CN114057238B - Composite ternary material and preparation method and application thereof - Google Patents
Composite ternary material and preparation method and application thereof Download PDFInfo
- Publication number
- CN114057238B CN114057238B CN202111308679.7A CN202111308679A CN114057238B CN 114057238 B CN114057238 B CN 114057238B CN 202111308679 A CN202111308679 A CN 202111308679A CN 114057238 B CN114057238 B CN 114057238B
- Authority
- CN
- China
- Prior art keywords
- ternary precursor
- ternary
- composite
- metal salt
- nickel
- 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
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/02—Magnesia
- C01F5/06—Magnesia by thermal decomposition of magnesium compounds
- C01F5/12—Magnesia by thermal decomposition of magnesium compounds by thermal decomposition of magnesium sulfate, with or without reduction
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/40—Magnesium sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/30—Preparation of aluminium oxide or hydroxide by thermal decomposition or by hydrolysis or oxidation of aluminium compounds
- C01F7/32—Thermal decomposition of sulfates including complex sulfates, e.g. alums
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/68—Aluminium compounds containing sulfur
- C01F7/74—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/008—Titanium- and titanyl sulfate
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- 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
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- 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
-
- 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
Abstract
The application relates to the technical field of lithium battery electrode materials, and provides a composite ternary material which has a core-shell structure and comprises a ternary precursor material and a doped metal salt layer coated on the surface of the ternary precursor material. The composite ternary precursor provided by the application contains the doped metal salt layer coated on the surface of the ternary precursor material, so that the ternary material with uniformly distributed doped metal elements and coated with the metal oxide layer can be formed after the composite ternary precursor is sintered with a lithium source, the metal doping can effectively inhibit the transition of the material surface crystal structure in the circulation process, the metal oxide layer coating can avoid the direct contact with electrolyte, the occurrence of side reaction is inhibited, and the circulation stability of the material can be improved.
Description
Technical Field
The application belongs to the technical field of lithium battery electrode materials, and particularly relates to a composite ternary material and a preparation method and application thereof.
Background
With the rapid growth of new energy automobiles, the demand of power batteries is also increasing continuously, and the performance of the ternary cathode material directly determines the performance of the batteries. High nickel materials and nickel-based cobalt-free materials are gaining popularity due to their high energy density and low cost.
However, in the process of charging and discharging, due to the problems of poor thermal stability, safety and the like of mixed-row nickel elements, although the safety performance of the material can be improved to a certain extent by doping a small amount of elements such as Al, mg, ti and the like, the electrical property of the material is affected and the improvement effect is difficult to achieve due to the fact that the doped elements are unevenly distributed in the ternary material.
When a coprecipitation method is used for preparing the doped ternary precursor material, the situation of uneven doping and even single precipitation of the doped elements exists due to too large difference of solubility products of the doped elements and nickel-cobalt-manganese elements, so that the electrochemical performance of the material is influenced, and the function of the doped elements cannot be exerted.
Disclosure of Invention
The application aims to provide a composite ternary material and a preparation method and application thereof, and aims to solve the problem that the electrochemical performance of the material is influenced due to uneven doping of a nickel-cobalt-manganese ternary material or independent precipitation of doped elements.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a composite ternary precursor, which has a core-shell structure and includes a ternary precursor material and a doped metal salt layer coated on the surface of the ternary precursor material.
In a second aspect, the present application provides a method for preparing a composite ternary precursor, the method comprising:
providing a nickel-cobalt-manganese ternary precursor;
carrying out first mixing treatment on the nickel-cobalt-manganese ternary precursor and an organic complexing agent to obtain an adsorption type ternary precursor mixture;
carrying out second mixing treatment on the doped metal salt solution and the adsorption type ternary precursor mixture to obtain a ternary precursor mixture adsorbed by the doped metal salt solution;
and drying the ternary precursor mixture adsorbed by the doped metal salt solution to obtain the ternary precursor adsorbed by the doped metal salt.
In a third aspect, the present application provides a ternary material, which is formed by sintering a mixture of the composite ternary precursor or the composite ternary precursor prepared by the preparation method of the composite ternary precursor and a lithium source.
In a fourth aspect, the present application provides a positive electrode comprising the ternary material described above. In a fifth aspect, the present application provides a secondary battery comprising the above-described positive electrode.
According to the composite ternary precursor provided by the first aspect of the application, the composite ternary precursor contains the doped metal salt layer coated on the surface of the ternary precursor material, so that the ternary material with uniformly doped metal elements and coated by the metal oxide layer is formed after the composite ternary precursor is sintered with a lithium source, the overcharge resistance and the thermal stability of the ternary material can be improved, and the electrical property of the material is improved.
Firstly, carrying out first mixing treatment on a nickel-cobalt-manganese ternary precursor and an organic complexing agent to form an adsorption type ternary precursor mixture with adsorption capacity, then carrying out second mixing treatment on the adsorption type ternary precursor mixture and a doped metal salt solution to uniformly disperse the doped metal salt on the surface of the ternary precursor to form a ternary precursor mixture adsorbed by the doped metal salt solution, and finally drying the ternary precursor mixture adsorbed by the doped metal salt solution to completely volatilize water and the organic complexing agent so as to obtain a core-shell structure of the ternary precursor adsorbed by the metal salt; when the ternary precursor adsorbed by the metal salt is sintered with a lithium source, a ternary material modified by uniformly doping metal elements and coating a metal oxide layer can be formed, the transition of the crystal structure of the surface layer of the material in the circulation process is effectively inhibited by doping the metal elements, the coating of the metal oxide layer can prevent the direct contact with an electrolyte, and the occurrence of interface side reaction is reduced, so that the circulation stability of the material can be improved.
