CN116375104A - Preparation method of large-particle high-nickel ternary precursor material and large-particle high-nickel ternary precursor material - Google Patents

Preparation method of large-particle high-nickel ternary precursor material and large-particle high-nickel ternary precursor material Download PDF

Info

Publication number
CN116375104A
CN116375104A CN202310223031.2A CN202310223031A CN116375104A CN 116375104 A CN116375104 A CN 116375104A CN 202310223031 A CN202310223031 A CN 202310223031A CN 116375104 A CN116375104 A CN 116375104A
Authority
CN
China
Prior art keywords
solution
precursor material
reaction
nickel
ternary precursor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310223031.2A
Other languages
Chinese (zh)
Inventor
左美华
邢王燕
阳锐
宋方亨
蒋雪平
杜先锋
黄宇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yibin Guangyuan Lithium Battery Co ltd
Yibin Libao New Materials Co Ltd
Original Assignee
Yibin Guangyuan Lithium Battery Co ltd
Yibin Libao New Materials Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yibin Guangyuan Lithium Battery Co ltd, Yibin Libao New Materials Co Ltd filed Critical Yibin Guangyuan Lithium Battery Co ltd
Priority to CN202310223031.2A priority Critical patent/CN116375104A/en
Publication of CN116375104A publication Critical patent/CN116375104A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00Compounds of nickel
    • C01G53/006Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00Compounds of nickel
    • C01G53/40Nickelates
    • C01G53/42Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection 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
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/03Particle morphology depicted by an image obtained by SEM
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M2004/026Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028Positive electrodes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

The invention discloses a preparation method of a large-particle high-nickel ternary precursor material, which comprises the steps of introducing a metal salt solution, a complexing agent solution, a precipitant solution and nitrogen into a reaction kettle, circularly concentrating materials between a thickener and the reaction kettle, and performing coprecipitation reaction to prepare crystal nuclei; adding a metal salt solution, a complexing agent solution and a precipitant solution into the bottom solution of the reaction kettle, simultaneously adding crystal nuclei to continue the coprecipitation reaction until the average particle size of the particles grows to the target particle size, and continuously and stably discharging to obtain a solution containing a precursor material; in the reaction process, the content of free nickel ions in the reaction liquid in the reaction kettle is controlled to be 10-35 mg/L. According to the invention, the content of free nickel ions in the reaction liquid in the reaction process is controlled to be 10-35 mg/L, so that the stress of the internal structure of the crystal is reduced, and the secondary particles of the synthesized ternary precursor material cannot crack to generate cracks.

