CN115133016A - Preparation method of high-nickel single crystal cathode material of lithium ion battery - Google Patents

Preparation method of high-nickel single crystal cathode material of lithium ion battery Download PDF

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CN115133016A
CN115133016A CN202110314205.7A CN202110314205A CN115133016A CN 115133016 A CN115133016 A CN 115133016A CN 202110314205 A CN202110314205 A CN 202110314205A CN 115133016 A CN115133016 A CN 115133016A
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sintering
precursor
single crystal
temperature
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王帅刚
韩玉振
王霞霞
董林涛
安孝坤
张洁
刘逸群
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Wanhua Chemical Group Co Ltd
Wanhua Chemical Sichuan Co Ltd
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Wanhua Chemical Sichuan Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy

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Abstract

The invention belongs to the technical field of anode materials, and particularly relates to a preparation method of a high-nickel single crystal anode material of a lithium ion battery. Firstly, sintering a precursor, a modifier and a flocculating agent for the first time, and then mixing the modified precursor and a lithium source for the second time to obtain the high-nickel single crystal cathode material. The method of the invention keeps the polycrystalline morphology of the precursor during one-time sintering, and the formed fast ion conductor can also greatly improve the ion diffusion rate in the solid phase reaction, thereby obviously reducing the sintering temperature and time of the high nickel single crystal. In addition, the fast ion conductor has large molecular weight and stable structure, and is distributed on the surface of the particles to prevent the surface structure of the single crystal particles from being degraded at high temperature, and the concentration gradient doping and surface coating of the particles are synchronously completed along with the sintering process, so that the electrochemical performance of the material is effectively improved.

Description

Preparation method of high-nickel single crystal cathode material of lithium ion battery
Technical Field
The invention belongs to the technical field of anode materials, and particularly relates to a preparation method of a high-nickel single crystal anode material of a lithium ion battery.
Background
In recent years, with the popularization of the green economic model and the increasing environmental pressure, the new energy industry is developed vigorously. The industries, such as the travel transportation field, have developed a trend toward electric driving, which is the main development direction, and the large-scale application of lithium ion batteries follows. With the wide popularization of lithium ion batteries, the market demand for lithium ion batteries with high energy density, good cycle stability and excellent safety performance is also increasing. The positive electrode material is used as a core material of a lithium ion battery system, and the property of the positive electrode material directly determines the working performance of the battery and even an automobile. The conventional positive electrode material is a polycrystalline secondary spherical particle in which primary particles are sintered and stacked, and which includes numerous grain boundaries, and has isotropic characteristics. During the lithium ion deintercalation process, the crystal lattice of the primary particles may periodically expand and contract, and thus the polycrystalline material may continuously accumulate structural stress generated by the lattice change at the grain boundary, thereby causing pulverization and breakage of the particles. On one hand, the phenomenon can cause the aggravation of side reactions (such as gas generation, heat generation and the like) between the surface of the material and the electrolyte, on the other hand, partial particles can not contact with a conductive network, and water jump occurs in the capacity, and the problems can directly influence the safety performance and the cycle performance of the battery.
In order to solve these problems of the polycrystalline secondary sphere material, it was found that various items can be obtained by promoting the secondary recrystallization between the primary particles by increasing the sintering temperature and extending the sintering timeAn anisotropic single crystal material. Single crystal materials have many significant advantages over polycrystalline materials, such as: the contact area with the electrolyte is small, and the side reaction is less; the method has the advantages of no crystal boundary, good stress release, good particle integrity, and good avoidance of the problems of the polycrystalline material in safety and cycling stability. However, unlike the preparation process of the secondary sphere polycrystalline material, the single crystal material generally needs to be sintered at a higher temperature for a longer time to accelerate the diffusion rate of ions and promote fusion between primary particles. Such process conditions are used to prepare single crystal positive electrode materials (e.g., LiNi) with low nickel content 0.5 Co 0.2 Mn 0.3 O 2 ) And when the material is used, the performance of the material cannot be greatly influenced. But when preparing high nickel single crystal materials (e.g. LiNi) with higher nickel content, especially nickel content greater than 0.75 0.8 Co 0.1 Mn 0.1 O 2 ) Due to the low sintering temperature of the material itself and Ni 3+ The ion content is high, and the structure of the material is extremely unstable at high temperature. Although the high-temperature and long-time sintering method can prepare the single crystal material, the surface structure of the high-nickel single crystal cathode material is degraded, oxygen evolution and phase separation occur, so that a large amount of rock salt phase or spinel phase impurities are formed, and simultaneously, mixed arrangement of cations in the layered material is more serious, and the factors cause that the high-nickel single crystal cathode material is difficult to realize by simply increasing the calcining temperature or prolonging the sintering time when being prepared.
Based on the limitation of the problems, at present, two methods are mainly used for preparing the high-nickel single crystal anode material, wherein the high-temperature molten salt method is adopted, and the sintering temperature is adjusted by adopting a fluxing agent (which is also a doping agent).
The high-temperature molten salt method is a method for mixing a precursor, a lithium salt and one or more molten salts, and mixing a large amount of molten salts to reduce the sintering temperature so that the reaction of the precursor and the lithium salt is carried out in a molten state, thereby obtaining the high-nickel single crystal cathode material with good crystallinity. For example, chinese patent nos. CN 111200129 a and CN109879333A both adopt a high temperature molten salt method to prepare a high nickel single crystal positive electrode material, but the molten salt used in the high temperature molten salt method is generally halide or sulfate, which causes severe corrosion to the equipment in the actual production process, and in addition, because the amount of the molten salt is large, the sintered byproducts are hardened together with the positive electrode material, and a large amount of solvent is needed for cleaning and environmental protection, which increases the production cost.