The ternary material provided by the third aspect of the present application is a ternary material formed by sintering the mixture of the composite ternary precursor and the lithium source, wherein the mixture is doped with a metal element and coated with a metal oxide layer, and the method of double modification through doping with a metal element and coating with a metal oxide layer can improve the structural stability of the material and reduce the interface side reaction, thereby improving the cycle stability of the material.
According to the anode provided by the fourth aspect of the application, as the anode material comprises the ternary material, the mixture of the composite ternary precursor and the lithium source is sintered, so that the ternary material is doped with metal elements, and the metal oxide coating layer is constructed, the stability of the material can be improved, the side reaction can be reduced, and the circulation stability of the material can be improved.
In the secondary battery provided by the fifth aspect of the present application, since the positive electrode of the secondary battery is the positive electrode described above, the secondary battery has an electrochemical performance with good cycle stability.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a preparation flow chart of a preparation method of a composite ternary precursor provided in an embodiment of the present application;
FIG. 2 is a representation of Ti-doped and TiO materials provided in example 1 of the present application 2 SEM picture of ternary material formed by cladding;
FIG. 3 is a graph of Ti doping and TiO provided in example 1 of the present application 2 XRD patterns of the ternary material before and after coating modification;
FIG. 4 is a graph of cycle number versus discharge capacity for the ternary materials provided in examples 1-3 herein.
Detailed Description
In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the specification of the embodiments of the present application may not only refer to the specific content of each component, but also refer to the proportional relationship of the weight of each component, and therefore, the proportional enlargement or reduction of the content of the related components according to the specification of the embodiments of the present application is within the scope disclosed in the specification of the embodiments of the present application. Specifically, the mass described in the specification of the embodiments of the present application may be a mass unit known in the chemical industry field such as μ g, mg, g, kg, etc.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
The first aspect of the embodiments of the present application provides a composite ternary precursor, which has a core-shell structure and includes a ternary precursor material and a doped metal salt layer coated on the surface of the ternary precursor material.
The composite ternary precursor provided by the embodiment of the application contains the doped metal salt layer coated on the surface of the ternary precursor material, so that the ternary material with uniformly distributed metal doped elements and coated by the metal oxide layer can be formed after the composite ternary precursor is sintered with a lithium source, the metal element doping can effectively inhibit the conversion of the crystal structure of the surface layer of the material in the circulation process, the metal oxide layer coating can avoid the direct contact with electrolyte, the occurrence of side reaction is inhibited, and the circulation stability of the material can be improved.
In an embodiment, the molecular formula of the ternary precursor material is: ni x Co y Mn 1-x-y (OH) 2 Wherein x is more than or equal to 0.3 and less than or equal to 0.9, and y is more than or equal to 0.1 and less than or equal to 0.6. In particular embodiments, the ternary precursor material may have the formula Ni 0.7 Co 0.1 Mn 0.2 (OH) 2 And may also be Ni 0.8 Co 0.15 Mn 0.05 (OH) 2 And may also be Ni 0.6 Co 0.2 Mn 0.2 (OH) 2 . The ternary precursor material contained in the composite ternary precursor of the embodiment is a high-nickel ternary precursor, the specific capacitance of the battery can be improved to a certain extent, and the surface of the ternary precursor material can be coated with doped metal salt to form a composite ternary precursor coated with doped metal salt, so that the composite ternary precursor and a lithium source can form a ternary material doped with metal elements and coated with metal oxides under high-temperature sintering.
In some embodiments, the doped metal salt layer has a thickness of 0.15-0.45 μm; in a specific embodiment, the thickness of the doped metal salt layer is, but not limited to, 0.15 μm,0.2 μm,0.25 μm,0.3 μm,0.35 μm,0.4 μm,0.45 μm. With the increase of the thickness of the doped metal salt layer in this embodiment, the thickness of the metal oxide layer in the metal oxide layer-coated ternary material formed by sintering the composite ternary precursor and the lithium source is also increased, so that the dissolution of the electrolyte to the metal oxide coating layer in a long cycle can be reduced, but the excessive thickness of the doped metal salt layer reduces the filling amount of particles under the same volume, thereby affecting the energy density of the battery and reducing the capacity, and therefore, the thickness of the doped metal salt layer is controlled within a proper range, and the capacity of the battery can be improved.
In some embodiments, the composite ternary precursor has a particle size of 1.8-3.5 μm; the composite ternary precursor material in the embodiment is a small-particle precursor, and can be sintered with a lithium source at a lower temperature to form a ternary material.
In some embodiments, the specific surface area of the composite ternary precursor is from 8.5 to 12m 2 (ii)/g; the tap density of the composite ternary precursor is 1.6-1.9g/cm 3 (ii) a By adopting the ternary material formed by sintering the composite ternary precursor with the specific surface area and the tap density in the range of the embodiment and the lithium source, the energy density of the lithium battery can be increased, the interface reaction of the electrode active material and the electrolyte can be slowed down, and the cycle life of the lithium battery can be prolonged.
