CN114684874B - Doped high-magnification 5-series single crystal precursor and preparation method thereof - Google Patents

Doped high-magnification 5-series single crystal precursor and preparation method thereof Download PDF

Info

Publication number
CN114684874B
CN114684874B CN202210221578.4A CN202210221578A CN114684874B CN 114684874 B CN114684874 B CN 114684874B CN 202210221578 A CN202210221578 A CN 202210221578A CN 114684874 B CN114684874 B CN 114684874B
Authority
CN
China
Prior art keywords
preparing
solution
single crystal
series single
doped high
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.)
Active
Application number
CN202210221578.4A
Other languages
Chinese (zh)
Other versions
CN114684874A (en
Inventor
张燕辉
邢王燕
杜先锋
朱婷婷
王政强
孙宏
宋方亨
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 CN202210221578.4A priority Critical patent/CN114684874B/en
Publication of CN114684874A publication Critical patent/CN114684874A/en
Application granted granted Critical
Publication of CN114684874B publication Critical patent/CN114684874B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G55/00—Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
    • C01G55/002—Compounds containing, besides ruthenium, rhodium, palladium, osmium, iridium, or platinum, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/50—Agglomerated particles
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention discloses a doped high-magnification 5-series monocrystalline precursor and a preparation method thereof, wherein the molecular general formula of the precursor is LiNi 0.5(1‑x‑y) Co 0.2(1‑x‑y) Mn 0.3(1‑x‑y) Ir x Zr y (OH) 2 Wherein 3.5X10 ‑4 ≤x+y≤3.0×10 ‑3 ，4.8×10 ‑5 ＜x＜3.9×10 ‑4 ，3×10 ‑4 ＜y＜3×10 ‑3 And sequentially preparing ternary salt solution, first accompanying liquid, second accompanying liquid, preparing liquid alkali and ammonia water, preparing reaction kettle base solution, enabling main metal ions and doped element ions to perform coprecipitation reaction, filtering to form a filter cake after particles reach a target particle size, washing the filter cake, drying, screening and performing demagnetizing treatment to obtain the precursor. The precursor prepared by the method has high stability of the layered structure, good sphericity, porosity, primary particle crystallization morphology and high rate capability, and the preparation method is favorable for controlling the precision of the content of the final doping element.