Flux-assisted sintering, which generally refers to mixing a precursor, a lithium source and a small amount of flux, and using the flux action to lower the sintering temperature, for example, chinese patent CN 110867580 a proposes that a strontium-containing compound is used as the flux and dopant to prepare a single crystal positive electrode material. Such fluxing agents are limited as dopants because the fluxing elements are doped into the crystal lattice of the material with high temperature calcination, are not too much used and are difficult to enrich at the surface, and thus have limited fluxing and protecting effects. When a high nickel single crystal material with nickel content more than 0.75 and low sintering temperature is prepared, the stability of the surface of the material is difficult to maintain at high temperature, and the problems of surface degradation and low capacity still exist in the sintering process. Therefore, the method mainly aims at improving the electrochemical performance of the sintered material, and cannot well solve the essential defects in the sintering process of the high-nickel single crystal material.
In addition, some researches have been conducted to mix and sinter the precursor and the flux (also a dopant) first to form a single crystal-like precursor, and then mix and sinter the single crystal-like precursor with a lithium source to obtain a high nickel single crystal material. For example, the chinese patent CN 107768619 a proposes mixing and sintering a hydroxide precursor with a zirconium source, a dopant, and a wetting agent to form a single crystal-like oxide precursor, and then mixing and sintering the single crystal-like oxide precursor with a lithium source to obtain a high nickel single crystal positive electrode material. The method has the advantages that a zirconium source and a doping agent can be uniformly doped into a dehydrated precursor through the dispersion of a wetting agent and one-time high-temperature calcination, so that the precursor forms element-doped quasi-single crystal oxide particles, and then the element-doped quasi-single crystal oxide particles are mixed with a lithium source for sintering to form the single crystal cathode material on the basis of keeping the shape of a single crystal. The method has the disadvantages that the precursor can be changed into single crystal particles after primary sintering, and although uniform doping of elements is realized in advance, the single crystal morphology can greatly limit the diffusion of lithium ions during secondary sintering, no grain boundary diffusion exists, and only part of crystal faces (such as (111) crystal faces of oxides) can provide diffusion channels. In addition, the single crystal precursor obtained by the method is poor in processability, and a crushing and screening process is additionally added before lithium is prepared, so that the method can effectively improve the electrochemical performance of the material by better solving the problem of difficulty in secondary recrystallization of polycrystal in the multi-element doping and sintering processes, but sacrifices the diffusion rate of ions in the solid reaction process and cannot solve the problem of surface degradation.
Therefore, how to accelerate the diffusion rate of ions in the solid state reaction and the recrystallization reaction rate of the single crystal fused by polycrystal, effectively reduce the sintering temperature of the high-nickel single crystal anode material, ensure the stability of the surface structure of the material in the sintering process, and optimize the single crystal preparation process is a problem which needs to be solved urgently for industrially obtaining the high-nickel single crystal anode material with good crystallinity and excellent electrochemical performance at present.
Disclosure of Invention
Under the background, the invention provides a preparation method of a high-nickel single crystal anode material of a lithium ion battery, which reserves the polycrystalline morphology of a precursor, and the formed fast ion conductor can greatly improve the ion diffusion rate in solid phase reaction, accelerate the secondary recrystallization of the polycrystalline precursor and obviously reduce the sintering temperature and time of the high-nickel single crystal. In addition, the fast ion conductor has large molecular weight and stable structure, and can prevent the surface structure of the single crystal particles from being degraded in the sintering process by being distributed on the surfaces of the particles, and the concentration gradient doping and surface coating of the particles are synchronously completed along with the sintering process, so that the electrochemical performance of the material is effectively improved.
In order to achieve the above purpose, the invention provides a preparation method of a high nickel single crystal anode material of a lithium ion battery, which comprises the following steps:
(1) dispersing the hydroxide precursor and the flocculating agent in water, adding a modifier into the water, and uniformly stirring the mixed slurry;
(2) stirring and heating the uniformly mixed slurry at a certain temperature, then evaporating the slurry to dryness, and sintering the obtained powder at a high temperature to obtain a modified polycrystalline precursor material;
(3) and mixing the modified precursor material with a lithium source, and performing secondary sintering in an oxygen-containing atmosphere to obtain the high-nickel single crystal cathode material.
Preferably, the hydroxide precursor in step (1) is Ni x Co y M z (OH) 2 Wherein x is more than or equal to 0.75, y is more than or equal to 0 and less than or equal to 0.25, z is more than or equal to 0 and less than or equal to 0.25, x + y + z is 1, and the M element is one or more of Mn, Al and Ti.
Preferably, the precursor in the step (1) is polycrystalline secondary spherical particles formed by agglomeration of primary particles, and the BET of the polycrystalline secondary spherical particles is preferably 4-10 m 2 A ratio of (i)/g, more preferably 6 to 8m 2 /g。
Preferably, the particle diameter D of the precursor in the step (1) 50 Preferably 3-8 um, and more preferably 4-6 um.
Preferably, the modifier in step (1) is a compound comprising elements Li, O and element a, said element a being one or more of Zr, Ti, Al, La, Ba, Ga, Ta, Nb.
The modifier may be a compound or a combination of compounds, preferably a combination of compounds, such as oxides, hydroxides or inorganic salts which may be lithium or a.
Preferably, the modifier produces a fast ion conductor that allows lithium to pass through quickly after sintering.
In some preferred embodiments of the present invention, the fast ion conductor has a general structural formula of Li t La u B w O p Wherein t is more than or equal to 0.3 and less than or equal to 7, u is more than or equal to 0.5 and less than or equal to 5, w is more than or equal to 1 and less than or equal to 3, p is more than or equal to 2 and less than or equal to 12, and the B element is one or more of Zr, Ti, Al, Ba, Ga, Ta and Nb.
The fast ion conductor may be Li 7 La 3 Zr 2 O 12 、Li 6 BaLa 2 Ta 2 O 12 、Li 5 La 3 Nb 2 O 12 、Li 5 La 3 Ta 2 O 12 、Li 0.34 La 0.51 TiO 2.94 Or fast ion conductors containing other a elements as doping elements.