In an embodiment, the metal element contained in the doped metal salt layer includes: at least one of Ti, cu, mg, ca, zn, al, pb, cr and Mo. In specific embodiments, the metal element contained in the doped metal salt layer may be, but is not limited to, ti, cu, mg, ca, zn, al, pb, cr, and Mo. In the embodiment, the surface of the ternary precursor is coated with the doped metal salt layer, so that the ternary material coated with metal and metal oxide can be further formed, the transformation of the crystal structure of the surface layer of the material in the circulation process can be effectively inhibited, and the circulation stability of the material is improved.
A second aspect of the embodiments of the present application provides a method for preparing a composite ternary precursor, including:
s10: providing a nickel-cobalt-manganese ternary precursor;
s20: carrying out first mixing treatment on a nickel-cobalt-manganese ternary precursor and an organic complexing agent to obtain an adsorption type ternary precursor mixture;
s30: carrying out second mixing treatment on the doped metal salt solution and the adsorption type ternary precursor mixture to obtain a ternary precursor mixture adsorbed by the doped metal salt solution;
s40: and drying the ternary precursor mixture adsorbed by the doped metal salt solution to obtain the ternary precursor adsorbed by the doped metal salt.
According to the preparation method of the composite ternary precursor, firstly, the nickel-cobalt-manganese ternary precursor and an organic complexing agent are subjected to first mixing treatment, so that an adsorption type ternary precursor mixture with adsorption capacity can be formed; then carrying out second mixing treatment on the adsorption type ternary precursor mixture and the doped metal salt solution, so that the doped metal salt can be uniformly dispersed on the surface of the ternary precursor to form the ternary precursor mixture adsorbed by the doped metal salt solution; finally, drying the ternary precursor mixture adsorbed by the doped metal salt solution at a certain temperature for a certain time to completely volatilize water and the organic complexing agent so as to form a metal salt coated ternary precursor; the composite ternary precursor coated by the metal salt is of a core-shell structure, and a ternary material modified by metal element doping and metal oxide layer coating can be formed by sintering the composite ternary precursor and a lithium source for one time; in addition, the metal doping effectively inhibits the conversion of the crystal structure of the surface layer of the material in the circulation process, the stability of the material is improved, the doped metal oxide layer can avoid the direct contact with the electrolyte, and the occurrence of interface side reaction is reduced, so that the ternary material prepared by the embodiment has good circulation stability.
In step S10, the preparation method of the nickel-cobalt-manganese ternary precursor includes: and mixing the nickel salt solution, the cobalt salt solution and the manganese salt solution with a complexing agent and a precipitator in an inert atmosphere, and carrying out precipitation reaction to generate the nickel-cobalt-manganese ternary precursor. Wherein the inert atmosphere may be nitrogen. In a specific embodiment, according to the stoichiometric ratio of the nickel-cobalt-manganese ternary material, respectively dissolving cobalt salt, nickel salt and manganese salt in water, and mixing to obtain a nickel-cobalt-manganese salt solution; under the nitrogen atmosphere, adding a nickel-cobalt-manganese salt solution, an ammonia water solution and a sodium hydroxide solution into a reaction kettle for mixing, controlling the temperature in the reaction kettle to be 50 ℃ and the pH value to be 12, and carrying out precipitation reaction for 7 hours to generate a nickel-cobalt-manganese ternary precursor. In the embodiment, the temperature and the pH in the reaction kettle are controlled within a range suitable for precipitation reaction, so that the nickel-cobalt-manganese ternary precursor with good structural stability and particle size uniformity can be generated.
In the examples, the temperature in the precipitation reaction is 50-65 ℃; specifically, the precipitation reaction temperature may be, but is not limited to, 50 ℃,51 ℃,52 ℃,53 ℃,54 ℃,55 ℃,56 ℃,57 ℃,58 ℃,59 ℃,60 ℃,61 ℃,62 ℃,63 ℃,64 ℃,65 ℃. The embodiment properly increases the temperature of the precipitation reaction, and is beneficial to accelerating the nucleation and growth speed of the nickel-cobalt-manganese ternary precursor, so that the temperature of the precipitation reaction is controlled within a proper range, and the nucleation and growth of the nickel-cobalt-manganese ternary precursor are facilitated.
In the examples, the precipitation reaction time is 6-8h; specifically, the time of the precipitation reaction may be, but is not limited to, 6.5h,7h,7.5h,8h. In this embodiment, the time of the precipitation reaction is properly prolonged, which is beneficial to increase of the particle size and tap density of the nickel-cobalt-manganese ternary precursor, however, the time of the precipitation reaction is too long, which may cause the particle size of the nickel-cobalt-manganese ternary precursor to be too large, and although the increase of the tap density of the nickel-cobalt-manganese ternary precursor tends to be gentle after a certain time is exceeded, the particle size may be agglomerated due to the high conversion rate of the precipitate, so that the time of the precipitation reaction is controlled within a suitable range, and the particle size and tap density of the nickel-cobalt-manganese ternary precursor are easily made to reach predetermined values.