Description

Preparation method of large-particle high-nickel ternary precursor material and large-particle high-nickel ternary precursor material
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to a preparation method of a large-particle high-nickel ternary precursor material.
Background
As power battery technology continues to mature, consumer acceptance for new energy vehicles is increasing, and new energy vehicle markets have been driven by policies to turn to markets. Meanwhile, the new energy automobile has high requirements on the endurance mileage, and has high requirements on the energy density, the high cycle performance and the high safety performance of the lithium ion battery. The main research direction is to increase the gram capacity of materials, wherein high nickel ternary materials (LiNi x Co y M 1-x-y O 2 (X.gtoreq.0.80)) has been the focus of attention for positive electrode materials because of its relatively high capacity. To achieve a high energy density battery, it is necessary to use a higher capacity high nickel material.
High nickel ternary positive electrode material LiNixCoyM1-x-yO 2 In the preparation process (X is more than or equal to 0.80), the preparation process of the precursor accounts for 60 percent, and the advantages and disadvantages of the precursor directly influence the performance of the positive electrode material. The general ternary positive electrode material is formed by mixing secondary spherical particles formed by agglomeration of fine crystal grains of nickel cobalt manganese hydroxide with lithium hydroxide and calcining. At present, a coprecipitation method is mainly adopted for producing a precursor, namely nickel salt, cobalt salt, manganese salt or aluminum salt is prepared into a salt solution according to a certain proportion, cobalt nickel manganese/aluminum hydroxide precipitate is formed under the existence of alkali liquor and complexing agent, and qualified products are obtained through the steps of centrifugal washing, slurrying, drying and the like. During the coprecipitation process, intense stirring causes disorder division of primary particlesThe cloth agglomerates and thus there are different degrees of stress and distortion in the secondary particles sufficient to cause propagating cracks near the grain boundaries inside the particles. The volume change of the high-nickel ternary material in the circulation process is larger, so that the material failure is more easily caused by the expansion of microcracks, the formation of the microcracks and the charge and discharge depth of particles in the long circulation process are directly related, the deeper the charge and discharge depth is, the faster the crack expansion of the material is, the faster the attenuation of the circulation capacity is, the fresh surface is exposed by new cracks continuously appearing in the particles, the side reaction is continuously carried out with electrolyte, and finally the pulverization of the electrode material and the battery failure are caused. Therefore, while improving the nickel content and improving the battery capacity, the problem of cracks in the secondary spherical particles of the high-nickel ternary precursor material is urgently needed to be solved.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a large-particle high-nickel ternary precursor material, and solves the problem that secondary spherical particles of the large-particle high-nickel ternary precursor are easy to crack.
The technical scheme adopted for solving the technical problems is as follows: the preparation method of the large-particle high-nickel ternary precursor material comprises the following steps of:
(1) Preparing a metal salt solution, a precipitator solution and a complexing agent solution, wherein the metal salt solution is an aqueous solution containing nickel salt, cobalt salt and manganese salt;
(2) Adding water, complexing agent solution and precipitant solution into a reaction kettle, preparing reaction kettle bottom solution, introducing nitrogen for replacement, stirring, heating and then keeping constant temperature; introducing a metal salt solution, a complexing agent solution, a precipitator solution and nitrogen into the bottom solution of the reaction kettle, performing coprecipitation reaction to prepare crystal nuclei, and stopping the reaction when the grain diameter D50 of the crystal nuclei is 2-4 mu m;