If the compound is Li 7 La 3 Zr 2 O 12 The fast ion conductor Li can be formed by doping partial Al, Ga and other elements 6.25 Al 0.3 La 3 Zr 2 O 12 、Li 6.5 Al 0.3 La 3 Zr 1.9 O 12 、Li 6.55 La 3 Zr 2 Ga 0.15 O 12 。
The fast ion conductor is preferably Li 7 La 3 Zr 2 O 12 、Li 6.25 Al 0.3 La 3 Zr 2 O 12 、Li 6.5 Al 0.3 La 3 Zr 1.9 O 12 、Li 6.55 La 3 Zr 2 Ga 0.15 O 12 、Li 6 BaLa 2 Ta 2 O 12 、Li 5 La 3 Nb 2 O 12 、Li 5 La 3 Ta 2 O 12 、Li 0.34 La 0.51 TiO 2.94 One or more of (a).
The addition amount of each A element and each lithium element in the modifier is added according to the molar ratio of each element in the target fast ion conductor.
Specifically, if the chemical composition of the modifier after sintering is selected to be Li 7 La 3 Zr 2 O 12 Adding the modifier into the Li, La and Zr according to the proportion of a chemical formula, wherein the molar ratio of the three elements is 7: 3: 2 addition of nano oxides, hydroxides or inorganic salts of the corresponding elements, e.g. LiOH. H 2 O, nano-La 2 O 3 And ZrO 2 。
The molar fraction of the amount of the target compound in the modifier is 0.0001 to 0.005 based on the molar amount of the hydroxide precursor. Too small a content thereof does not contribute to acceleration of ion transport rate and improvement of stability of surface structure of the material, and too much may limit electrochemical properties of the material.
Preferably, the flocculant in step (1) is one or more of citric acid, glucose, maleic acid, oxalic acid and sucrose, and the function of the flocculant is to make the modifier uniformly distributed on the surface and in the pores of the precursor during the heating flocculation process, so as to prevent the agglomeration of the nanoparticles. In addition, the flocculating agent can generate self-propagating combustion decomposition reaction in the primary sintering process, so that the local temperature can be instantly increased, the reaction between the nano particles is promoted to generate the oxide nano crystal cluster containing lithium, and the decomposition products are carbon dioxide and water, so that the element content of the main material is not influenced.
Preferably, the adding amount of the flocculating agent in the step (1) is 1-5% of the mass of the hydroxide precursor.
Preferably, the mixed slurry of the precursor, the modifier and the flocculating agent in the step (2) is heated to 50-80 ℃ for flocculation, and the drying is carried out after the slurry is in a gel state.
Preferably, in the step (2), the flocculated and dried powder is sintered by rapidly heating, preferably, the sintering temperature in the step (2) is 700-1000 ℃, preferably 800-900 ℃, and the sintering time is 2-5 h, preferably 2.5-4 h. Then cooling to room temperature, and sintering in oxygen-containing atmosphere, such as air and oxygen.
Preferably, in the step (2), the temperature of the flocculated and dried powder is raised at a temperature raising speed of more than 8 ℃/min, preferably 8-20 ℃/min, and preferably, the highest temperature raising speed is not more than 25 ℃/min.
The rapid heating sintering in the step can enable the flocculating agent to rapidly generate self-propagating combustion reaction, improve the local temperature and further enable the modifier nano particles to form the nanocrystalline clusters in a short time. Meanwhile, the nanocrystalline clusters can grow to a certain extent due to the rapid heating sintering and the short sintering time, the crystallinity is improved, the nanocrystalline clusters cannot be subjected to crystal grain fusion due to the overlong sintering time, the dispersity is reduced, and in addition, the residue of a flocculating agent can also be reduced.
Preferably, the modified precursor material obtained after the modification sintering in the step (2) is Ni wrapped by fast ion conductor nano crystal cluster x Co y M z O 2 Oxide and still maintain the morphology of the polycrystalline secondary spheres. Wherein Ni x Co y M z O 2 Oxide as hydroxide precursor Ni x Co y M z (OH) 2 Dehydrated at high temperature, and is characterized by containing more crystal boundary polycrystalline secondary spherical particles and more pores; the fast ion conductor nanocrystalline cluster is a compound containing Li, O and A elements, such as Li, formed by rapid crystallization of an added modifier in a primary sintering process 7 La 3 Zr 2 O 12 、Li 6.25 Al 0.3 La 3 Zr 2 O 12 、Li 6.5 Al 0.3 La 3 Zr 1.9 O 12 、Li 6.55 La 3 Zr 2 Ga 0.15 O 12 、Li 6 BaLa 2 Ta 2 O 12 、Li 5 La 3 Nb 2 O 12 、Li 5 La 3 Ta 2 O 12 、Li 0.34 La 0.51 TiO 2.94 The sintered modifier compound can be partially doped in the crystal lattice of the main material in a concentration gradient form in the final sintered product, and partially coated on the surface of the main material in a chemical bonding form, but the chemical composition of the main material is kept unchanged, and the ionic conductivity is excellent and uniformly distributed in Ni x Co y M z O 2 The surface and grain boundary of the oxide polycrystalline grains.
Compared with the prior dopant-assisted sintering scheme, the method of the invention greatly accelerates the ion diffusion rate in the solid phase reaction by generating the fast ion conductor nanocrystalline clusters on the surface of the modified precursor material, rather than a simple fluxing effect, thereby ensuring the crystallinity, greatly reducing the sintering temperature and time of the high nickel single crystal, and simultaneously protecting the surface of the high nickel single crystal by the fast ion conductor on the surface to prevent the degradation of the annealing structure of the high nickel single crystal at high temperature. In addition, because the temperature is lower and the time is shorter during the calcination of the method, the fast ion conductor metal element on the surface can be partially doped in the crystal lattice of the main body material in a concentration gradient manner, and partially coated on the surface of the main body material in a chemical bonding manner, namely, the coating modification is synchronously completed.