Description

Doped high-magnification 5-series single crystal precursor and preparation method thereof
Technical Field
The invention relates to a doped high-magnification 5-series single crystal precursor, in particular to a high-magnification 5-series single crystal precursor simultaneously doped with Ir and Zr and a preparation method thereof.
Background
The molar ratio of nickel in the metal composition of the 5-series single crystal precursor is about 0.5, the capacity is ensured, and the compaction density is high. In addition, due to the monocrystal structure, the prepared positive electrode material can keep equiaxial change of expansion and contraction of crystals in the charge-discharge process, so that the positive electrode material has higher stability of a layered structure, prolonged service life, and improved charge-discharge cut-off voltage and high-temperature cycle performance. Therefore, the preparation of positive electrode materials from 5-series single-crystal type precursors is an excellent research method.
However, due to the cation mixing effect between nickel ions and lithium ions in the ternary positive electrode material, namely Ni 2+ Ion radius of (1) and Li + The radius of the Ni-Li alloy is close to 0.69nm and 0.76nm, ni occupies Li positions easily in the actual circulation process, the problem of Ni/Li mixed discharge is caused, and one Ni obstructs Li at 7 positions + And the material enters the battery, so that the capacity of the battery is attenuated, the capacity and the cycle performance of the material can be gradually reduced, and particularly the material is obviously reduced in the high-rate charge and discharge process. How to further improve the cycle performance at high rate is one direction of research and development by researchers at present.
Many researchers carry out doping modification on the anode material so as to reduce cation mixing and discharging, thereby improving the electrochemical performance of the material.
The main doping elements are Ti, mg, al, etc., and the doping elements can replace the positions of the main elements in the material, so that the LiNi is formed x Co y Mn z O 2 Is increased, thereby increasing the interlayer spacing of the crystal structure, decreasing Li + Migration resistance of (c); and the stability of the crystal structure of the material can be enhanced or the capacity of the material can be increased by some elements, and finally the capacity, the rate capability and the thermal stability of the material are improved. But most of the above are doped with the precursor and TiO 2 Or MgO, and Li 2 CO 3 The mixture is sintered in a reaction furnace after being uniformly mixed, and the doping uniformity in the actual particles is uncontrollable, so that the electrochemical performance of the anode is affected.
Based on this, researchers have mixed doping elements into the material by co-precipitation during the precursor preparation stage, and the precursor synthesis is performed in a solution state, so that the doping uniformity can be greatly improved. In particular, the doping of the large particle precursor, which is difficult to dope by the process of sintering the positive electrode, may not have doping elements at all in the center of the particle after sintering and doping. In addition to the mainstream doping elements, researchers have tried other element doping, such as one or more of Sr, ba, al, mg, zr, ca, la, ce, ti, si, hf, Y, nb, W and Ta in chinese patent CN112794370 a; one or more selected from Mg, W, mo, ag, cu, zr, la, bi, sn, Y, sr in chinese patent CN 111547780B; chinese patent CN113582249a is selected from at least one of beryllium, scandium, titanium, vanadium, aluminum, yttrium, zirconium, niobium, molybdenum, copper, zinc, gallium, indium, tantalum, and tungsten; researchers have also tried doping of Cr, zr, zn, W, nb, ta, V, mo, ru, ir, ca, sr, etc., and have achieved some expected results in terms of doping uniformity. However, not all doping can be performed in the precursor preparation stage, and some metal elements cannot effectively co-precipitate with the main metal element or form precipitates in an alkaline environment, but exist in the form of soluble salts or complex insoluble salts, and the like, so that the doping in the precursor preparation stage is not suitable.
In summary, finding one or more doping metals to reduce the cation mixing effect, stabilize the crystal structure, and achieve the uniformity of the actual doping inside the particles, thereby improving the electrochemical performance of the cathode material, and becoming a technical problem to be solved by those skilled in the art.
Disclosure of Invention
Obviously, in a plurality of doping elements, no research on the technical problems of reducing the cation mixing effect and controlling the actual doping uniformity in the particles by co-doping Ir and Zr is seen, and the ratio and the method for carrying out combined doping on the Ir and Zr are not mentioned, so that the invention provides a high-magnification 5-series single crystal precursor product with a specific Ir and Zr doping ratio and a preparation method thereof.
The technical scheme adopted for solving the technical problems is as follows: a doped high-magnification 5-series monocrystal precursor is characterized in that the molecular general formula is LiNi 0.5(1-x-y) Co 0.2(1-x-y) Mn 0.3(1-x-y) Ir x Zr y (OH) 2 Wherein 3.5X10 -4 ≤x+y≤3.0×10 -3 Wherein 4.8X10 -5 ＜x＜3.9×10 -4 ，3×10 -4 ＜y＜3×10 -3 The doping metal is Ir and Zr, and the precursor is a secondary spherical or spheroidic particle formed by longitudinally stacking elongated hexagonal primary particles; wherein, the primary particles have the length of 0.5-1.5 mu m, the width of 0.05-0.2 mu m, the particle diameter of the secondary spherical particles or the quasi-spherical particles is 3.3-3.8 mu m, and the pore size is 0.1-0.5 mu m; the mass of Ir and the mass of Zr respectively account for 0.01 to 0.08 percent and 0.03 to 0.3 percent of the total mass of the precursor.
Preferably, ir accounts for 0.03 percent of the total mass of the precursor, and Zr accounts for 0.072 percent of the total mass of the precursor, so that the positive electrode rate performance prepared by the precursor is improved most obviously. This is probably due to Ir after the two elements are embedded in the precursor at positions that replace part of the main metal element 4+ Balance due to Ni 2+ The dislocation defect is caused, and Ni can be restrained 2+ Further migration into the lithium layer reduces cation mixing, thereby improving the integrity and stability of the material crystal structure. Compared with Ni-O, co-O and Mn-O bonds, zr-O bonds formed by Zr are more stable, and the crystal structure of the material can be stabilized. However, when the doping elements are excessive, the generation of the inversion defects in the precursor layered structure is induced, and the generation amount of the inversion defects is in linear relation with the doping amount. The proper amount of inversion defects can improve the structural stability of the material, and the material performance is reduced when the doping is excessive.
The preparation method of the doped high-magnification 5-series single crystal precursor comprises the following steps:
(1) Preparing a solution: preparing Ni, co and Mn ternary salt solution according to a designed proportion; preparing a salt solution of Ir as a first companion liquid; preparing a salt solution of Zr as a second companion liquid; preparing an alkali solution; preparing an ammonia water solution;
(2) Preparing a reaction kettle base solution: preparing pure water, alkali solution and ammonia water solution into kettle bottom solution in an inert gas environment;
(3) Coprecipitation reaction: uniformly pumping the ternary salt solution, the first accompanying liquid and the second accompanying liquid, and the alkali solution and the ammonia water into a reaction kettle for coprecipitation reaction until the particles reach the target particle size;
(4) Post-treatment: filtering the precipitate slurry generated by the reaction to form a filter cake, and then washing, drying, screening and demagnetizing the filter cake to obtain the precursor;
wherein the concentration of the metal Ir in the first accompanying liquid is 0.3-2.4 g/L, and the concentration of the metal Zr in the second accompanying liquid is 1.2-12 g/L, and the concentration is selected to be convenient for adapting to the size and flow setting of the equipment. Because the doping amount is small, the concentration of the first accompanying liquid and the second accompanying liquid is not proper to be too large, otherwise, the first accompanying liquid and the second accompanying liquid cannot play a role in coordination with the flow of the ternary salt solution. Under the concentration, the first accompanying liquid and the second accompanying liquid can enter the reaction kettle together with the ternary salt solution at the flow rate of 160 ml/h to 600ml/h, the flow rate of the first accompanying liquid and the flow rate of the second accompanying liquid are controlled to be 1:2.5-50, and finally, the mixing is more uniform.
The first liquid is IrCl 4 ·xH 2 O is added to SO-containing 2 Forming a solution with a metal Ir concentration of 0.3-2.4 g/L in the pure water solution, wherein IrCl 4 ·xH 2 The addition of O can be one or more times, each time IrCl is added 4 ·xH 2 After O, the Ir content in the solution is detected. Wherein, due to IrCl 4 Water is readily absorbed, so x has no definite value and the manufacturer in the labeling of the product of the purchased reagent is also expressed as x.
The second liquid is ZrOCl 2 ·8H 2 O is added to SO-containing 2 Forming a solution with a metal Zr concentration of 1.2-12 g/L in the pure water solution, wherein ZrOCl 2 ·8H 2 The adding mode of O can be one or more times, and ZrOCl is added each time 2 ·8H 2 The Zr content in the solution was measured after O.
The SO 2 Is slowly introduced into pure water, and can be used for preparing the water containing SO at one time 2 Divided into two parts for preparing a first and a second feed-stock solution, respectively, e.g. SO 2 Slowly introducing into 50L of pure waterThe amount is 9L, and the mixture is divided into two parts of 4.5L which are respectively used for preparing a first accompanying liquid and a second accompanying liquid; or preparing SO-containing solution by dividing into two steps 2 Then preparing a first and a second feed-stock solution, respectively, e.g. dividing SO in two 2 Slowly introducing into 25L pure water with an amount of 4.5L to obtain two parts of solution containing SO 2 Is a pure water solution of (a).
Introducing SO into the pure water solution 2 The purpose of (a) is to make the solution a weak acidic solution for suppressing IrCl 4 ·xH 2 O and ZrOCl 2 ·8H 2 And the hydrolysis of O avoids that doping elements enter a reaction kettle in a form of tiny water-insoluble matters after the hydrolysis, are not finally embedded into precursor particles in a coprecipitation mode, but are attached to the surfaces of the precursor particles or suspended in slurry, and the doping elements which are not coprecipitated are lost through the treatment of washing, drying and the like. The concomitant liquid of Ir and Zr is prepared in weak acid environment, so that the doped elements tend to keep ionic state before entering the reaction kettle, and the control of the final precipitation element content accuracy is facilitated. Under the same flow control, the content of the doping element is closer to the design value.
The molar ratio of Ni, co and Mn in the ternary salt solution is Ni:Co:Mn=5:2:3, and the ternary salt solution uses Ni, co and Mn salts as NiSO 4 ·6H 2 O，CoSO 4 ·7H 2 O，MnSO 4 ·H 2 And the concentration of the main metal of the ternary salt solution corresponding to the O is 100-130 g/L. Of course, other proportions of Ni, co, mn may be used, such as: 5:2.5:2.5, 5:1:4, etc.
The concentration of the alkali solution is 6-12 mol/L, the concentration of the ammonia water solution is 6-10 mol/L, and the alkali solution is prepared by dissolving a NaOH precipitator by pure water;
the preparation method of the reaction kettle base solution comprises the steps of injecting 60 percent of pure water with the volume of the reaction kettle into the reaction kettle, starting stirring at 600-900 rpm, heating to 45-65 ℃, and continuously bubbling N with the purity of 99.99 percent into the reaction kettle 2 And adding ammonia water solution and alkali solution into the gas until the ammonia concentration of the system is 0.1-0.2mol/L and the PH value is 11.8-11.9.
In the coprecipitation reaction, the molar ratio of Ir to Zr is 1:3-6, and the preferable molar ratio is 1:5.
In the coprecipitation reaction, the feeding flow rate of the ternary salt solution is 1.5-6L/h, and the feeding flow rates of the first accompanying liquid and the second accompanying liquid are 2-10 ml/min.
In the coprecipitation reaction, the flow rate of an ammonia water solution is controlled to be 70-100 ml/h before the reaction, the flow rate of an alkali solution is controlled to be 600-900 ml/h, the PH value is kept within the range of 11.85+/-0.05, and the ammonia value is kept within the range of 0.1-0.2mol/L for carrying out the nucleation reaction. Increasing the ammonia flow by 20-40 ml per hour from 1h, reducing the alkali flow by 40-80 ml, increasing the ammonia value by 0.05-0.1 mol/L per hour, reducing the PH value by 0.03-0.08 per hour, enabling the ammonia value to reach 0.35-0.45 mol/L when the reaction is carried out for 6-9 h, enabling the PH value of the solution to reach 11.5-11.6, stabilizing the ammonia concentration to be 0.4+/-0.05 mol/L, stabilizing the PH to be 11.55+/-0.05, and enabling the system to enter a stable synthesis stage. The process for controlling the ammonia value and the PH is data summarized by multiple experiments before the research of the invention, and the method can ensure that particles with good initial crystallization state can be formed in the initial nucleation reaction process, and particles with certain sphericity, morphology, tap and specific surface can be formed in the middle and later growth processes.
In the coprecipitation reaction, when the granularity reaches 2.0-2.5 mu m, N is added 2 The air flow is from 0.8 to 1m 3 The ratio of the catalyst/h is reduced to 0.4-0.6 m 3 Introducing air at a fixed flow rate of 5-15L/h, and continuously reacting until the particle size reaches 3.3-3.8 mu m; such control may refine the primary particles and may create a porosity in the precursor particles.