(3) Adding water, complexing agent solution and precipitant solution into a reaction kettle, preparing reaction kettle bottom solution, introducing nitrogen for replacement, stirring, heating and then keeping constant temperature; adding a metal salt solution, a complexing agent solution and a precipitant solution into the bottom solution of the reaction kettle, simultaneously adding crystal nuclei to continue the coprecipitation reaction until the average particle size of the particles grows to the target particle size, and continuously and stably discharging to obtain a solution containing a precursor material; controlling the content of free nickel ions in the reaction liquid in the reaction kettle to be 10-35 mg/L in the reaction process; in the coprecipitation reaction process, free nickel ions are mainly influenced by the complexation of ammonia concentration and pH value, under the condition that the other conditions are unchanged, the ammonia concentration of a complexing agent is increased, more complex nickel ions are obtained, the higher the content of free nickel ions in a reaction system is, the higher the pH value is, the more complete the coprecipitation of high alkali metal ions is, and the lower the content of free nickel ions is; controlling the free nickel ion content within the pH value and ammonia concentration range by adjusting the pH value and the ammonia concentration range during the reaction;
(4) And (3) stirring the solution containing the precursor material obtained in the step (3) for ageing, washing, drying, screening and removing iron to obtain the ternary precursor material.
Further, when the ternary nickel-cobalt-manganese precursor is prepared, the metal salt solution is an aqueous solution containing nickel salt, cobalt salt and manganese salt, wherein the molar ratio of nickel, cobalt and manganese in the metal salt solution is x (1-x-y), wherein x is more than or equal to 0.8 and less than or equal to 0.95,0.01 and y is more than or equal to 0.1, and the total concentration of metal ions in the metal salt solution is 1.5-2 mol/L; the nickel salt, cobalt salt and manganese salt are at least one of sulfate, nitrate and halogen salt.
Further, the precipitant solution is a sodium hydroxide solution with the mass concentration of 30% -40%, and the complexing agent solution is an ammonia water solution with the mass concentration of 10% -20%.
Further, in the step (2), the reaction temperature is controlled to be 50-80 ℃, the pH value is controlled to be 10-12, the ammonia concentration is controlled to be 1.5-3.5 g/L, and the stirring speed is controlled to be 800-1000 rpm.
Further, in the step (3), the reaction temperature is controlled to be 50-80 ℃, the pH value is controlled to be 10-12, the ammonia concentration is controlled to be 2.5-6.5 g/L, and the stirring rotating speed is controlled to be 200-550 rpm.
Further, the average particle diameter of the particles in the step (3) is a particle size distribution D50 value, and the target particle diameter is 9-11 mu m.
Further, the washing method in the step (4) adopts a centrifuge for alkali washing and water washing, the aged materials are filtered to obtain a filter cake, the obtained filter cake is pulped and washed by 1-3 times of alkali solution, and is washed by 3-6 times of deionized water for times, and after the impurity content reaches the standard, the filter cake is obtained by filtering; drying at 90-140 deg.c for 5-24 hr.
The large-particle high-nickel ternary precursor material is prepared by the preparation method of the large-particle high-nickel ternary precursor material.
The beneficial effects of the invention are as follows: according to the invention, the content of free nickel ions in the reaction solution in the reaction process is controlled to be 10-35 mg/L, so that the stress of the internal structure of the crystal is reduced, and secondary particles of the synthesized ternary precursor material cannot crack due to cracking on a crystal boundary, so that after the ternary precursor material is synthesized into a lithium ion battery, side reactions with the electrolyte are reduced, and pulverization of the electrode material and battery failure can be prevented.
Drawings
FIG. 1 is an SEM of a ternary precursor material obtained according to example 1 of the present invention;
FIG. 2 is an SEM of a ternary precursor material obtained according to example 2 of the present invention;
FIG. 3 is an SEM of a ternary precursor material obtained according to comparative example 1 of the present invention;
fig. 4 shows the ratio performance comparison of ternary precursor materials obtained in example 1, example 2 and comparative example 1 according to the present invention.
Detailed Description
The invention is further illustrated by the following examples and examples.
Example 1:
(1) Preparing nickel sulfate, cobalt sulfate and manganese sulfate into a metal salt solution with the concentration of 2mol/L by adopting pure water; the metal salt solution is an aqueous solution containing nickel salt, cobalt salt and manganese salt; 32% sodium hydroxide solution is used as precipitant solution, and ammonia water solution with the mass concentration of 16% is used as complexing agent solution; the molar ratio of nickel, cobalt and manganese in the metal salt solution is 92:5.5:2.5;