The lithium source in the step (3) is selected from lithium carbonate, lithium hydroxide and lithium hydroxide monohydrate, and preferably lithium hydroxide monohydrate.
Preferably, in the step (3), the amount of the lithium source added is 1.005 to 1.05 in terms of a molar ratio of Li/(Ni + Co + M) to the metal element in the precursor.
Preferably, the oxygen-containing atmosphere in step (3) is an oxygen-containing atmosphere such as air or oxygen, and preferably an atmosphere containing oxygen at 95% or more.
Preferably, the sintering temperature in step (3) is not higher than the sintering temperature in step (2), specifically: firstly, preserving heat for 1-3 h at 300-500 ℃, then heating to 600-800 ℃, preferably 650-800 ℃, sintering for 6-10 h, and finally naturally cooling to room temperature to obtain the high-nickel single crystal anode material.
The invention also provides a high-nickel single crystal cathode material prepared by the method, and the chemical formula of the material is LiNi x Co y M z (Li α A β O γ ) ζ O 2 Wherein x is more than or equal to 0.75, y is more than or equal to 0 and less than or equal to 0.25, z is more than or equal to 0 and less than or equal to 0.25, alpha is more than or equal to 0.3 and less than or equal to 7, beta is more than or equal to 1.5 and less than or equal to 6, gamma is more than or equal to 2 and less than or equal to 12, zeta is more than or equal to 0.0001 and less than or equal to 0.005, and x + y + z is equal to 1. The element A is the combination of one or more elements of Zr, Ti, Al, La, Ba, Ga, Ta and Nb.
Preferably, Li α A β O γ Is Li 7 La 3 Zr 2 O 12 、Li 6.25 Al 0.3 La 3 Zr 2 O 12 、Li 6.5 Al 0.3 La 3 Zr 1.9 O 12 、Li 6.55 La 3 Zr 2 Ga 0.15 O 12 、Li 6 BaLa 2 Ta 2 O 12 、Li 5 La 3 Nb 2 O 12 、Li 5 La 3 Ta 2 O 12 、Li 0.34 La 0.51 TiO 2.94 One or more of them.
The preparation method for preparing the high-nickel single crystal cathode material of the lithium ion battery provided by the invention has the following advantages that:
1. effectively reduces the sintering temperature of the high-nickel single crystal anode material. The method disclosed by the invention reserves the polycrystalline morphology of the precursor through high-temperature rapid modified sintering, and the grain boundary and the widely exposed crystal face in the precursor are favorable for the diffusion of lithium ions in the secondary sintering process; in addition, along with the self-propagating combustion reaction of the flocculating agent, the modifier forms a fast ion conductor nanocrystalline cluster at the crystal boundary and the surface of the flocculating agent, the nanocrystalline cluster can reduce the specific surface energy of the whole particles, promote the mass transfer rate in the recrystallization process, greatly improve the ion diffusion rate in the solid state reaction, and further obviously reduce the sintering temperature and the sintering time of the high-nickel single crystal anode material.
2. The surface stability of the high-nickel single crystal cathode material in the sintering process is improved. The fast ion conductor formed in the primary sintering of the method of the invention is an oxide containing lithium, which can be combined with the main material through a metal-oxygen bond, and because of good thermal stability, the fast ion conductor can exist on the surface of the main material more stably in the secondary sintering process, thereby reducing Ni 3+ The concentration and activity of the catalyst, and further stabilizes the surface structure and prevents the formation of spinel phase or halite phase impurities.
3. The electrochemical performance of the material is improved. The secondary sintering process with long time and high temperature inevitably leads to the complete doping of modifier elements and the crystal lattice of the main material, but the low-temperature short-time scheme provided by the method can lead part of the modifier elements to be diffused into the crystal lattice of the main material in a concentration gradient manner, and the entropy value of the material can be improved by the element doping, so that the cycling stability of the material is further improved; meanwhile, the fast ion conductor has good stability, and part of the fast ion conductor can be retained on the surface of the main material in a coating mode, so that the fast ion conductor can accelerate the lithium ion deintercalation rate in the charge and discharge process, and the rate capability and the safety performance of the material are effectively improved.
Drawings
Fig. 1 is an SEM image of the positive electrode material obtained in example 1 of the present invention.
Fig. 2 is an SEM image of the positive electrode material obtained in comparative example 1.
Fig. 3 is an SEM image of the positive electrode material obtained in comparative example 2.
It can be seen that the sintering time and temperature are the sameNext, by the method provided by the present invention, a well-defined particle D can be obtained 50 The high nickel single crystal anode material can not be obtained from the high nickel single crystal material with the thickness of about 4-5um by directly mixing and calcining the precursor and a lithium source or calcining the mixture after adding a fluxing agent.
Fig. 4 is an HR-TEM image of the high nickel single crystal material in example 1 of the present invention, it can be seen that the metal elements in the (003) plane of the layered material are arranged regularly and present in the typical O3 phase, and neither the crystal surface nor bulk phase has other element arrangements caused by the presence of rock salt phase or spinel phase impurities, which indicates that the method provided by the present invention can effectively prevent the surface degradation of the high nickel single crystal positive electrode material during the sintering process.
Fig. 5 is XRD patterns of the cathode materials obtained in example 1, comparative example 3 and comparative example 4 of the present invention, and it can be seen that the XRD patterns of the single crystal materials obtained in example 1 have good crystallinity and no impurity phase is generated, while the XRD patterns of the single crystal materials obtained in comparative examples 3 and 4 have a distinct NiO impurity peak.