In the post-treatment, the precipitation slurry generated by the precipitation reaction is pumped to a filtering device and is spin-dried to form a filter cake, the filter cake is centrifugally washed by alkali solution with the concentration of 0.5-2 mol/L, the filter cake is washed by pure water, and after the impurity content reaches less than or equal to 200ppm and less than or equal to 1800ppm, the precursor product particles are obtained by drying, screening and demagnetizing.
In the post-treatment, the drying temperature is 90-140 ℃, and the screening mesh number is 300-400.
The beneficial effects of the invention are as follows:
1. the positive electrode prepared by the precursor has more stable multiplying power performance after the Ir and the Zr are simultaneously doped, and particularly when the molar ratio of the Ir to the Zr is 1:5, the multiplying power performance is obviously improved when the ratio of the Ir to the Zr in the total mass of the precursor is 0.03 percent and the ratio of the Ir to the Zr in the total mass of the precursor is 0.072 percent respectively, as shown in figure 11; this is because Ir, zr elements replace the positions of the main elements in the precursor, so that the stability of the layered structure of the precursor is enhanced, while Ir may have a Ni-like effect, and may provide a small capacity for the material by valence variation.
2. According to the invention, ir and Zr are simultaneously doped in the precursor synthesis stage, so that the element distribution is more uniform than that of conventional sintering doping, and the precursor synthesis stage is shown in fig. 7; meanwhile, the precursor has good sphericity, porosity and primary particle crystallization morphology through the micro-oxidation in the middle and later stages of synthesis and the control of reaction parameters, and is shown in fig. 5, 6 and 8.
3. In general, the dissolution of metal salts in pure water is accompanied by hydrolysis, e.g If the doping elements are excessively hydrolyzed before the reaction, the doping elements enter the reaction kettle in a form of tiny water insoluble matters, are not finally embedded into the precursor particles in a coprecipitation mode, and are attached to the surfaces of the precursor particles or suspended in the slurry. These non-co-precipitated doping elements are lost by washing, baking, etc. In the process of preparing the first accompanying liquid and the second accompanying liquid, SO is introduced 2 The weak acid environment is formed, the hydrolysis can be restrained, so that the doped elements tend to keep an ionic state before entering the reaction kettle, and the precision control of the content of the final precipitated elements is facilitated. The doping element content was closer to the design value for the same flow control, see table 6.
Drawings
FIG. 1 shows the morphology of the particles of the product A of example 1 (Ir: zr=1:3, ir-containing 0.02%).
FIG. 2 is the morphology of the B product particles of example 1 (Ir: zr=1:4, ir-containing 0.02%).
FIG. 3 shows the morphology of the particles of the C product of example 1 (Ir: zr=1:5, ir-containing 0.02%).
FIG. 4 is the morphology of the D product particles of example 1 (Ir: zr=1:6, ir-containing 0.02%).
Fig. 5 is the morphology of the E product particles of example 2 (Ir: zr=1:5, ir0.01%).
FIG. 6 is the morphology of the F product particles of example 2 (Ir: zr=1:5, ir-containing 0.03%).
FIG. 7 is a graph showing the Zr and Ir element distribution of the F product particles in example 2.
Fig. 8 is the morphology of the G product particles of example 2 (Ir: zr=1:5, ir0.06%).
FIG. 9 is the particle morphology of the Fn product of comparative example 1 (Ir: zr=1:5, ir-containing 0.03%).
Fig. 10 is the Fm product particle morphology (undoped) of comparative example 2.
Fig. 11 is a comparison of the rate performance of the product after fabrication as a positive electrode and testing.
Detailed Description
The invention will be further described with reference to the drawings and examples.
Example 1:
preparing ternary salt solution with concentration of 2mol/L and molar ratio of Ni to Co to Mn of 5:2:3 by pure water, wherein the ternary salt solution uses Ni, co and Mn salt as NiSO 4 ·6H 2 O，CoSO 4 ·7H 2 O，MnSO 4 ·H 2 O, wherein the main metal concentration of the ternary salt solution is 100-130 g/L; slowly pass through 9L SO 2 To 50L of pure water, 50L of the mixture containing SO 2 After the pure water solution is divided equally, irCl is added again 4 ·xH 2 O、ZrOCl 2 ·8H 2 Adding O-salt into two 25L SO-containing parts respectively 2 After each addition, the element content was measured to prepare a first feed solution having an Ir salt concentration of 0.6g/L and a second feed solution having a Zr salt concentration of 3 g/L.
Preparing NaOH precipitant into 10mol/L alkali solution by pure water, and diluting ammonia water into 9.5mol/L solution.
Injecting 60% pure water into the reaction kettle, stirring at 900rpm, heating to 60deg.C, and bubbling into the kettle with 99.99% N 2 And (3) air.
After nitrogen is blown in for 2 hours, ammonia water solution and alkali solution are added until the ammonia concentration of the system is 0.2mol/L and the PH value is 11.85. According to the requirements that the mass of Ir is 0.02 percent of the total mass of the precursor, the molar ratio of Ir to Zr is 1:3, 1:4, 1:5 and 1:6, the flow rates of the ternary salt solution, the first accompanying liquid and the second accompanying liquid are respectively set, the flow rates of the ammonia solution and the alkali solution are set according to the nucleation and growth requirements, and the ternary salt solution, the first accompanying liquid, the second accompanying liquid, the ammonia solution and the alkali solution are uniformly pumped into a reaction kettle for synthesis reaction. Wherein, the feeding flow rate of the ternary salt solution is 1.5-6L/h, and the feeding flow rates of the first accompanying liquid and the second accompanying liquid are 2-10 ml/min; the flow rate of the ternary salt solution is 1.5-2L/h in the nucleation stage, the stable synthesis stage is 4-6L/h, and the flow rates of the first accompanying liquid and the second accompanying liquid are increased cooperatively when the flow rate of the ternary salt solution is regulated, so that the Ir content in each stage is ensured to be 0.02% in mass ratio. The four experiments were all performed with the same ternary salt solution flow and first companion liquid flow, and the second companion liquid flow was adjusted according to different Ir: zr moles. The process time node, the process ammonia value, the PH value and the like are kept uniform.
The flow rate of the ammonia water solution is controlled to be 70-100 ml/h before the synthesis reaction, the flow rate of the alkali solution is controlled to be 600-900 ml/h, the ammonia value is kept within the range of 0.1-0.2mol/L, and the PH value is kept within the range of 11.85+/-0.05 for the nucleation reaction. Increasing the flow rate of ammonia water solution by 20-40 ml per hour from 1h, reducing the flow rate of alkali solution by 40-80 ml, increasing the ammonia value by 0.05-0.1 mol/L per hour, reducing the PH value by 0.03-0.08 per hour, enabling the ammonia value to reach 0.35-0.45 mol/L when the reaction is carried out for 6-9 h, enabling the PH value of solution to reach 11.5-11.6, stabilizing the ammonia concentration to be 0.4+/-0.05 mol/L, stabilizing the PH to be 11.55+/-0.05, and enabling the system to enter a stable synthesis stage. And after the system enters a stabilizing and forming stage, increasing the ternary salt flow once every 4 hours, increasing 1-2L/h of each adjusting node, and synchronously adjusting the flow of the first accompanying liquid and the flow of the second accompanying liquid according to the process design until the flow of the ternary salt solution reaches 5-6L/h, wherein the flow of the accompanying liquid reaches 3-8 ml/min, namely the stabilizing flow. When the liquid level reaches 85% -90% of the kettle body, the reaction is carried out by a batch method.