In the examples, the pH of the precipitation reaction system is 12-12.15; specifically, the pH of the precipitation reaction system may be 12 or 12.15. In the embodiment, the crystal nucleation speed of the nickel-cobalt-manganese ternary precursor can be increased by properly increasing the pH value of the reaction system, particles with better morphology are formed, but too high pH value of the reaction system can result in too high nucleation speed of the nickel-cobalt-manganese ternary precursor, the primary particles are small and compact, and the particle size distribution of the secondary particles can be widened, so that the pH value of the reaction system is controlled in a proper range, and the nickel-cobalt-manganese ternary precursor with good morphology and uniform particle size distribution is easily obtained.
In an embodiment, the complexing agent comprises at least one of ammonia, ammonium sulfate, ammonium chloride; the precipitator comprises at least one of sodium hydroxide and potassium hydroxide; the precipitant can be sodium hydroxide or potassium hydroxide. Specifically, the complexing agent can be ammonia water, ammonium sulfate and ammonium chloride; in a specific embodiment, the components and the addition amount of the components can be added according to the existing preparation method of the nickel-cobalt-manganese ternary precursor. The complexing agent in the embodiment can effectively complex metal ions, so that the disturbance of the addition of raw materials on the balance of precipitation is relieved, the excessive saturation of precipitates in the solution is controlled, the nucleation and growth speeds can be reduced, crystals can slowly grow, and the regulation and the control are convenient.
In step S20, mixing the nickel-cobalt-manganese ternary precursor with the organic complexing agent according to a ratio of 1: (0.2-0.5) to obtain a ternary precursor mixture adsorbed by the doped metal salt solution. The molar ratio of the nickel-cobalt-manganese ternary precursor to the organic complexing agent needs to be controlled to be 120% -160% of the stoichiometric amount of the doped metal salt, so that the nickel-cobalt-manganese ternary precursor is completely coated by the doped metal salt, too small molar ratio of the nickel-cobalt-manganese ternary precursor to the organic complexing agent can result in insufficient adsorption capacity of a ternary precursor mixture, and poor effect of coating the nickel-cobalt-manganese ternary precursor by the doped metal salt is caused, while too large molar ratio of the nickel-cobalt-manganese ternary precursor to the organic complexing agent can result in too long drying treatment time in the step S40 and difficulty in completely volatilizing the organic complexing agent. Wherein the organic complexing agent comprises: at least one of alcohol amine, amino carboxylic acid, carboxyl carboxylic acid, organic phosphonic acid and polyacrylic acid complexing agent; specifically, the organic complexing agent can be, but is not limited to, 8-hydroxyquinoline, methylenephosphonic acid, isopar-bonylphosphonic acid, and carboxylphosphonic acid. In a specific example, a nickel-cobalt-manganese ternary precursor is mixed with a carboxylic phosphonic acid according to a ratio of 1: and (3) carrying out first mixing treatment at a molar ratio of 0.2 to obtain a ternary precursor mixture adsorbed by the doped metal salt solution. In the embodiment, the nickel-cobalt-manganese ternary precursor and the organic complexing agent are mixed according to a certain molar ratio, so that a ternary precursor mixture with adsorption capacity can be formed, and the doped metal salt solution can be uniformly dispersed on the surface of the ternary precursor mixture.
In step S30, the metal salt and nickel-cobalt-manganese doped ternary precursor is mixed according to the ratio of (0.01-0.02): 1, and carrying out second mixing treatment to obtain a ternary precursor mixture adsorbed by the doped metal salt solution. The mass ratio of the doped metal salt to the nickel-cobalt-manganese ternary precursor is improved within a certain range, so that the stability of the coating structure is improved, and the conductivity of the further obtained ternary material is improved. Wherein the doped metal salt comprises Ti 2+ 、Cu 2+ 、Mg 2+ 、Ca 2+ 、Zn 2+ 、Al 2+ 、Pb 2+ 、Cr 2+ And Mo 2+ At least one soluble salt of (a); specifically, the doped metal salt may be, but is not limited to, tiCO 3 ，TiSO 4 ，MgSO 4 ，MgCO 3 ，Al 2 (CO 3 ) 3 And Al 2 (SO 4 ) 3 . In specific embodiments, tiCO 3 The solution and the nickel-cobalt-manganese ternary precursor are mixed according to the proportion of 0.01:1 to obtain TiCO 3 Solution adsorbed ternary precursor mixture.
In step S40, drying the ternary precursor mixture adsorbed by the doped metal salt solution at the temperature of 75-85 ℃ for 3.5-5h to obtain a ternary precursor adsorbed by the doped metal salt; specifically, the drying temperature may be, but is not limited to, 75 ℃,76 ℃,77 ℃,78 ℃,79 ℃,80 ℃,81 ℃,82 ℃,83 ℃,84 ℃,85 ℃; the drying time may be, but is not limited to, 3.5h,4h,4.5h,5h; in the embodiment, the drying temperature and the drying time are controlled within a proper range, so that the moisture and the organic solvent in the ternary precursor mixture adsorbed by the doped metal salt solution can be completely volatilized to obtain the ternary precursor adsorbed by the doped metal salt, the doped metal can be easily oxidized in advance due to overlong drying time or overhigh drying temperature, and the ternary material doped with the metal element and coated with the metal oxide can be formed by sintering the doped metal salt and the lithium source.