Fig. 6 is a comparison graph of cycle performance of the positive electrode materials obtained in example 1, comparative example 3 and comparative example 4 of the present invention, the test conditions are half cell, voltage window of 3.0-4.3V, temperature is 25 ℃, 1C nominal current is 190mA/g, after two weeks of charge and discharge at 0.2C, cycle is performed for 48 cycles at 1C, and it can be seen that the single crystal positive electrode material prepared by the method of the present invention is significantly improved in capacity and cycle stability. Compared with the method of directly mixing the precursor and the lithium source and sintering at high temperature or directly sintering at high temperature after adding the dopant, the modification process provided by the invention has the advantages that the recrystallization rate is accelerated, the sintering temperature and time of the high-nickel single crystal cathode material can be greatly reduced, and the material can be sintered at a higher rate at a lower temperature. The process reduces the surface degradation and lithium-nickel mixed discharge of the material at high temperature to the maximum extent, improves the crystallinity, and obviously improves the electrochemical performance of the material by the surface coating and the gradient doping.
Fig. 7 is an SEM image of the cathode material of comparative example 5 of the present invention, and it can be seen that after the temperature increase rate of the modification step is decreased, a part of particles still have a polycrystalline secondary sphere morphology due to non-uniform dispersion of the nanocrystal clusters of the fast ion conductor.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
The raw material sources are as follows: ni 0.83 Co 0.12 Mn 0.05 (OH) 2 、Ni 0.75 Co 0.15 Mn 0.10 (OH) 2 、Ni 0.80 Co 0.10 Mn 0.10 (OH) 2 From Zhongwei New materials Ltd, Ni 0.90 Co 0.05 Mn 0.05 (OH) 2 、Ni 0.95 Co 0.02 Mn 0.03 (OH) 2 From greens, inc.
Example 1:
the preparation process of the material of this example includes the following steps:
1. taking 10mol, BET is 7m 2 /g，D 50 Is 5um Ni 0.83 Co 0.12 Mn 0.05 (OH) 2 Dissolved in water, 30g of citric acid, 1.3735g of LiOH H were added thereto 2 O, 2.4435g La 2 O 3 1.2322g of ZrO 2 And 0.0703g of Ga 2 O 3 Fully and uniformly stirring;
2. heating and stirring the slurry uniformly mixed in the step 1 at 65 ℃, and evaporating to dryness after the slurry is in a gel state;
3. sintering the powder material obtained in the step 2 in a muffle furnace for 3.5h at an average heating rate of 11 ℃/min to 850 ℃, wherein the sintering atmosphere is air, then naturally cooling to room temperature, and crushing to obtain a modified precursor material;
4. the modified precursor material is mixed with 10.35mol of LiOH & H 2 Mixing the O;
5. preserving the temperature of the mixed powder in the step 4 at 450 ℃ for 2h in the atmosphere of 98% oxygen, then heating to 750 ℃ for sintering for 8h, then naturally cooling to room temperature, and crushing to obtain the high-nickel single crystal positive electrode material LiNi 0.83 Co 0.12 Mn 0.05 (Li 6.55 La 3 Zr 2 Ga 0.15 O 12 ) 0.0005 O 2 。
Example 2:
the preparation process of the material of this example includes the following steps:
1. taking 10mol, BET is 6m 2 /g，D 50 Is 6um Ni 0.75 Co 0.15 Mn 0.10 (OH) 2 Dissolved in water, 10g of glucose and 0.5494g of LiOH. H were added thereto 2 O, 0.9774g La 2 O 3 0.4929g of ZrO 2 And Ga 0.0282g 2 O 3 Fully and uniformly stirring;
2. heating and stirring the slurry uniformly mixed in the step 1 at 80 ℃, and evaporating to dryness after the slurry is in a gel state;
3. sintering the powder material obtained in the step 2 in a muffle furnace for 2.5h at an average heating rate of 15 ℃/min to 850 ℃, wherein the sintering atmosphere is air, then naturally cooling to room temperature, and crushing to obtain a modified precursor material;
4. the modified precursor material is mixed with 10.15mol of LiOH & H 2 Mixing the O;
5. preserving the heat of the mixed powder in the step 4 at 500 ℃ for 3h in 96% oxygen atmosphere, then heating to 800 ℃ for sintering for 10h, then naturally cooling to room temperature, and crushing to obtain the high-nickel single crystal positive electrode material LiNi 0.75 Co 0.15 Mn 0.10 (Li 6.55 La 3 Zr 2 Ga 0.15 O 12 ) 0.0002 O 2 。
Example 3:
the preparation process of the material of this example includes the following steps:
1. taking 10mol, BET is 6m 2 /g，D 50 Is 5um Ni 0.75 Co 0.15 Mn 0.10 (OH) 2 Dissolved in water, 10g of oxalic acid, 2.9358g of LiOH H were added thereto 2 O, 4.8870g La 2 O 3 And 2.4644g of ZrO 2 Fully and uniformly stirring;
2. heating and stirring the slurry uniformly mixed in the step 1 at 80 ℃, and evaporating to dryness after the slurry is in a gel state;
3. sintering the powder material obtained in the step 2 in a muffle furnace for 2.5h at an average heating rate of 18 ℃/min to 900 ℃, wherein the sintering atmosphere is air, then naturally cooling to room temperature, and crushing to obtain a modified precursor material;
4. mixing the modified precursor material with 10.10mol of LiOH & H 2 Mixing the O;
5. preserving the heat of the mixed powder in the step 4 at 500 ℃ for 3h in 96% oxygen atmosphere, then heating to 800 ℃ for sintering for 10h, then naturally cooling to room temperature, and crushing to obtain the high-nickel single crystal positive electrode material LiNi 0.75 Co 0.15 Mn 0.10 (Li 7 La 3 Zr 2 O 12 ) 0.001 O 2 。