When the granularity reaches 2.0-2.5 mu m, N is added 2 The air flow is from 0.8 to 1m 3 The ratio of the catalyst/h is reduced to 0.4-0.6 m 3 And/h, introducing air at a fixed flow rate of 5-15L/h, and continuously reacting until the particle size reaches 3.3-3.8 mu m.
Four slurries A (Ir: zr=1:3), B (Ir: zr=1:4), C (Ir: zr=1:5) and D (Ir: zr=1:6) are put into an aging kettle for aging for 4 hours, then pumped into a centrifuge and spin-dried to form a filter cake, the filter cake is centrifugally washed by 1mol/L alkali solution with 8 times of weight, centrifugally washed by 6 times of pure water with the weight, after the impurity content is less than or equal to 200ppm and S is less than or equal to 1800ppm, the filter cake is dried in an oven with 130 ℃, after the water content is qualified, the filter cake is sieved by a sieve tray with 300 meshes, and finally the magnetic removal is carried out by an iron remover with 12000GS, thus obtaining A, B, C, D four precursors, and the product shapes of the four precursors are respectively shown in figures 1, 2, 3 and 4. As can be seen from the figures, the A, B, C, D particles have similar crystal forms, and the primary particles are in an elongated shape, so that the particles have better sphericity and more uniform porosity. The product A is the first test, the process control is not complete and fine, the sphericity is not as good as that of other three products, and the pore size is not uniform. The multiplying power performance of the four products can be higher than that of the undoped product correspondingly in the charge-discharge cycle, which shows that the structural stability of the precursor can be improved after Ir and Zr are doped, and the cation mixing effect is reduced to a certain extent.
The molecular general formula of the four products is LiNi 0.5(1-x-y) Co 0.2(1-x-y) Mn 0.3(1-x-y) Ir x Zr y (OH) 2 Wherein, the method comprises the steps of, wherein,
3.5×10 -4 ≤x+y≤3.0×10 -3 wherein 4.8X10 -5 ＜x＜3.9×10 -4 ，3×10 -4 ＜y＜3×10 -3 The product particles are secondary spherical particles or quasi-spherical particles which are formed by longitudinally stacking elongated hexagonal primary particles, wherein four product particle indexes are shown in the following table 1.
Table 1: A. b, C, D index table for four product particles
According to Li 2 CO 3 And (3) sintering the A, B, C, D precursor and lithium in a molar ratio of 4% -8% in a sintering furnace for 2 hours, wherein the primary sintering temperature is 400 ℃, the heating rate is 15 ℃/min, cooling, taking out, grinding and dispersing, calcining for 12 hours at 750 ℃, the heating rate is 25 ℃/min, cooling, taking out and crushing, finally obtaining anode materials A1, B1, C1 and D1, and then assembling the anode materials into a button cell for testing the rate performance. The results show that the rate performance is optimal when the molar ratio is Ir:Zr=1:5.
Further, the mass of Ir is selected to be 0.01%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07% and 0.08% of the total mass of the precursor, the precursor and the positive electrode material are prepared according to the above method according to the requirements that the molar ratio of Ir to Zr is 1:3, 1:4, 1:5 and 1:6, the morphology of the prepared precursor particles is similar to that of A, B, C, D, and the positive electrode assembly prepared by using the particles is similar to the result of multiplying power performance test of the button cell.
Example 2:
further, the precursor was prepared in the same manner as in example 1, except that the molar ratio of Ir: zr=1:5 was 0.01%, 0.03%, and 0.06% by mass of Ir based on the total mass of the precursor.
Three slurries E (Ir0.01%, zr0.024%), F (Ir0.03%, zr0.072%), G (Ir0.06%, zr0.144%) generated by the reaction are put into an aging kettle for aging for 4 hours, then pumped into a centrifuge and spin-dried to form a filter cake, the filter cake is centrifugally washed by 1mol/L alkali solution with the weight of 8 times, centrifugally washed by pure water with the weight of 6 times for a plurality of times, and the filter cake is dried in an oven at 130 ℃ after the impurity content reaches the standard; and screening the qualified water by using a 300-mesh screen disc, and finally performing demagnetization by using a 12000GS iron remover to obtain three precursors of E, F, G, wherein the product morphology is respectively shown in figures 5, 6 and 8. From the results, the crystal forms of the E, F, G product particles are similar, and the primary particles are slender, so that the product has good sphericity and uniform porosity. In addition, it can be observed from fig. 7 that Zr and Ir elements in the F product are uniformly distributed on the spherical particles.
The molecular general formula of the three products is LiNi 0.5(1-x-y) Co 0.2(1-x-y) Mn 0.3(1-x-y) Ir x Zr y (OH) 2 Wherein 3.5X10 -4 ≤x+y≤3.0×10 -3 Wherein 4.8X10 -5 ＜x＜3.9×10 -4 ，3×10 -4 ＜y＜3×10 -3 The particles are secondary spherical particles or quasi-spherical particles which are formed by longitudinally stacking elongated hexagonal primary particles, wherein three product particle indexes are shown in the following table 2.
Table 2: E. f, G index table for three products
According to Li 2 CO 3 The E, F, G precursor and lithium are sintered in a sintering furnace for 2 hours according to the molar ratio of 4% -8%, the primary sintering temperature is 400 ℃, and the heating rate is 15 ℃/min; taking out the mixture after cooling, grinding and dispersing, and calcining at 750 ℃ for 12 hours at a heating rate of 25 ℃/min. And cooling, taking out and crushing to finally obtain positive electrode materials E1, F1 and G1, and then assembling the positive electrode materials into a button cell for rate performance test. The results show that the rate performance is optimal when the mass ratio of Ir is 0.03%.
Further, according to the molar ratio of Ir to zr=1:5, the mass of Ir is selected to be 0.02%, 0.04% and 0.05% of the total mass of the precursor, the precursor and the positive electrode material are prepared according to the method, the morphology of the prepared product particles is similar to that of E, F, G particles, and the positive electrode prepared by using the particles is assembled into a button cell to perform the rate performance test.
Comparative example 1: the first and second companion liquids were not formulated for testing in a weak acid environment.
When preparing companion liquidIrCl is added to 4 ·xH 2 O、ZrOCl 2 ·8H 2 O was added to 50L of pure water to prepare a first feed solution having an Ir salt concentration of 0.6g/L and a second feed solution having a Zr salt concentration of 3g/L, respectively. The remaining procedure was consistent with the "F" product of "example 2" (Ir: zr=1:5, ir-containing 0.03%).
