/L 6 H 11 O 7 The flow rates of Na solution and LiOH solution with the concentration of 0.5-3 g/L are respectively adjusted to 15-22 ml/min, 5-12 ml/min, 18-23 ml/min, 3-10 Hz and 3-10 Hz, and the reaction is carried out to grow crystal grains;
s22, after 4-10 hours of reaction, adding 0.5-2 mol/L sodium hexametaphosphate solution at a flow rate of 5-10 Hz;
s23, stopping feeding when the grains grow to the grain size of 4-6 mu m.
4. The method for preparing a ternary positive electrode material according to claim 1, characterized in that it comprises, in the post-treatment stage of S3, in particular the following steps:
s31, standing and aging the slurry in the reaction kettle, and washing with 1-4 mol/L oxalic acid solution;
s32, after washing, drying the wet material, performing magnetic removal and sieving, and tabletting to obtain the target ternary positive electrode material.
5. The method for preparing a ternary positive electrode material according to claim 1, wherein the NCM solution is a ternary precursor of nickel, cobalt and manganese, and the chemical composition of the ternary positive electrode material is Ni x Co y Mn (1-x-y-z) Wherein x is more than or equal to 0.80 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.1, z is more than or equal to 0 and less than or equal to 0.1,0<1-x-y-z<0.1。
6. The method for preparing a ternary positive electrode material according to claim 1, wherein the C 6 H 11 O 7 Na is a chelating agent.
7. The method for preparing a ternary cathode material according to claim 1, wherein the sodium hexametaphosphate is a dispersing agent.
8. The method for preparing a ternary positive electrode material according to claim 1, comprising the following steps:
s1, respectively preparing the following concentration solutions: 1.7mol/L NCM solution, 4.0mol/L NaOH solution, 3.5mol/L ammonia solution, 0.15g/L C 6 H 11 O 7 Na solution and 1.3g/L LiOH solution; introducing the mixture into a 100L reaction kettle at flow rates of 6ml/min, 4.5ml/min, 3.7Hz and 2.8Hz respectively, controlling the pH in the reaction kettle system to be 10-12, controlling the reaction temperature to be 75 ℃, and granulating after 30 min;
s2, after granulation is finished, NCM solution, naOH solution, ammonia water solution and C 6 H 11 O 7 The flow rates of the Na solution and the LiOH solution are respectively adjusted to 17.5ml/min, 8.1ml/min, 15ml/min, 4.5Hz and 4.5Hz; after 6 hours of reaction, 1.5mol/L sodium hexametaphosphate solution is introduced at a flow rate of 6 Hz; stopping feeding when the grains grow to a grain size of 5 μm;
s3, standing and aging the slurry in the reaction kettle, and washing with 1mol/L oxalic acid solution; and after washing, drying the wet material, performing magnetic removal and sieving, and tabletting to obtain the target ternary positive electrode material.
9. The method for preparing a ternary positive electrode material according to claim 1, comprising the following steps:
s1, respectively preparing the following concentration solutions: 1mol/L NCM solution, 3mol/L NaOH solution, 3mol/L ammonia water solution, 0.1g/L C 6 H 11 O 7 Na solution and 0.5g/L LiOH solution; introducing the mixture into a 100L reaction kettle at flow rates of 5ml/min, 1ml/min, 2Hz and 2Hz respectively, controlling the pH in the reaction kettle system to be 10-12, and granulating after 30min at the reaction temperature of 75 ℃;
s2, after granulation is finished, NCM solution, naOH solution, ammonia water solution and C 6 H 11 O 7 The flow rates of the Na solution and the LiOH solution are respectively adjusted to 15ml/min, 5ml/min, 18ml/min, 3Hz and 3Hz; after 4 hours of reaction, introducing 0.5mol/L sodium hexametaphosphate solution at a flow rate of 5Hz; stopping feeding when the grains grow to a grain size of 4.5 μm;
s3, standing and aging the slurry in the reaction kettle, and washing with 1mol/L oxalic acid solution; and after washing, drying the wet material, performing magnetic removal and sieving, and tabletting to obtain the target ternary positive electrode material.
10. The high-nickel ternary cathode material is characterized by being prepared by adopting the preparation method of the ternary cathode material in any one of claims 1-9.
CN202310031497.2A 2023-01-04 2023-01-04 Preparation method of ternary positive electrode material based on liquid phase coprecipitation technology Pending CN116040696A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116462243A (en) * 2023-06-19 2023-07-21 宜宾光原锂电材料有限公司 Battery, ternary positive electrode material thereof, precursor thereof and preparation method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116462243A (en) * 2023-06-19 2023-07-21 宜宾光原锂电材料有限公司 Battery, ternary positive electrode material thereof, precursor thereof and preparation method
CN116462243B (en) * 2023-06-19 2023-09-26 宜宾光原锂电材料有限公司 Battery, ternary positive electrode material thereof, precursor thereof and preparation method

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