Example 4:
the preparation process of the material of this example includes the following steps:
1. 10mol of the powder is taken, and the BET is 6.5m 2 /g，D 50 Ni of 5um 0.80 Co 0.10 Mn 0.10 (OH) 2 Dissolved in water, and 20g of citric acid and 3.1455g of LiOH H were added thereto 2 O, 5.8644g La 2 O 3 2.9573g of ZrO 2 And 0.1835g of Al 2 O 3 Fully and uniformly stirring;
2. heating and stirring the slurry uniformly mixed in the step 1 at 75 ℃, and evaporating to dryness after the slurry is in a gel state;
3. sintering the powder material obtained in the step 2 in a muffle furnace for 3h at an average heating rate of 12 ℃/min to 900 ℃, wherein the sintering atmosphere is air, then naturally cooling to room temperature, and crushing to obtain a modified precursor material;
4. the modified precursor material is mixed with 10.30mol of LiOH & H 2 Mixing the O;
5. preserving the temperature of the mixed powder in the step 4 at 450 ℃ for 2h in the atmosphere of 97% oxygen, then heating to 780 ℃ and sintering for 9h, then naturally cooling to room temperature, and crushing to obtain the high-nickel single crystal positive electrode material LiNi 0.80 Co 0.10 Mn 0.10 (Li 6.25 Al 0.3 La 3 Zr 2 O 12 ) 0.0012 O 2 。
Example 5:
the preparation process of the material of this example includes the following steps:
1. taking 10mol of a BET of 6.5m 2 /g，D 50 Ni of 5um 0.80 Co 0.10 Mn 0.10 (OH) 2 Dissolved in water, and 20g of citric acid and 0.2516g of LiOH & H were added thereto 2 O, 0.3258g La 2 O 3 0.1973g of BaCO 3 And 0.4418g of Ta 2 O 5 Fully and uniformly stirring;
2. heating and stirring the slurry uniformly mixed in the step 1 at 70 ℃, and evaporating to dryness after the slurry is in a gel state;
3. sintering the powder material obtained in the step 2 in a muffle furnace for 2.5h at an average heating rate of 12 ℃/min to 900 ℃, wherein the sintering atmosphere is air, then naturally cooling to room temperature, and crushing to obtain a modified precursor material;
4. mixing the modified precursor material with 10.25mol of LiOH & H 2 Mixing the O;
5. keeping the mixed powder in the step 4 at the temperature of 450 ℃ for 2h under the atmosphere of 97% oxygen, then heating to 780 ℃ for sintering for 9h, then naturally cooling to room temperature, and crushing to obtain the high-nickel single crystal positive electrode material LiNi 0.80 Co 0.10 Mn 0.10 (Li 6 BaLa 2 Ta 2 O 12 ) 0.0001 O 2 。
Example 6:
the preparation process of the material of the embodiment comprises the following steps:
1. taking 10mol of a BET of 7.5m 2 /g，D 50 Ni of 4um 0.90 Co 0.05 Mn 0.05 (OH) 2 Dissolved in water, 40g of maleic acid, 3.1455g of LiOH H were added thereto 2 O, 7.3305g La 2 O 3 And 3.9873g of Nb 2 O 5 Fully and uniformly stirring;
2. heating and stirring the slurry uniformly mixed in the step 1 at 55 ℃, and evaporating to dryness after the slurry is in a gel state;
3. sintering the powder material obtained in the step 2 in a muffle furnace for 4 hours at an average heating rate of 10 ℃/min to 850 ℃, wherein the sintering atmosphere is air, then naturally cooling to room temperature, and crushing to obtain a modified precursor material;
4. the modified precursor material is mixed with 10.40mol of LiOH & H 2 Mixing the O;
5. keeping the mixed powder in the step 4 at 350 ℃ for 2h in 98% oxygen atmosphere, heating to 700 ℃ for sintering for 8h, naturally cooling to room temperature, and crushing to obtain the high-nickel single crystal positive electrode material LiNi 0.90 Co 0.05 Mn 0.05 (Li 5 La 3 Nb 2 O 12 ) 0.0015 O 2 。
Example 7:
the preparation process of the material of this example includes the following steps:
1. taking 10mol, BET is 8m 2 /g，D 50 Ni of 4um 0.95 Co 0.02 Mn 0.03 (OH) 2 Dissolved in water, and 45g of citric acid and 0.7130g of LiOH. H were added thereto 2 O, 4.1540g La 2 O 3 And 3.9935g of TiO 2 Fully and uniformly stirring;
2. heating and stirring the slurry uniformly mixed in the step 1 at 50 ℃, and evaporating to dryness after the slurry is in a gel state;
3. sintering the powder material obtained in the step 2 in a muffle furnace for 3.5 hours at an average heating rate of 9 ℃/min to 800 ℃, wherein the sintering atmosphere is air, then naturally cooling to room temperature, and crushing to obtain a modified precursor material;
4. mixing the modified precursor material with 10.45mol of LiOH & H 2 Mixing the O;
5. keeping the mixed powder obtained in the step 4 at 500 ℃ for 2h in the atmosphere of 99% oxygen, heating to 650 ℃, sintering for 10h, naturally cooling to room temperature, and crushing to obtain the high-nickel single crystal positive electrode material LiNi 0.95 Co 0.02 Mn 0.03 (Li 0.34 La 0.51 TiO 2.94 ) 0.005 O 2 。
Example 8:
the preparation process of the material of the embodiment comprises the following steps:
1. taking 10mol, BET is 8m 2 /g，D 50 Ni of 4um 0.95 Co 0.02 Al 0.03 (OH) 2 Dissolved in water, and 35g of sucrose, 1.049g of LiOH. H were added thereto 2 O, 2.4435g La 2 O 3 And 1.3291g of Nb 2 O 5 Fully and uniformly stirring;
2. heating and stirring the slurry uniformly mixed in the step 1 at 60 ℃, and evaporating to dryness after the slurry is in a gel state;
3. sintering the powder material obtained in the step 2 in a muffle furnace at an average heating rate of 8 ℃/min to 800 ℃ for 4h, wherein the sintering atmosphere is air, then naturally cooling to room temperature, and crushing to obtain a modified precursor material;