And (3) placing the slurry generated by the reaction into an ageing kettle for ageing for 4 hours, and then pumping the slurry into a centrifugal machine and spin-drying the slurry to obtain a filter cake. The filter cake was centrifugally washed with 8 times by weight of 1mol/L alkali solution and then with 6 times by weight of pure water. And after the impurity content reaches the standard, feeding the mixture into a baking oven at 130 ℃ for baking. And screening with a 300-mesh screen tray after the moisture is qualified, and finally, performing demagnetization with a 12000GS iron remover to obtain an Fn precursor, wherein the morphology of the Fn precursor is shown in figure 9. From the figure, the Fn appearance is similar to that of an F product, the crystallization form of the particles is good, and the primary particles are slender and have good sphericity and uniform porosity.
The molecular general formula of Fn product particles is LiNi 0.5(1-x-y) Co 0.2(1-x-y) Mn 0.3(1-x-y) Ir x Zr y (OH) 2 Wherein 3.5X10 -4 ≤x+y≤3.0×10 -3 Wherein 4.8X10 -5 ＜x＜3.9×10 -4 ，3×10 -4 ＜y＜3×10 -3 The particles are secondary spherical particles or quasi-spherical particles which are longitudinally stacked by elongated hexagonal primary particles, wherein the indexes of Fn product particles are shown in the following table 3.
Table 3: fn product particle index table
According to Li 2 CO 3 The precursor and lithium are sintered in a sintering furnace for 2 hours at a molar ratio of 4% -8% excess, the primary sintering temperature is 400 ℃, and the heating rate is 15 ℃/min; and cooling, taking out, grinding and dispersing, calcining for 12 hours at 750 ℃, heating at a rate of 25 ℃/min, cooling, taking out and crushing, finally obtaining a positive electrode material Fn1, and then assembling into a button cell for multiplying power performance test. The results show that the multiplying power performance is alsoThe method has the advantages that the improvement is realized, but the improvement is not optimal, the design value is compared, and the doping element content is slightly lower than that of an F product.
Comparative example 2: no accompanying liquid was disposed and no doping test was performed.
The precursor was prepared as in example 1, omitting the first and second dope preparation steps, i.e., without doping, to prepare a precursor slurry.
Placing the slurry generated by the reaction into an ageing kettle for ageing for 4 hours, then pumping the slurry into a centrifugal machine and spin-drying the slurry to obtain a filter cake, centrifugally washing the filter cake by using 1mol/L alkali solution with the weight being 8 times that of the slurry, centrifugally washing the filter cake by using pure water with the weight being 6 times that of the slurry for several times, feeding the filter cake into a baking oven with the temperature of 130 ℃ for drying after the impurity content reaches the standard, sieving the filter cake with a 300-mesh sieve tray after the water content is qualified, and finally carrying out demagnetization by using a 12000GS iron remover to obtain the Fm precursor, wherein the Fm precursor has the morphology as shown in figure 10, has good grain crystallization morphology, and the primary grains are in an elongated shape and have good sphericity and uniform porosity.
The molecular formula of the Fm product particles is LiNi 0.5 Co 0.2 Mn 0.3 (OH) 2 The Fm product particles are secondary spherical particles or quasi-spherical particles which are formed by longitudinally stacking elongated hexagonal primary particles, wherein the Fm product particles are indicated in the following table 4.
Table 4: fm product particle index table
According to Li 2 CO 3 The precursor and lithium are sintered in a sintering furnace for 2 hours at a molar ratio of 4% -8% excess, the primary sintering temperature is 400 ℃, and the heating rate is 15 ℃/min; and cooling, taking out, grinding and dispersing, calcining for 12 hours at 750 ℃, heating at a rate of 25 ℃/min, cooling, taking out and crushing, finally obtaining a positive electrode material Fm1, and then assembling into a button cell for rate performance test. The result shows that the high rate performance of the material is obviously reduced compared with the doped positive electrode material.
The detection method comprises the following steps:
the nine positive electrode materials A1, B1, C1, D1, E1, F1, G1, fn1, fm1 prepared in examples 1 to 2 and comparative examples 1 to 2 were mixed with a conductive agent, a dispersing agent, and the like, respectively, according to a certain mass: 25g of positive electrode material +10g of PVDF glue (17.18 g of NMP mixed with 1gKF 9700) +3.5g of conductive agent slurry (10 g of XC-72 conductive agent, 7.5g of dispersant +50g of NMP) +0.05g of maleic acid +0.8g of KS6L. The coating material is obtained after uniform mixing.
Coating the material on a positive pole piece to prepare the anode plate with the surface density of 12mg/cm 2 Then cut into wafers of 14mm diameter. The lithium metal sheet was used as a negative electrode, and after drying, a button cell of CR2016 was assembled in a glove box.
And (3) testing the cycle performance: by LiPF 6 As a solute, EC: DEC: dmc=1:1:1v% mixed solution was used as a solvent to prepare a 1M electrolyte, and the coin cell was charged and discharged twice at 0.1C and 1 time at 0.5C, respectively, and then charged at 0.5C, and then discharged once at 1.0C, 2.0C, and 5.0C, respectively, to activate. Finally, the process is respectively circulated for 100 times under the multiplying power of 0.1C, 0.5C, 1C, 2C and 5C, and the cut-off voltage is 4.5V. The discharge capacity at the 1 st cycle and the discharge capacity at the 100 th cycle were measured, respectively, and the capacity retention rate was calculated. The calculation formula is as follows: 100 cycles of capacity retention (%) =discharge capacity at 100 th cycle/(discharge capacity at 1 st cycle × 100%. Specific capacity and cycle retention of the material were obtained, and electrochemical properties after product testing are shown in table 5 and fig. 11.
Table 5: product electrochemical test result table
The comparison of the rate performance after the product test is shown in fig. 11, and it can be seen from the results of table 1 and fig. 11: compared with undoped product Fm, the high-rate performance of the high-rate 5-series monocrystalline precursor prepared by doping Ir and Zr is obviously improved. The F1 product has optimal multiplying power performance, and the corresponding precursor F is characterized in that Ir:Zr=1:5, contains Ir0.03 percent and Zr0.076 percent, and the accompanying liquid is configured in a weak acid environment; compared with Fn products with liquid inlet prepared under conventional operation, the contents of Ir in the Fn products are respectively 0.0308% and 0.0278%, the contents of Zr in the Fn products are respectively 0.0771% and 0.0682%, the contents of doping elements in the F products are obviously closer to design values (Ir: 0.03% and Zr: 0.076%), and the final doping contents are more accurate, as shown in Table 6. The energy spectrum scanning of the precursor F shows that the doping of Ir and Zr in the precursor preparation stage can ensure the uniformity of element distribution.
Table 6: final doping content comparison table of F product and Fn product particles