In a third aspect of the embodiments of the present application, a ternary material is provided, and is formed by sintering a mixture of a lithium source and the composite ternary precursor provided in the embodiments of the present application or the composite ternary precursor prepared by the preparation method of the composite ternary precursor provided in the embodiments of the present application.
The ternary material provided by the embodiment of the application has a core-shell structure formed by coating of the metal oxide layer, and is formed by sintering a mixture of a composite ternary precursor and a lithium source.
In a specific embodiment, the composite ternary precursor provided in the embodiment of the present application or the mixture of the composite ternary precursor prepared by the preparation method of the composite ternary precursor provided in the embodiment of the present application and a lithium source is placed in a muffle furnace, and the temperature is raised to 500-700 ℃ at a temperature-raising speed of 3-8 ℃/min and calcined for 6-10h, so as to obtain the ternary material.
In the examples, the composite ternary precursor was mixed with a lithium source according to (1.03-1.08): 1, sintering to form a ternary material; specifically, the mass ratio of the composite ternary precursor to the lithium source may be, but is not limited to, 1.03: 1. 1.04: 1. 1.04: 1. 1.05: 1. 1.06: 1. 1.07: 1. 1.08:1. in the embodiment, the composite ternary precursor and the lithium source are controlled in a proper proportion range, so that the specific capacity and the cycling stability of the battery can be improved, and the mass ratio of the composite ternary precursor to the lithium source is too high, so that the battery is easy to operateLithium forms LiO upon sintering 2 At the surface of the material with CO 2 ，H 2 O reaction to form Li 2 CO 3 And LiOH, which easily causes battery gassing and raises safety problems.
In the embodiment, the thickness of the metal oxide coating layer formed by sintering is 0.2-0.5 μm; in particular embodiments, the metal oxide coating layer may have a thickness of, but is not limited to, 0.2 μm,0.3 μm,0.4 μm, 0.5 μm. With the increase of the thickness of the metal oxide coating layer in this embodiment, the dissolution of the metal oxide coating layer by the electrolyte in a long cycle can be reduced, but the too high thickness of the metal oxide coating layer can reduce the filling amount of the particles under the same volume, thereby affecting the energy density of the battery and reducing the capacity, and therefore, the thickness of the metal oxide coating layer is controlled within a proper range, and the capacity of the battery can be improved.
In the examples, the particle size of the ternary material is 2-4 μm; the specific surface area of the ternary material is 8-10.2m 2 (ii)/g; the tap density of the ternary material is 1.65-1.85g/cm 3 . The ternary material with the granularity, the specific surface area and the tap density in the range of the embodiment is used as the raw material to manufacture the battery, so that the energy density of the battery can be increased, the interface reaction of the electrode active material and the electrolyte can be slowed down, and the cycle life of the lithium battery can be prolonged.
A fourth aspect of the embodiments of the present application provides a positive electrode including the ternary material provided in this embodiment.
According to the anode provided by the embodiment of the application, the material of the anode comprises the ternary material provided by the embodiment of the application, and the mixture of the composite ternary precursor and the lithium source is sintered, so that the metal element doping is carried out on the ternary material, the metal oxide coating layer is constructed, the stability of the material is improved, and the occurrence of side reactions is reduced, so that the cycle stability of the material is improved.
A fifth aspect of the embodiments of the present application provides a secondary battery including the positive electrode provided in the present embodiment.
According to the secondary battery provided by the embodiment of the application, the positive electrode of the secondary battery is the positive electrode provided by the embodiment of the application, so that the secondary battery has good electrochemical performance of cycle stability.
The following description will be given with reference to specific examples.
Example 1
The embodiment provides a preparation method of a composite ternary precursor and a ternary material, which comprises the following steps:
1. a preparation method of a composite ternary precursor comprises the following steps:
s10: the preparation method of the nickel-cobalt-manganese ternary precursor comprises the following steps: respectively dissolving nickel salt, cobalt salt and manganese salt in water according to the weight ratio of 6:2:2 to obtain a nickel-cobalt-manganese mixed solution; and carrying out coprecipitation reaction on the nickel-cobalt-manganese mixed solution, sodium hydroxide and ammonia water in a nitrogen atmosphere to obtain a nickel-cobalt-manganese ternary precursor.
S20: mixing the nickel-cobalt-manganese ternary precursor with 8-hydroxyquinoline, continuously stirring for 3 hours, and reacting to generate an adsorption type ternary precursor mixture.
S30: mixing TiSO 4 The solution is gradually added into the adsorption type ternary precursor mixture under the stirring state, ultrasonic vibration is carried out, and TiSO is obtained by continuous stirring reaction 4 Solution adsorbed ternary precursor mixture.
S40: mixing TiSO 4 Heating the ternary precursor mixture adsorbed by the solution in hot water circulation at 75-85 ℃, and completely volatilizing water and an organic complexing agent to obtain TiSO 4 And (3) coating a ternary precursor.
2. A preparation method of a composite ternary precursor comprises the following steps:
s50: mixing TiSO 4 Mixing the coated ternary precursor with a lithium source according to a molar ratio of 1.06 2 A coated ternary material.