4. the modified precursor material is mixed with 10.50mol of LiOH & H 2 O, mixing;
5. keeping the mixed powder obtained in the step 4 at 500 ℃ for 2h in the atmosphere of 99% oxygen, heating to 650 ℃, sintering for 7h, naturally cooling to room temperature, and crushing to obtain the high-nickel single crystal positive electrode material LiNi 0.95 Co 0.02 Al 0.03 (Li 5 La 3 Nb 2 O 12 ) 0.0005 O 2 。
Comparative example 1:
the preparation process of the comparative example material comprises the following steps:
1. taking 10mol, BET is 7m 2 /g，D 50 Is 5um Ni 0.83 Co 0.12 Mn 0.05 (OH) 2 With 10.35mol of LiOH. H 2 O, mixing;
2. preserving the heat of the mixed powder in the step 1 at 450 ℃ for 2h under the atmosphere of 98% oxygen, then heating to 750 ℃ for sintering for 8h, then naturally cooling to room temperature, and crushing to obtain the cathode materialLiNi 0.83 Co 0.12 Mn 0.05 O 2 。
Comparative example 2:
the preparation process of the comparative example material comprises the following steps:
1. taking 10mol, BET is 7m 2 /g，D 50 Is 5um Ni 0.83 Co 0.12 Mn 0.05 (OH) 2 And 10.35mol of LiOH. H 2 O was mixed with 1.3735g of LiOH H 2 O, 2.4435g La 2 O 3 1.2322g of ZrO 2 And 0.0703g of Ga 2 O 3 Mixing;
2. preserving the heat of the mixed powder in the step 1 at 450 ℃ for 2h in the atmosphere of 98% oxygen, then heating to 750 ℃ for sintering for 8h, then naturally cooling to room temperature, and crushing to obtain the anode material LiNi doped with the La, Zr and Ga 0.83 Co 0.12 Mn 0.05 (La 3 Zr 2 Ga 0.15 ) 0.0005 O 2 。
Comparative example 3:
the preparation process of the comparative example material comprises the following steps:
1. taking 10mol, BET is 7m 2 /g，D 50 Is 5um Ni 0.83 Co 0.12 Mn 0.05 (OH) 2 With 10.35mol of LiOH. H 2 Mixing the O;
2. preserving the temperature of the mixed powder in the step 1 at 450 ℃ for 2h in the atmosphere of 98% oxygen, heating to 8000 ℃ for sintering for 12h, naturally cooling to room temperature, and crushing to obtain the high-nickel single crystal positive electrode material LiNi 0.83 Co 0.12 Mn 0.05 O 2 。
Comparative example 4:
the preparation process of the comparative example material comprises the following steps:
1. taking 10mol, BET is 7m 2 /g，D 50 Is 5um Ni 0.83 Co 0.12 Mn 0.05 (OH) 2 And 10.35mol of LiOH. H 2 O was mixed with 1.3735g of LiOH H 2 O, 2.4435g La 2 O 3 1.2322g of ZrO 2 And 0.0703g of Ga 2 O 3 Mixing;
2. preserving the heat of the mixed powder in the step 1 at 450 ℃ for 2h in the atmosphere of 98% oxygen, then heating to 790 ℃ for sintering for 12h, then naturally cooling to room temperature, and crushing to obtain the high-nickel single crystal anode material LiNi doped with three elements of La, Zr and Ga 0.83 Co 0.12 Mn 0.05 (La 3 Zr 2 Ga 0.15 ) 0.0005 O 2 。
Comparative example 5:
the preparation process of the comparative example material comprises the following steps:
1. taking 10mol, BET is 7m 2 /g，D 50 Is 5um Ni 0.83 Co 0.12 Mn 0.05 (OH) 2 Dissolved in water, 30g of citric acid, 1.3735g of LiOH H were added thereto 2 O, 2.4435g La 2 O 3 1.2322g of ZrO 2 And 0.0703g of Ga 2 O 3 Fully and uniformly stirring;
2. heating and stirring the slurry uniformly mixed in the step 1 at 65 ℃, and evaporating to dryness after the slurry is in a gel state;
3. sintering the powder material obtained in the step 2 in a muffle furnace at an average heating rate of 2 ℃/min to 850 ℃ for 3.5h, wherein the sintering atmosphere is air, then naturally cooling to room temperature, and crushing to obtain a modified precursor material;
4. the modified precursor material is mixed with 10.35mol of LiOH & H 2 O, mixing;
5. preserving the heat of the mixed powder in the step 4 at 450 ℃ for 2h in the atmosphere of 98% oxygen, then heating to 750 ℃ for sintering for 8h, then naturally cooling to room temperature, and crushing to obtain the high-nickel anode material LiNi 0.83 Co 0.12 Mn 0.05 (Li 6.55 La 3 Zr 2 Ga 0.15 O 12 ) 0.0005 O 2 。

Claims (8)

1. A preparation method of a high-nickel single crystal cathode material of a lithium ion battery is characterized by comprising the following steps:
(1) dispersing the hydroxide precursor and the flocculating agent in water, adding a modifier into the water, and uniformly stirring the mixed slurry;
(2) stirring and heating the uniformly mixed slurry at a certain temperature, then evaporating the slurry to dryness, and sintering the obtained powder at a high temperature to obtain a modified polycrystalline precursor material;
(3) and mixing the modified precursor material with a lithium source, and performing secondary sintering in an oxygen-containing atmosphere to obtain the high-nickel single crystal cathode material.
2. The method according to claim 1, wherein the hydroxide precursor in step (1) is Ni x Co y M z (OH) 2 Wherein x is more than or equal to 0.75, y is more than or equal to 0 and less than or equal to 0.25, z is more than or equal to 0 and less than or equal to 0.25, x + y + z is 1, and M element is one or more of Mn, Al and Ti;
preferably, the precursor in the step (1) is polycrystalline secondary spherical particles formed by agglomeration of primary particles, and the BET of the polycrystalline secondary spherical particles is preferably 4-10 m 2 A concentration of 6 to 8m 2 /g；
Preferably, the particle diameter D of the precursor in the step (1) 50 Preferably 3-8 um, and more preferably 4-6 um.