Claims (23)

1. A doped high-magnification 5-series single crystal precursor is characterized in that: the molecular general formula is LiNi 0.5(1-x-y) Co 0.2(1-x-y) Mn 0.3(1-x-y) Ir x Zr y (OH) 2 Wherein 3.5X10 -4 ≤x+y≤3.0×10 -3 Wherein 4.8X10 -5 ＜x＜3.9×10 -4 ，3×10 -4 ＜y＜3×10 -3 The doping metal is Ir and Zr, and the precursor is a secondary spherical or spheroid particle formed by longitudinally stacking elongated hexagonal primary particles.
2. The doped high-magnification 5-series single crystal precursor according to claim 1, wherein: the primary particles are 0.5-1.5 mu m long and 0.05-0.2 mu m wide, the particle size of the secondary spherical particles or quasi-spherical particles is 3.3-3.8 mu m, and the pore size is 0.1-0.5 mu m.
3. The doped high-magnification 5-series single crystal precursor according to claim 1, wherein: the mass of Ir and the mass of Zr respectively account for 0.01-0.08% and 0.03-0.3% of the total mass of the precursor.
4. The doped high-magnification 5-series single crystal precursor according to claim 1, wherein: the mass of Ir and the mass of Zr respectively account for 0.03 percent and 0.072 percent of the total mass of the precursor.
5. The method for preparing a doped high-magnification 5-series single crystal precursor according to claim 1, 2, 3 or 4, comprising the steps of:
preparing a solution: preparing Ni, co and Mn ternary salt solution according to a designed proportion; preparing a salt solution of Ir as a first companion liquid; preparing a salt solution of Zr as a second companion liquid; preparing an alkali solution; preparing an ammonia water solution;
preparing a reaction kettle base solution: preparing pure water, alkali solution and ammonia water solution into reaction kettle base solution in an inert gas environment;
coprecipitation reaction: uniformly pumping the ternary salt solution, the first accompanying liquid and the second accompanying liquid, and the alkali solution and the ammonia water into a reaction kettle for coprecipitation reaction until the particles reach the target particle size;
post-treatment: filtering the precipitate slurry generated by the reaction to form a filter cake, and then washing, drying, screening and demagnetizing the filter cake to obtain the precursor;
the method is characterized in that: the concentration of metal Ir in the first accompanying liquid is 0.3-2.4 g/L, the concentration of metal Zr in the second accompanying liquid is 1.2-12 g/L, and in the coprecipitation reaction, the flow rate of the first accompanying liquid and the flow rate of the second accompanying liquid are controlled to be 1:2.5-50 with the flow rate ratio of the ternary salt solution.
6. The method for preparing a doped high magnification 5-series single crystal precursor according to claim 5, wherein: the first liquid is IrCl 4 ·xH 2 O is added to SO-containing 2 Is formed in pure water solution of ZrOCl 2 ·8H 2 O is added to SO-containing 2 Is formed in a pure water solution of (2), said SO-containing 2 Is to make SO 2 Slowly introducing the mixture into pure water to form the mixture, and dividing the mixture into two parts to prepare a first accompanying liquid and a second accompanying liquid.
7. The method for preparing a doped high magnification 5-series single crystal precursor according to claim 5, wherein: the first liquid is IrCl 4 ·xH 2 O is added to SO-containing 2 Forming a solution with a metal Ir concentration of 0.3-2.4 g/L in the pure water solution, wherein IrCl 4 ·xH 2 The addition of O is one or more times, each time IrCl is added 4 ·xH 2 After O, the Ir content in the solution is detected.
8. The method for preparing a doped high magnification 5-series single crystal precursor according to claim 5, wherein: the second liquid is ZrOCl 2 ·8H 2 O is added to SO-containing 2 Forming a solution with a metal Zr concentration of 1.2-12 g/L in the pure water solution, wherein ZrOCl 2 ·8H 2 The adding mode of O is one or more times, and ZrOCl is added each time 2 ·8H 2 The Zr content in the solution was measured after O.
9. The method for preparing a doped high magnification 5-series single crystal precursor according to claim 7, wherein: the said SO-containing 2 Is to make SO 2 Slowly introducing into 25L of pure water to form the product, wherein the introducing amount is 4.5L.
10. The method for preparing a doped high magnification 5-series single crystal precursor according to claim 8, wherein: the said SO-containing 2 Is to make SO 2 Slowly introducing into 25L of pure water to form the product, wherein the introducing amount is 4.5L.
11. The method for preparing a doped high magnification 5-series single crystal precursor according to claim 5, wherein: the mole ratio of Ni, co and Mn in the ternary salt solution is Ni to Co to Mn=5 to 2 to 3.
12. The method for preparing a doped high magnification 5-series single crystal precursor according to claim 5, wherein: the Ni, co and Mn salts used in the ternary salt solution are NiSO 4 ·6H 2 O，CoSO 4 ·7H 2 O，MnSO 4 ·H 2 O。
13. The method for preparing a doped high magnification 5-series single crystal precursor according to claim 5, wherein: the concentration of the alkali solution is 6-12 mol/L, and the concentration of the ammonia water solution is 6-10 mol/L.
14. The method for preparing a doped high magnification 5-series single crystal precursor according to claim 13, wherein: the alkali solution is prepared by dissolving a NaOH precipitator by pure water.
15. The method for preparing a doped high magnification 5-series single crystal precursor according to claim 5, wherein: the preparation method of the reaction kettle base solution comprises the following steps: injecting 60% pure water with the volume of the reaction kettle, starting stirring at 600-900 rpm, heating to 45-65 ℃, and continuously bubbling N with the purity of 99.99% into the kettle 2 And adding ammonia water solution and alkali solution into the gas until the ammonia concentration of the system is 0.1-0.2mol/L and the pH value is 11.8-11.9.
16. The method for preparing a doped high magnification 5-series single crystal precursor according to claim 5, wherein: the molar ratio of Ir to Zr in the coprecipitation reaction is 1:3-6.
17. The method for preparing a doped high magnification 5-series single crystal precursor according to claim 16, wherein: the molar ratio of Ir to Zr in the coprecipitation reaction is 1:5.
18. The method for preparing a doped high magnification 5-series single crystal precursor according to claim 5, wherein: in the coprecipitation reaction, the feeding flow rate of the ternary salt solution is 1.5-6L/h, and the feeding flow rates of the first accompanying liquid and the second accompanying liquid are 2-10 mL/min.
19. The method for preparing a doped high magnification 5-series single crystal precursor according to claim 5, wherein: in the coprecipitation reaction, the flow rate of an ammonia water solution is controlled to be 70-100 mL/h before the reaction, the flow rate of an alkali solution is controlled to be 600-900 mL/h, the pH value is kept to be 11.85+/-0.05, the ammonia value is 0.1-0.2mol/L, the nucleation reaction is carried out, the ammonia flow rate is increased by 20-40 mL per hour from 1h, the alkali flow rate is reduced by 40-80 mL, the ammonia value is increased by 0.05-0.1 mol/L per hour, the pH value is reduced by 0.03-0.08 per hour, the ammonia value reaches 0.35-0.45 mol/L when the reaction is carried out for 6-9 h, the pH value of the solution reaches 11.5-11.6, then the ammonia concentration is stabilized to be 0.4+/-0.05 mol/L, the pH value is stabilized to be 11.55+/-0.05, and the system is enabled to enter a stable synthesis stage.
20. The method for preparing a doped high magnification 5-series single crystal precursor according to claim 5, wherein: in the coprecipitation reaction, when the granularity reaches 2.0-2.5 mu m, N is added 2 The air flow is from 0.8 to 1m 3 The/h is reduced to 0.4-0.6 m 3 And (h) introducing air at a fixed flow rate of 5-15L/h, and continuously reacting until the particles reach the target particle size.
21. The method for preparing a doped high magnification 5-series single crystal precursor according to claim 20, wherein: the target particle size is 3.3-3.8 mu m.
22. The method for preparing a doped high magnification 5-series single crystal precursor according to claim 5, wherein: in the post-treatment, the precipitation slurry generated by the coprecipitation reaction is pumped to a filtering device and is spin-dried to form a filter cake, the filter cake is centrifugally washed by alkali solution with the concentration of 0.5-2 mol/L, the filter cake is washed by pure water, and after the impurity content reaches less than or equal to 200ppm and less than or equal to 1800ppm, the precursor product particles are obtained by drying, screening and demagnetizing.
23. The method for preparing a doped high magnification 5-series single crystal precursor according to claim 5, wherein: in the post-treatment, the drying temperature is 90-140 ℃, and the screening mesh number is 300-400.
CN202210221578.4A 2022-03-08 2022-03-08 Doped high-magnification 5-series single crystal precursor and preparation method thereof Active CN114684874B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210221578.4A CN114684874B (en) 2022-03-08 2022-03-08 Doped high-magnification 5-series single crystal precursor and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210221578.4A CN114684874B (en) 2022-03-08 2022-03-08 Doped high-magnification 5-series single crystal precursor and preparation method thereof