(2) Adding water, complexing agent solution and precipitant solution into a reaction kettle, preparing reaction kettle bottom solution, introducing nitrogen for replacement, starting stirring, heating, keeping the constant temperature at 65 ℃, and setting the stirring rotation speed of the reaction kettle at 950rpm; regulating the pH value of the bottom solution of the reaction kettle to 11.0, and regulating the ammonia concentration to 3g/L; introducing a metal salt solution, a complexing agent solution, a precipitator solution and nitrogen into the bottom solution of the reaction kettle, performing coprecipitation reaction to prepare crystal nuclei, and stopping the reaction when the grain diameter D50 of the crystal nuclei is 3 mu m;
(3) Adding water, complexing agent solution and precipitant solution into a reaction kettle, preparing reaction kettle bottom solution, introducing nitrogen for replacement, stirring, heating, keeping the constant temperature at 65 ℃, and setting the stirring rotation speed of the reaction kettle to 330rpm; adding a metal salt solution, a complexing agent solution and a precipitant solution into the bottom solution of the reaction kettle, simultaneously adding crystal nuclei to continue coprecipitation reaction until the average particle size of the particles grows to be 10 mu m, and continuously and stably discharging to obtain a solution containing a precursor material; filtering the material-taking slurry by using filter paper in the reaction process, detecting the content of metal nickel ions in the obtained filtrate by using ICP, controlling the content of free nickel ions in the reaction liquid in the reaction kettle to be 12mg/L, controlling the pH value of the reaction system to be 10.90-11.10 and the ammonia concentration to be 4.0-5.0 g/L;
(4) And (3) separating the solution containing the precursor material obtained in the step (3) by a centrifugal machine, centrifugally washing the obtained filter cake by using an alkali solution with the weight being 3 times that of the solution, centrifugally washing the filter cake by using pure water with the weight being 6 times that of the solution, dehydrating the filter cake to obtain the filter cake, and drying the filter cake at 90 ℃ for 16 hours to obtain a dried product, namely the ternary precursor material.
The grain diameter of the obtained ternary precursor material product is D50=10.05 mu m, the content of sulfur element in the product is 1779 mu g/g, and a scanning electron microscope shows no crack.
Example 2:
(1) Preparing nickel sulfate, cobalt sulfate and manganese sulfate into a metal salt solution with the concentration of 2mol/L by adopting pure water; the metal salt solution is an aqueous solution containing nickel salt, cobalt salt and manganese salt; 32% sodium hydroxide solution is used as precipitant solution, and ammonia water solution with the mass concentration of 16% is used as complexing agent solution; the molar ratio of nickel, cobalt and manganese in the metal salt solution is 90:6:4;
(2) Adding water, complexing agent solution and precipitant solution into a reaction kettle, preparing reaction kettle bottom solution, introducing nitrogen for replacement, starting stirring, heating, keeping the constant temperature at 65 ℃, and setting the stirring rotation speed of the reaction kettle at 950rpm; regulating the pH value of the bottom solution of the reaction kettle to 11.0, and regulating the ammonia concentration to 3g/L; introducing a metal salt solution, a complexing agent solution, a precipitator solution and nitrogen into the bottom solution of the reaction kettle, performing coprecipitation reaction to prepare crystal nuclei, and stopping the reaction when the grain diameter D50 of the crystal nuclei is 3 mu m;
(3) Adding water, complexing agent solution and precipitant solution into a reaction kettle, preparing reaction kettle bottom solution, introducing nitrogen for replacement, stirring, heating, keeping the constant temperature at 65 ℃, and setting the stirring rotation speed of the reaction kettle to 330rpm; adding a metal salt solution, a complexing agent solution and a precipitant solution into the bottom solution of the reaction kettle, simultaneously adding crystal nuclei to continue coprecipitation reaction until the average particle size of the particles grows to be 10 mu m, and continuously and stably discharging to obtain a solution containing a precursor material; in the reaction process, regularly taking slurry, carrying out suction filtration by using filter paper, detecting the content of metal nickel ions by using ICP (inductively coupled plasma), controlling the content of free nickel ions in the reaction liquid in a reaction kettle to be 15mg/L, controlling the pH value of a reaction system to be 10.90-11.10 and the ammonia concentration to be 4.0-5.0 g/L;