3. The ternary material provided in the embodiment 1 is used as a raw material to assemble a battery, and a constant current charge and discharge test is performed at room temperature; the reversible discharge capacity retention rate is 93.43% after 100 cycles of activation for 2 cycles by 0.2C multiplying power and then cycling in a voltage range of 3.0-4.5V by 0.5C multiplying power.
Example 2
The embodiment provides a preparation method of a composite ternary precursor and a ternary material, which comprises the following steps:
1. a preparation method of a composite ternary precursor comprises the following steps:
s10: the preparation method of the nickel-cobalt-manganese ternary precursor comprises the following steps: respectively dissolving nickel salt, cobalt salt and manganese salt in water according to the ratio of 6:2:2 to obtain a nickel-cobalt-manganese mixed solution; and carrying out coprecipitation reaction on the nickel-cobalt-manganese mixed solution, sodium hydroxide and ammonia water under the nitrogen atmosphere to obtain a nickel-cobalt-manganese ternary precursor.
S20: mixing the nickel-cobalt-manganese ternary precursor with 8-hydroxyquinoline, continuously stirring for 3 hours, and reacting to generate an adsorption type ternary precursor mixture.
S30: mgSO (MgSO) 4 Gradually adding the solution into the adsorption type ternary precursor mixture under stirring, ultrasonically vibrating, and continuously stirring for reaction to obtain MgSO 4 Solution adsorbed ternary precursor mixture.
S40: mgSO (MgSO) will 4 Heating the ternary precursor mixture adsorbed by the solution in hot water circulation at 75-85 ℃, and completely volatilizing water and an organic complexing agent to obtain MgSO 4 A coated ternary precursor.
2. A preparation method of a composite ternary precursor comprises the following steps:
s50: mgSO (MgSO) 4 And mixing the coated ternary precursor with a lithium source according to a molar ratio of 1.06.
3. A battery assembled by taking the ternary material provided in the embodiment 2 as a raw material is subjected to constant-current charge and discharge test at room temperature; activating for 2 circles by 0.2C multiplying power, and then circulating within a voltage range of 3.0-4.5V by 0.5C multiplying power, wherein after 100 circles of circulation, the reversible discharge capacity retention rate is 92.75%.
Example 3
The embodiment provides a preparation method of a composite ternary precursor and a ternary material, which comprises the following steps:
1. a preparation method of a composite ternary precursor comprises the following steps:
s10: the preparation method of the nickel-cobalt-manganese ternary precursor comprises the following steps: respectively dissolving nickel salt, cobalt salt and manganese salt in water according to the ratio of 6:2:2 to obtain a nickel-cobalt-manganese mixed solution; and carrying out coprecipitation reaction on the nickel-cobalt-manganese mixed solution, sodium hydroxide and ammonia water under the nitrogen atmosphere to obtain a nickel-cobalt-manganese ternary precursor.
S20: mixing the nickel-cobalt-manganese ternary precursor with 8-hydroxyquinoline, continuously stirring for 3h, and reacting to generate an adsorption type ternary precursor mixture.
S30: mixing Al 2 (SO 4 ) 3 The solution is gradually added into the adsorption type ternary precursor mixture under the stirring state, ultrasonic vibration is carried out, and Al is obtained by continuous stirring reaction 2 (SO 4 ) 3 Solution adsorbed ternary precursor mixture.
S40: mixing Al 2 (SO 4 ) 3 Heating the ternary precursor mixture adsorbed by the solution in hot water circulation at 75-85 ℃, and completely volatilizing water and an organic complexing agent to obtain Al 2 (SO 4 ) 3 And (3) coating a ternary precursor.
2. A preparation method of a composite ternary precursor comprises the following steps:
s50: mixing Al 2 (SO 4 ) 3 Mixing the coated ternary precursor with a lithium source according to a molar ratio of 1.06 2 O 3 A coated ternary material.
3. A battery is assembled by using the ternary material provided in the embodiment 3 as a raw material, and a constant-current charge-discharge test is performed at room temperature; the reversible discharge capacity retention rate is 91.61% after 100 cycles of activation for 2 cycles by 0.2C multiplying power and then cycling in a voltage range of 3.0-4.5V by 0.5C multiplying power.
Experimental comparative analysis of ternary materials based on different doped metal and metal oxide coatings formed from different doped metal salt solutions and ternary precursors:
example 1 shown in FIG. 2 provides Ti doping and TiO 2 SEM image of ternary material formed by cladding and Ti shown in FIG. 3Doping and TiO 2 XRD patterns of the ternary material before and after coating modification show that: tiO2 2 Uniformly coating the surface of the ternary material, and doping Ti and TiO 2 After the coating modification, the 003 diffraction peak shifts to a low angle, indicating Ti 4+ Successfully doped into the lattice of the ternary material, resulting in an increase in the c-axis layer spacing of the ternary material.