Publications (2)

Publication Number Publication Date
CN114684874A CN114684874A (en) 2022-07-01
CN114684874B true CN114684874B (en) 2023-08-08

Family

ID=82136661

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210221578.4A Active CN114684874B (en) 2022-03-08 2022-03-08 Doped high-magnification 5-series single crystal precursor and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114684874B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117276534B (en) * 2023-11-21 2024-02-13 宜宾光原锂电材料有限公司 High-cycle positive electrode material precursor, preparation method thereof, positive electrode material and battery

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1135097A (en) * 1994-10-21 1996-11-06 佳能株式会社 Improved anode, rechargeable battery and method for mfg. anode above mentioned
CN101285197A (en) * 2008-05-29 2008-10-15 金川集团有限公司 Preparing method for precursor of lithium ionic cell positive material
CN101379637A (en) * 2006-04-07 2009-03-04 三菱化学株式会社 Lithium transition metal-based compound powder for positive electrode material in lithium rechargeable battery, method for manufacturing the powder, spray dried product of the powder, firing precursor
CN105655144A (en) * 2016-01-08 2016-06-08 丹东思诚科技有限公司 Preparation method for preparing lithium-rich composite cathode material of lithium ion super capacitor
CN107151142A (en) * 2017-05-26 2017-09-12 中电科技德清华莹电子有限公司 A kind of polycrystal material synthetic method of high-melting-point doped chemical
AU2020101817A4 (en) * 2020-08-14 2020-10-01 Foshan University Mg-Zr co-doped high nickel ternary cathode material and preparation method and application thereof
CN112794378A (en) * 2021-01-04 2021-05-14 昆山宝创新能源科技有限公司 Lithium-rich manganese-based doped positive electrode material and preparation method and application thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1135097A (en) * 1994-10-21 1996-11-06 佳能株式会社 Improved anode, rechargeable battery and method for mfg. anode above mentioned
CN101379637A (en) * 2006-04-07 2009-03-04 三菱化学株式会社 Lithium transition metal-based compound powder for positive electrode material in lithium rechargeable battery, method for manufacturing the powder, spray dried product of the powder, firing precursor
CN101285197A (en) * 2008-05-29 2008-10-15 金川集团有限公司 Preparing method for precursor of lithium ionic cell positive material
CN105655144A (en) * 2016-01-08 2016-06-08 丹东思诚科技有限公司 Preparation method for preparing lithium-rich composite cathode material of lithium ion super capacitor
CN107151142A (en) * 2017-05-26 2017-09-12 中电科技德清华莹电子有限公司 A kind of polycrystal material synthetic method of high-melting-point doped chemical
AU2020101817A4 (en) * 2020-08-14 2020-10-01 Foshan University Mg-Zr co-doped high nickel ternary cathode material and preparation method and application thereof
CN112794378A (en) * 2021-01-04 2021-05-14 昆山宝创新能源科技有限公司 Lithium-rich manganese-based doped positive electrode material and preparation method and application thereof

Also Published As

Publication number Publication date
CN114684874A (en) 2022-07-01

Similar Documents

Publication Publication Date Title
CN110127777B (en) Wet zirconium-doped nickel-cobalt-aluminum ternary precursor with gradient concentration and preparation method thereof
WO2022227903A1 (en) High-nickel precursor and preparation method therefor, and high-nickel positive electrode material and preparation method therefor
CN110518220A (en) A kind of nickelic gradient nickel cobalt manganese aluminium quaternary positive electrode and preparation method
CN115000399B (en) Spherical-like sodium ion battery positive electrode material, preparation method thereof and sodium ion battery
CN109686970A (en) A kind of no cobalt richness lithium tertiary cathode material NMA and preparation method thereof
CN111170377A (en) Preparation method of lithium-rich manganese-based positive electrode material
WO2024066892A1 (en) Manganese-rich oxide precursor, preparation method therefor, and use thereof
CN107963672B (en) The preparation method of partial size nickel cobalt manganese hydroxide in a kind of coarse-grain palpus
CN114349068B (en) Preparation method of large-particle-size nickel-cobalt-aluminum ternary positive electrode material precursor
CN113387399A (en) High-nickel ternary positive electrode material precursor and preparation method thereof
CN111540898A (en) Preparation method and application of precursor with good primary particle uniformity
WO2024066445A1 (en) Precursor for sodium-ion battery positive electrode material and preparation method therefor, sodium-ion battery positive electrode material, sodium-ion battery, and electrical device
CN113644272A (en) Cerium-bismuth composite oxide doped lithium ion battery positive electrode material and preparation method thereof
KR102346042B1 (en) Beta-nickel hydroxide doped with aluminum
CN113603153A (en) Tungsten-doped high-nickel cobalt-free precursor and preparation method thereof
CN114583141A (en) Precursor material with three-layer structure, preparation method thereof and anode material
CN114684874B (en) Doped high-magnification 5-series single crystal precursor and preparation method thereof
CN114220959B (en) Preparation method of component-controllable multielement doped high-nickel ternary positive electrode material
CN114620777A (en) Ultrahigh nickel ternary precursor and preparation method thereof
CN114426313A (en) High-energy-density ternary cathode material and preparation method and application thereof
CN114455647A (en) Preparation method of surface confinement treatment full-concentration gradient quaternary high-nickel NCMA positive electrode material
CN116588993B (en) Ternary precursor, preparation method thereof, lithium battery positive electrode material and lithium battery
WO2024055513A1 (en) Positive electrode material precursor, positive electrode material, method for preparing same, and use thereof
CN112624209A (en) Na-Ti-Mg co-doped ternary material and preparation method and application thereof
CN112279310A (en) Preparation method of ternary cathode material precursor

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
GR01 Patent grant
GR01 Patent grant