3. The preparation method according to claim 1, wherein the modifier in step (1) is a compound comprising elements Li, O and element A, wherein the element A is one or more of Zr, Ti, Al, La, Ba, Ga, Ta and Nb;
the modifier is one compound or a combination of a plurality of compounds, preferably a combination of a plurality of compounds.
4. The method of claim 1, wherein the modifier produces a fast ion conductor that allows lithium to pass through rapidly after sintering; preferably, the general structural formula of the fast ion conductor is Li t La u B w O p Wherein t is more than or equal to 0.3 and less than or equal to 7, u is more than or equal to 0.5 and less than or equal to 5, w is more than or equal to 1 and less than or equal to 3, p is more than or equal to 2 and less than or equal to 12, B elementIs one or more of Zr, Ti, Al, Ba, Ga, Ta and Nb;
preferably, the fast ion conductor is Li 7 La 3 Zr 2 O 12 、Li 6 BaLa 2 Ta 2 O 12 、Li 5 La 3 Nb 2 O 12 、Li 5 La 3 Ta 2 O 12 、Li 0.34 La 0.51 TiO 2.94 Or a fast ion conductor containing other A elements as doping elements;
preferably, the fast ion conductor is Li 7 La 3 Zr 2 O 12 、Li 6.25 Al 0.3 La 3 Zr 2 O 12 、Li 6.5 Al 0.3 La 3 Zr 1.9 O 12 、Li 6.55 La 3 Zr 2 Ga 0.15 O 12 、Li 6 BaLa 2 Ta 2 O 12 、Li 5 La 3 Nb 2 O 12 、Li 5 La 3 Ta 2 O 12 、Li 0.34 La 0.51 TiO 2.94 One or more of (a);
preferably, the addition amount of each element A and the lithium element in the modifier is added according to the molar ratio of each element in the target fast ion conductor;
preferably, the molar fraction of the amount of the objective compound in the modifier is 0.0001 to 0.005 based on the molar amount of the hydroxide precursor.
5. The preparation method according to claim 1, characterized in that the adding amount of the flocculating agent in the step (1) is 1-5% of the mass of the hydroxide precursor;
preferably, the flocculant in step (1) is one or more of citric acid, glucose, maleic acid, oxalic acid and sucrose.
6. The preparation method according to claim 1, wherein the mixed slurry of the precursor, the modifier and the flocculant in the step (2) is heated to 50-80 ℃ for flocculation, and is dried after the slurry is in a gel state;
preferably, in the step (2), the flocculated and dried powder is quickly heated for sintering, preferably, the sintering temperature in the step (2) is 700-1000 ℃, preferably 800-900 ℃, and the sintering time is 2-5 hours, preferably 2.5-4 hours; the sintering atmosphere is oxygen-containing atmosphere;
preferably, in the step (2), the temperature of the flocculated and dried powder is raised at a temperature raising speed of more than 8 ℃/min, preferably 8-20 ℃/min, and preferably, the highest temperature raising speed is not more than 25 ℃/min.
7. The method according to claim 1, wherein the lithium source in the step (3) is selected from lithium carbonate, lithium hydroxide monohydrate, preferably lithium hydroxide monohydrate;
preferably, the lithium source is added in the step (3) according to a molar ratio of Li/(Ni + Co + M) to the metal element in the precursor of 1.005-1.05;
preferably, the oxygen-containing atmosphere in step (3) is an oxygen-containing atmosphere such as air and oxygen, preferably an atmosphere containing oxygen of 95% or more;
preferably, the sintering temperature in the step (3) is not higher than the sintering temperature in the step (2);
preferably, in the step (3), the temperature is maintained at 300-500 ℃ for 1-3 h, then the temperature is raised to 600-800 ℃, preferably 650-800 ℃, sintering is carried out for 6-10 h, and finally the temperature is naturally reduced to room temperature.
8. A high-nickel single-crystal positive electrode material having a chemical formula of LiNi prepared by the method according to claim 1 x Co y M z (Li α A β O γ ) ζ O 2 Wherein x is more than or equal to 0.75, y is more than or equal to 0 and less than or equal to 0.25, z is more than or equal to 0 and less than or equal to 0.25, alpha is more than or equal to 0.3 and less than or equal to 7, beta is more than or equal to 1.5 and less than or equal to 6, gamma is more than or equal to 2 and less than or equal to 12, zeta is more than or equal to 0.0001 and less than or equal to 0.005, and x + y + z is equal to 1;
the preferable M element is one or more of Mn, Al and Ti, and the A element is one or more of Zr, Ti, Al, La, Ba, Ga, Ta and Nb;
preference is given toOf (1), Li α A β O γ Is Li 7 La 3 Zr 2 O 12 、Li 6.25 Al 0.3 La 3 Zr 2 O 12 、Li 6.5 Al 0.3 La 3 Zr 1.9 O 12 、Li 6.55 La 3 Zr 2 Ga 0.15 O 12 、Li 6 BaLa 2 Ta 2 O 12 、Li 5 La 3 Nb 2 O 12 、Li 5 La 3 Ta 2 O 12 、Li 0.34 La 0.51 TiO 2.94 One or more of them.
CN202110314205.7A 2021-03-24 2021-03-24 Preparation method of high-nickel single crystal cathode material of lithium ion battery Pending CN115133016A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024192936A1 (en) * 2023-03-21 2024-09-26 万华化学(烟台)电池材料科技有限公司 Preparation method for high-nickel single-crystal ternary positive electrode material

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024192936A1 (en) * 2023-03-21 2024-09-26 万华化学(烟台)电池材料科技有限公司 Preparation method for high-nickel single-crystal ternary positive electrode material

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