TABLE 1
| Doping element | Test conditions | Capacity of 100 th circle | Capacity retention rate | |
| Example 1 | Ti doped- |
3.0-4.5V，0.5C | 187.1mA·h/g | 93.43％ |
| Example 2 | Mg doped-MgO cladding | 3.0-4.5V，0.5C | 184.0mA·h/g | 92.75％ |
| Example 3 | Al doped-Al 2O3 coating | 3.0-4.5V，0.5C | 178.2mA·h/g | 91.61％ |
The comparative analysis of the results of the battery performance tests after the battery is assembled by using the ternary materials of different doped metals and metal oxide coating layers in the table 1 as raw materials and the cycle number-discharge capacity curve diagram of the ternary materials provided in fig. 4 leads to the following conclusions:
the ternary material doped with the metal element and the metal oxide coating layer is used as a raw material to assemble a battery, after 100 cycles, the capacity is over 178.2mA.h/g, and the capacity retention rate is over 91.6 percent, which shows that the ternary material doped with the metal element and the metal oxide coating layer can improve the stability of the material structure, and further the capacity has high retention rate; the ternary material forming the layer structure has small structural change and good reversibility in the charge and discharge processes, so that the cycle performance of the battery can be improved.
The above description is only a preferred embodiment of the present application and should not be taken as limiting the present application, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A preparation method of a composite ternary precursor is characterized by comprising the following steps:
providing a nickel-cobalt-manganese ternary precursor; the molecular formula of the nickel-cobalt-manganese ternary precursor is as follows: ni x Co y Mn 1-x-y (OH) 2 Wherein x is more than or equal to 0.3 and less than or equal to 0.9, and y is more than or equal to 0.1 and less than or equal to 0.6;
mixing the nickel-cobalt-manganese ternary precursor with an organic complexing agent according to the weight ratio of 1: (0.2-0.5) carrying out first mixing treatment to obtain an adsorption type ternary precursor mixture;
carrying out second mixing treatment on the doped metal salt solution and the adsorption type ternary precursor mixture to obtain a ternary precursor mixture adsorbed by the doped metal salt solution;
and drying the ternary precursor mixture adsorbed by the doped metal salt solution to obtain the ternary precursor adsorbed by the doped metal salt, wherein the thickness of the doped metal salt layer is 0.15-0.45 mu m.
2. The method for preparing a composite ternary precursor according to claim 1,
the doped metal salt and the nickel-cobalt-manganese ternary precursor are prepared according to the following steps of (0.01-0.02): 1, the second mixing treatment is carried out; and/or
The organic complexing agent comprises: at least one of alcohol amine, amino carboxylic acid, carboxyl carboxylic acid, organic phosphonic acid and polyacrylic acid complexing agent; and/or
The doped metal salt comprises Ti 2+ 、Cu 2+ 、Mg 2+ 、Ca 2+ 、Zn 2+ 、Al 2+ 、Pb 2+ 、Cr 2+ And Mo 2+ At least one soluble salt of (a).
3. The method for preparing the composite ternary precursor according to claim 1 or 2, wherein the method for preparing the nickel-cobalt-manganese ternary precursor comprises:
and mixing the nickel salt solution, the cobalt salt solution and the manganese salt solution with a complexing agent and a precipitator in an inert atmosphere, and carrying out precipitation reaction to generate the nickel-cobalt-manganese ternary precursor.
4. The method for preparing the composite ternary precursor according to claim 3, wherein the temperature of the precipitation reaction is 50-65 ℃; and/or
The time of the precipitation reaction is 6-8h; and/or
The pH value of the precipitation reaction system is 12-12.15; and/or
The complexing agent comprises at least one of ammonia water, ammonium sulfate and ammonium chloride; and/or
The precipitant comprises at least one of sodium hydroxide and potassium hydroxide.
5. A composite ternary precursor is characterized in that the composite ternary precursor is prepared by the preparation method of the composite ternary precursor according to any one of claims 1 to 4, has a core-shell structure, and comprises a ternary precursor material and a doped metal salt layer coated on the surface of the ternary precursor material;
the molecular formula of the ternary precursor material is as follows: ni x Co y Mn 1-x-y (OH) 2 Wherein x is more than or equal to 0.3 and less than or equal to 0.9, and y is more than or equal to 0.1 and less than or equal to 0.6; the thickness of the doped metal salt layer is 0.15-0.45 μm.
6. The composite ternary precursor of claim 5, wherein the particle size of said composite ternary precursor is 1.8-3.5 μm; and/or
The specific surface area of the composite ternary precursor is 8.5-12m 2 (iv) g; and/or
The tap density of the composite ternary precursor is 1.6-1.9g/cm 3 (ii) a And/or
The metal elements contained in the doped metal salt layer comprise: at least one of Ti, cu, mg, ca, zn, al, pb, cr and Mo.
7. A ternary material, characterized by being formed by sintering a mixture comprising a complex ternary precursor prepared by the preparation method according to any one of claims 1 to 4 and a lithium source.
8. The ternary material according to claim 7, wherein the mass ratio of the composite ternary precursor to the lithium source is (1.03-1.08): 1; and/or
The thickness of the metal oxide coating layer formed by sintering is 0.2-0.5 μm; and/or