(4) And (3) separating the solution containing the precursor material obtained in the step (3) by a centrifugal machine, centrifugally washing the obtained filter cake by using an alkali solution with the weight being 3 times that of the solution, centrifugally washing the filter cake by using pure water with the weight being 6 times that of the solution, dehydrating the filter cake to obtain the filter cake, and drying the filter cake at 90 ℃ for 16 hours to obtain a dried product, namely the ternary precursor material.
The particle size of the obtained ternary precursor material product is D50=10.mu.m, the content of sulfur element in the product is 1880 mu g/g, and a scanning electron microscope shows no crack.
Example 3:
(1) Preparing nickel sulfate, cobalt sulfate and manganese sulfate into a metal salt solution with the concentration of 2mol/L by adopting pure water; the metal salt solution is an aqueous solution containing nickel salt, cobalt salt and manganese salt; 32% sodium hydroxide solution is used as precipitant solution, and ammonia water solution with the mass concentration of 16% is used as complexing agent solution; the molar ratio of nickel, cobalt and manganese in the metal salt solution is 92:5.5:2.5;
(2) Adding water, complexing agent solution and precipitant solution into a reaction kettle, preparing reaction kettle bottom solution, introducing nitrogen for replacement, starting stirring, heating, keeping the constant temperature at 65 ℃, and setting the stirring rotation speed of the reaction kettle at 950rpm; regulating the pH value of the bottom solution of the reaction kettle to 11.0, and regulating the ammonia concentration to 3g/L; introducing a metal salt solution, a complexing agent solution, a precipitator solution and nitrogen into the bottom solution of the reaction kettle, performing coprecipitation reaction to prepare crystal nuclei, and stopping the reaction when the grain diameter D50 of the crystal nuclei is 3 mu m;
(3) Adding water, complexing agent solution and precipitant solution into a reaction kettle, preparing reaction kettle bottom solution, introducing nitrogen for replacement, stirring, heating, keeping the constant temperature at 65 ℃, and setting the stirring rotation speed of the reaction kettle to 330rpm; adding a metal salt solution, a complexing agent solution and a precipitant solution into the bottom solution of the reaction kettle, simultaneously adding crystal nuclei to continue coprecipitation reaction until the average particle size of the particles grows to be 10 mu m, and continuously and stably discharging to obtain a solution containing a precursor material; in the reaction process, regularly taking slurry, carrying out suction filtration by using filter paper, detecting the content of metal nickel ions by using ICP (inductively coupled plasma), controlling the content of free nickel ions in the reaction liquid in a reaction kettle to be 30mg/L, controlling the pH value of a reaction system to be 10.90-11.10 and the ammonia concentration to be 4.0-5.0 g/L;
(4) And (3) separating the solution containing the precursor material obtained in the step (3) by a centrifugal machine, centrifugally washing the obtained filter cake by using an alkali solution with the weight being 3 times that of the solution, centrifugally washing the filter cake by using pure water with the weight being 6 times that of the solution, dehydrating the filter cake to obtain the filter cake, and drying the filter cake at 90 ℃ for 16 hours to obtain a dried product, namely the ternary precursor material.
The grain diameter of the obtained ternary precursor material product is D50=10.05 mu m, the content of sulfur element in the product is 1750 mu g/g, and a scanning electron microscope shows no crack.
Comparative example 1:
(1) Preparing nickel sulfate, cobalt sulfate and manganese sulfate into a metal salt solution with the concentration of 2mol/L by adopting pure water; the metal salt solution is an aqueous solution containing nickel salt, cobalt salt and manganese salt; 32% sodium hydroxide solution is used as precipitant solution, and ammonia water solution with the mass concentration of 16% is used as complexing agent solution; the molar ratio of nickel, cobalt and manganese in the metal salt solution is 92:5.5:2.5;
(2) Adding water, complexing agent solution and precipitant solution into a reaction kettle, preparing reaction kettle bottom solution, introducing nitrogen for replacement, starting stirring, heating, keeping the constant temperature at 65 ℃, and setting the stirring rotation speed of the reaction kettle at 950rpm; regulating the pH value of the bottom solution of the reaction kettle to 11.0, and regulating the ammonia concentration to 3g/L; introducing a metal salt solution, a complexing agent solution, a precipitator solution and nitrogen into the bottom solution of the reaction kettle, performing coprecipitation reaction to prepare crystal nuclei, and stopping the reaction when the grain diameter D50 of the crystal nuclei is 3 mu m;
(3) Adding water, complexing agent solution and precipitant solution into a reaction kettle, preparing reaction kettle bottom solution, introducing nitrogen for replacement, stirring, heating, keeping the constant temperature at 65 ℃, and setting the stirring rotation speed of the reaction kettle to 330rpm; adding a metal salt solution, a complexing agent solution and a precipitant solution into the bottom solution of the reaction kettle, simultaneously adding crystal nuclei to continue coprecipitation reaction until the average particle size of the particles grows to be 10 mu m, and continuously and stably discharging to obtain a solution containing a precursor material; in the reaction process, regularly taking slurry, carrying out suction filtration by using filter paper, detecting the content of metal nickel ions by using ICP (inductively coupled plasma), controlling the content of free nickel ions in the reaction liquid in a reaction kettle to be 38mg/L, controlling the pH value of a reaction system to be 10.90-11.10 and the ammonia concentration to be 4.0-5.0 g/L;
(4) And (3) separating the solution containing the precursor material obtained in the step (3) by a centrifugal machine, centrifugally washing the obtained filter cake by using an alkali solution with the weight being 3 times that of the solution, centrifugally washing the filter cake by using pure water with the weight being 6 times that of the solution, dehydrating the filter cake to obtain the filter cake, and drying the filter cake at 90 ℃ for 16 hours to obtain a dried product, namely the ternary precursor material.
The particle size of the obtained ternary precursor material product is D50=10μm, the sulfur content of the product is 1880 mug/g, and a scanning electron microscope shows cracks.
The detection method comprises the following steps:
1. the ternary precursor materials obtained in example 1, example 2 and comparative example 1 and lithium carbonate were uniformly mixed in a molar ratio of M (ni+co+mn): M (Li) =1:1.05, pre-sintered at 450 ℃ for 4 hours, taken out, ground, calcined at 800 ℃ for 20 hours, taken out, and crushed to obtain positive electrode materials, respectively designated as A1, A2 and D1, and three positive electrode materials, A1, A2 and D1, were prepared according to the positive electrode materials: conductive carbon: polyvinylidene fluoride (PVDF) =90: 5:5 preparing into slurry to prepare a positive pole piece (the compacted density of the pole piece is 3.3 g/cm) 2 ) And a metal lithium sheet is selected as a negative electrode material, and the 2025 button cell is assembled.
2. Cycle performance: after three circles of activation are performed under the multiplying power of 0.1, 0.5, 1.0, 2.0, 5.0, 8.0 and 10C respectively, the cycle is performed for 100 times by XC multiplying power, the discharge capacity at the 1 st cycle and the discharge capacity at the 100 th cycle are measured respectively, and the 100-time capacity retention rate of the cycle is calculated; the calculation formula is as follows: cycle 100 capacity retention (%) = discharge capacity at cycle 100/discharge capacity at cycle 1 x 100%, specific capacity and cycle retention of the material are obtained; as can be seen from fig. 4 (the lower line in the figure is D1, and the upper two lines almost coincide with each other are A1 and A2), the high-nickel large-particle ternary precursor obtained in example 1 and example 2 does not crack NCM products, and the charge-discharge cycle performance is significantly improved, and after 100 cycles, the capacity retention rate of the high-nickel NCM non-crack positive electrode materials in example 1 and example 2 is higher than that of the high-nickel large-particle ternary positive electrode material in comparative example 1 NCM; compared with the cracking ternary cathode material of the comparative example 1, the cracking-free material particles are reduced to generate side reactions with electrolyte, so that pulverization of the electrode material and failure of the battery are prevented. The high-nickel non-cracking NCM product positive electrode material has more stable cycle performance and obviously improves the multiplying power performance.

Claims (8)

1. The preparation method of the large-particle high-nickel ternary precursor material is characterized by comprising the following steps of:
(1) Preparing a metal salt solution, a precipitator solution and a complexing agent solution, wherein the metal salt solution is an aqueous solution containing nickel salt, cobalt salt and manganese salt;
(2) Adding water, complexing agent solution and precipitant solution into a reaction kettle, preparing reaction kettle bottom solution, introducing nitrogen for replacement, stirring, heating and then keeping constant temperature; introducing a metal salt solution, a complexing agent solution, a precipitator solution and nitrogen into the bottom solution of the reaction kettle, performing coprecipitation reaction to prepare crystal nuclei, and stopping the reaction when the grain diameter D50 of the crystal nuclei is 2-4 mu m;
(3) Adding water, complexing agent solution and precipitant solution into a reaction kettle, preparing reaction kettle bottom solution, introducing nitrogen for replacement, stirring, heating and then keeping constant temperature; adding a metal salt solution, a complexing agent solution and a precipitant solution into the bottom solution of the reaction kettle, simultaneously adding crystal nuclei to continue the coprecipitation reaction until the average particle size of the particles grows to the target particle size, and continuously and stably discharging to obtain a solution containing a precursor material; controlling the content of free nickel ions in the reaction liquid in the reaction kettle to be 10-35 mg/L in the reaction process;
(4) And (3) stirring the solution containing the precursor material obtained in the step (3) for ageing, washing, drying, screening and removing iron to obtain the ternary precursor material.
2. The method for preparing the large-particle high-nickel ternary precursor material according to claim 1, wherein the method comprises the following steps: the metal salt solution is an aqueous solution containing nickel salt, cobalt salt and manganese salt when preparing the nickel-cobalt-manganese ternary precursor, wherein the molar ratio of nickel, cobalt and manganese in the metal salt solution is x (1-x-y), wherein x is more than or equal to 0.8 and less than or equal to 0.95,0.01 and y is less than or equal to 0.1, and the total concentration of metal ions in the metal salt solution is 1.5-2 mol/L; the nickel salt, cobalt salt and manganese salt are at least one of sulfate, nitrate and halogen salt.
3. The method for preparing the large-particle high-nickel ternary precursor material according to claim 1, wherein the method comprises the following steps: the precipitant solution is 30-40% sodium hydroxide solution, and the complexing agent solution is 10-20% ammonia solution.
4. The method for preparing the large-particle high-nickel ternary precursor material according to claim 1, wherein the method comprises the following steps: in the step (2), the reaction temperature is controlled to be 50-80 ℃, the pH value is controlled to be 10-12, the ammonia concentration is controlled to be 1.5-3.5 g/L, and the stirring rotating speed is controlled to be 800-1000 rpm.
5. The method for preparing the large-particle high-nickel ternary precursor material according to claim 1, wherein the method comprises the following steps: in the step (3), the reaction temperature is controlled to be 50-80 ℃, the pH value is controlled to be 10-12, the ammonia concentration is controlled to be 2.5-6.5 g/L, and the stirring rotating speed is controlled to be 200-550 rpm.
6. The method for preparing the large-particle high-nickel ternary precursor material according to claim 1, wherein the method comprises the following steps: the average particle diameter of the particles in the step (3) is the D50 value of the particle size distribution, and the target particle diameter is 9-11 mu m.
7. The method for preparing the large-particle high-nickel ternary precursor material according to claim 1, wherein the method comprises the following steps: the washing method of the step (4) adopts a centrifuge for alkali washing and water washing, the aged materials are filtered to obtain a filter cake, the obtained filter cake is pulped and washed by alkali solution with the weight of 1-3 times, and is washed by deionized water with the weight of 3-6 times, and the filter cake is obtained after the impurity content reaches the standard; drying at 90-140 deg.c for 5-24 hr.
8. A large-particle high-nickel ternary precursor material produced by the method for producing a large-particle high-nickel ternary precursor material of claims 1 to 7.
CN202310223031.2A 2023-03-09 2023-03-09 Preparation method of large-particle high-nickel ternary precursor material and large-particle high-nickel ternary precursor material Pending CN116375104A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310223031.2A CN116375104A (en) 2023-03-09 2023-03-09 Preparation method of large-particle high-nickel ternary precursor material and large-particle high-nickel ternary precursor material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310223031.2A CN116375104A (en) 2023-03-09 2023-03-09 Preparation method of large-particle high-nickel ternary precursor material and large-particle high-nickel ternary precursor material

Publications (1)

Publication Number Publication Date
CN116375104A true CN116375104A (en) 2023-07-04

Family

ID=86964778

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310223031.2A Pending CN116375104A (en) 2023-03-09 2023-03-09 Preparation method of large-particle high-nickel ternary precursor material and large-particle high-nickel ternary precursor material

Country Status (1)

Country Link
CN (1) CN116375104A (en)

Similar Documents

Publication Publication Date Title
CN110048118B (en) High-nickel cobalt lithium manganate single crystal precursor, preparation method thereof and high-nickel cobalt lithium manganate single crystal positive electrode material
CN110534719B (en) Preparation method of aluminum-doped magnesium-nickel-manganese spherical cobaltosic oxide
CN105271441A (en) Preparation method of battery-grade large-grained cobaltosic oxide
WO2023207281A1 (en) Method for preparing magnesium-titanium co-doped cobalt carbonate and use thereof
WO2024066892A1 (en) Manganese-rich oxide precursor, preparation method therefor, and use thereof
CN114349068B (en) Preparation method of large-particle-size nickel-cobalt-aluminum ternary positive electrode material precursor
CN110611098B (en) High-radiation and high-tap-density nickel-cobalt lithium aluminate precursor and preparation method thereof
CN115133003B (en) Sodium ion battery positive electrode material and preparation method thereof
CN108987740B (en) Nickel-cobalt lithium aluminate anode material, preparation method thereof and battery applying nickel-cobalt lithium aluminate anode material
CN113603159A (en) Multilayer aluminum-doped nickel-cobalt-manganese precursor and preparation method thereof
CN115403074B (en) High-nickel type nickel cobalt lithium manganate precursor and preparation method thereof
CN111540898A (en) Preparation method and application of precursor with good primary particle uniformity
CN112838205B (en) Method for recovering fine powder of lithium ion battery cathode material
WO2023179247A1 (en) Ultrahigh-nickel ternary precursor and preparation method therefor
CN105742568B (en) A kind of nickel cobalt aluminum oxide and preparation method thereof
KR102346042B1 (en) Beta-nickel hydroxide doped with aluminum
CN114426313A (en) High-energy-density ternary cathode material and preparation method and application thereof
CN114220959B (en) Preparation method of component-controllable multielement doped high-nickel ternary positive electrode material
CN114927656A (en) Preparation method and application of electrochemical material
CN112952056A (en) Lithium-rich manganese-based composite cathode material and preparation method and application thereof
CN114684874B (en) Doped high-magnification 5-series single crystal precursor and preparation method thereof
CN111661879A (en) Nickel-cobalt-tungsten oxide, preparation method thereof and lithium ion battery
CN116375104A (en) Preparation method of large-particle high-nickel ternary precursor material and large-particle high-nickel ternary precursor material
CN115286050A (en) Ternary precursor material and preparation method thereof
CN115012036A (en) Fine-whisker small-particle-size nickel-cobalt-manganese hydroxide and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
CB02 Change of applicant information

Country or region after: China

Address after: 644200 yangchunba Industrial Park, Jiang'an County, Yibin City, Sichuan Province

Applicant after: YIBIN GUANGYUAN LITHIUM BATTERY CO.,LTD.

Applicant after: Yibin Lithium Treasure New Materials Co.,Ltd.

Address before: 644200 yangchunba Industrial Park, Jiang'an County, Yibin City, Sichuan Province

Applicant before: YIBIN GUANGYUAN LITHIUM BATTERY CO.,LTD.

Country or region before: China

Applicant before: Yibin Libao New Materials Co.,Ltd.