The granularity of the ternary material is 2-4 mu m; and/or
The specific surface area of the ternary material is 8-10.2m 2 (ii)/g; and/or
Vibration of the ternary materialThe solid density is 1.65-1.85g/cm 3 。
9. A positive electrode comprising the ternary material according to claim 7 or 8.
10. A secondary battery comprising the positive electrode according to claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111308679.7A CN114057238B (en) | 2021-11-05 | 2021-11-05 | Composite ternary material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111308679.7A CN114057238B (en) | 2021-11-05 | 2021-11-05 | Composite ternary material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114057238A CN114057238A (en) | 2022-02-18 |
| CN114057238B true CN114057238B (en) | 2022-12-27 |
Family
ID=80274218
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111308679.7A Active CN114057238B (en) | 2021-11-05 | 2021-11-05 | Composite ternary material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114057238B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114759183A (en) * | 2022-05-30 | 2022-07-15 | 远景动力技术(江苏)有限公司 | Low-cobalt positive electrode active material, method for producing same, electrochemical device, and electronic device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111689528A (en) * | 2020-07-10 | 2020-09-22 | 湖北亿纬动力有限公司 | Ternary material precursor and preparation method and application thereof |
| CN113113588A (en) * | 2021-04-09 | 2021-07-13 | 合肥工业大学 | Method for preparing lithium fast ion conductor material coated high-nickel ternary layered oxide by using covalent interface engineering strategy |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109119611B (en) * | 2018-08-22 | 2021-12-24 | 广东工业大学 | Method for realizing co-modification of ternary cathode material by ion doping and surface coating through one-step method |
| CN110233253B (en) * | 2019-06-28 | 2020-09-18 | 中国科学院化学研究所 | Binary-doped single-crystal ternary positive electrode material and preparation method thereof |
| CN112850807B (en) * | 2019-11-28 | 2024-01-09 | 惠州比亚迪电池有限公司 | Ternary precursor, preparation method, ternary material and lithium ion battery |
| CN111129463B (en) * | 2019-12-26 | 2020-11-17 | 格林美股份有限公司 | Preparation method of MOF-coated single crystal ternary cathode material and precursor thereof |
| CN111370700B (en) * | 2020-03-16 | 2021-06-29 | 宁夏中化锂电池材料有限公司 | High-capacity long-circulation monocrystal ternary cathode material and preparation method thereof |
-
2021
- 2021-11-05 CN CN202111308679.7A patent/CN114057238B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111689528A (en) * | 2020-07-10 | 2020-09-22 | 湖北亿纬动力有限公司 | Ternary material precursor and preparation method and application thereof |
| CN113113588A (en) * | 2021-04-09 | 2021-07-13 | 合肥工业大学 | Method for preparing lithium fast ion conductor material coated high-nickel ternary layered oxide by using covalent interface engineering strategy |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114057238A (en) | 2022-02-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110931768B (en) | High-nickel monocrystal lithium ion battery positive electrode material and preparation method thereof | |
| WO2023169591A1 (en) | Sodium-containing oxide positive electrode material and preparation method therefor and use thereof, and positive electrode plate and use thereof | |
| CN110690416B (en) | High-nickel ternary positive electrode material for lithium secondary battery and preparation method thereof | |
| CN107546383B (en) | High-performance core-shell structure high-nickel material, preparation method thereof and application thereof in lithium ion battery | |
| CN109119611B (en) | Method for realizing co-modification of ternary cathode material by ion doping and surface coating through one-step method | |
| CN112736230B (en) | High-voltage composite spinel-coated cathode material and preparation method thereof | |
| JP2011096650A (en) | Cathode active material particle powder, method of manufacturing the same, and nonaqueous electrolyte secondary battery | |
| CN108878860B (en) | Nickel-based positive electrode material, precursor thereof, and preparation methods of nickel-based positive electrode material and precursor | |
| CN109273688B (en) | High-nickel cathode material with surface rich in rock salt phase and preparation method and application thereof | |
| CN115275127A (en) | High-nickel precursor and preparation method thereof, and high-nickel positive electrode material and preparation method thereof | |
| CN112952085B (en) | Gradient high-nickel single crystal ternary material, preparation method thereof and battery using material | |
| CN110085831A (en) | A kind of metatitanic acid lithium cladding nickel-cobalt-manganternary ternary anode material and preparation method thereof | |
| CN114057238B (en) | Composite ternary material and preparation method and application thereof | |
| WO2021146893A1 (en) | Nickel-rich anode material, nickel-cobalt precursor material and preparation method, lithium-ion battery | |
| CN115498147A (en) | Hafnium-modified high-nickel layered oxide electrode material and preparation method thereof | |
| CN116779854A (en) | Preparation method of neodymium and tetraethyl silicate co-modified lithium-rich manganese-based lithium ion battery anode material | |
| CN114560510B (en) | Modified 7-series ternary cathode material and preparation method and application thereof | |
| CN114300664B (en) | Lithium-rich single crystal positive electrode material with surface coated with lithium selenate, and preparation method and application thereof | |
| CN115663134A (en) | Novel surface nano-coating and gradient doping integrated modified ultra-high nickel ternary cathode material and preparation method thereof | |
| CN114864911A (en) | Modified high-nickel ternary cathode material and preparation method and application thereof | |
| CN114784265A (en) | Modified high-nickel monocrystal nickel cobalt lithium manganate cathode material, preparation method thereof and lithium ion battery | |
| CN114156463A (en) | Lithium ion battery composite lithium-rich manganese-based positive electrode material and preparation method thereof | |
| CN117374259B (en) | Modification method of high-nickel positive electrode material, positive electrode plate and lithium battery | |
| CN110380039B (en) | Lamellar object coated spherical lithium-rich manganese-based positive electrode material precursor and preparation method thereof | |
| CN113809280B (en) | Cathode material and preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |