CN114084915A - Ternary precursor composite material, preparation method, ternary material and secondary battery - Google Patents

Ternary precursor composite material, preparation method, ternary material and secondary battery Download PDF

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CN114084915A
CN114084915A CN202111310528.5A CN202111310528A CN114084915A CN 114084915 A CN114084915 A CN 114084915A CN 202111310528 A CN202111310528 A CN 202111310528A CN 114084915 A CN114084915 A CN 114084915A
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ternary precursor
ternary
nickel
composite material
cobalt
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袁杰
郑江峰
吴浩
高琦
黄仁忠
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Guangdong Jiana Energy Technology Co Ltd
Qingyuan Jiazhi New Materials Research Institute Co Ltd
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Guangdong Jiana Energy Technology Co Ltd
Qingyuan Jiazhi New Materials Research Institute Co Ltd
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    • 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
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/34—Preparation of aluminium hydroxide by precipitation from solutions containing aluminium salts
    • 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
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • 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
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    • C01P2006/11—Powder tap density

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Abstract

The application belongs to the technical field of batteries, and particularly relates to a ternary precursor composite material and a preparation method thereof, a ternary material and a secondary battery. The preparation method of the ternary precursor composite material comprises the following steps: preparing a nickel-cobalt-manganese ternary precursor; mixing the nickel-cobalt-manganese ternary precursor with meta-aluminate and alkali liquor for reaction to obtain the product coated with Al (OH)3Ternary precursor composite material of shell layer. The preparation method of the ternary precursor composite material takes metaaluminate as a raw material of a coating material, can directly react with hydroxide ions under the condition of not using a complexing agent, and forms Al (OH) on the surface of the ternary precursor by utilizing a liquid phase coating process3And (4) coating. The preparation process is simple and is suitable for large-scale production and application. Al (OH) in the prepared ternary precursor composite material3The shell layer can effectively inhibit the dissolution of transition metal ions in the ternary precursor materialStructural stability of the high ternary precursor material.

Description

Ternary precursor composite material, preparation method, ternary material and secondary battery
Technical Field
The application belongs to the technical field of batteries, and particularly relates to a ternary precursor composite material and a preparation method thereof, a ternary material and a secondary battery.
Background
Lithium ion batteries are a new generation of green high-energy batteries, and increasingly play an important role in various fields. The nickel-cobalt-manganese ternary material has the characteristics of high specific capacity, long cycle life, low toxicity, low price and the like due to good synergistic effect among the three elements, and is widely applied. Generally, the high-nickel ternary positive electrode material has the characteristics of high specific capacity and low cost, but Ni in a layered structure3+And Ni4+The state is very unstable. These unstable Ni3+And Ni4+Ions are easy to enter the electrolyte in the circulating process to generate side reaction with the electrolyte, so that the structure of the material is changed, and the safety performance of the product faces huge challenges. The ternary positive electrode material precursor is the most core upstream product for producing the ternary positive electrode material, and the ternary positive electrode material precursor is prepared into the ternary positive electrode material by mixing and sintering with lithium salt (lithium carbonate for common products and lithium hydroxide for high-nickel products) at high temperature. The performance of the ternary positive electrode material precursor is slightly influenced in the high-temperature lithium-mixed sintering process, namely the ternary positive electrode material has good inheritance to the precursor, so that the quality of the ternary precursor is ensured to have a key influence on the performance of the ternary material.
Many scientific researches show that the dissolution of transition metal ions in the ternary cathode material can be inhibited by carrying out surface modification on the ternary precursor material. In order to improve the performance of the high nickel cathode material, researchers have proposed various means, mainly including: optimizing the synthesis process, doping, coating and the like. Among these, Al is a common coating material in the coating means2O3、ZrO2、TiO2And the Al-containing material has the characteristics of low cost, wide source, good stability and the like, and is a commonly used coating material at present. But do notIs, at present, Al2O3When Al-containing materials coat the ternary precursor materials, complexing agents are often needed, the gram capacity of the ternary anode materials can be reduced due to the use of the complexing agents, the electrochemical performance of the ternary anode materials is reduced, and Al2O3And the coating layer formed by the Al-containing material has poor effect of inhibiting the dissolution of transition metal ions in the ternary precursor material. In addition, from the electrochemical point of view, because of Al2O3The electrical conductivity is low, the impedance is increased, the charge transfer impedance is mainly increased after coating, so that the specific capacity of the coated material is slightly reduced, and the discharge rate performance and the low-temperature performance are poor.
Disclosure of Invention
The application aims to provide a ternary precursor composite material and a preparation method thereof, a ternary material and a secondary battery, and aims to solve the problem that the existing coating material has poor dissolution inhibition effect on transition metal ions in the ternary precursor material to a certain extent.
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 method for preparing a ternary precursor composite material, comprising the steps of:
preparing a nickel-cobalt-manganese ternary precursor;
mixing the nickel-cobalt-manganese ternary precursor with meta-aluminate and alkali liquor for reaction to obtain the product coated with Al (OH)3Ternary precursor composite material of shell layer.
Further, the conditions of the mixing reaction include: reacting for 1-3 hours under the conditions that the pH value is 8.5-9.5 and the stirring speed is 100-140 r/min.
Further, the mole ratio of the metaphosphate ions in the meta-aluminate to the hydroxide ions in the alkali liquor is 1: (6-7).
Further, the meta-aluminate is selected from: at least one of aluminum sulfate, sodium metaaluminate and potassium metaaluminate.
Further, the alkali liquor contains sodium hydroxide.
Further, the step of preparing the nickel-cobalt-manganese ternary precursor comprises: and mixing and reacting a nickel source solution, a cobalt source solution, a manganese source solution, a second alkali liquor and ammonia water to obtain the nickel-cobalt-manganese ternary precursor.
Further, the reaction conditions include: reacting at the temperature of 50-55 ℃ and the pH value of 11.5-12 until the particle size D50 of the precursor reaches a target value.
Further, according to NixCoyMnz(OH)2Adding the nickel source solution, the cobalt source solution and the manganese source solution into the reaction system according to the stoichiometric ratio of nickel, cobalt and manganese in the ternary precursor, wherein x + y + z is 1, x is more than or equal to 0.6 and less than or equal to 0.8, y is more than or equal to 0.1 and less than or equal to 0.2, and z is more than or equal to 0.2 and less than or equal to 0.3.
Further, the molar ratio of the ammonia water to the nickel source in the nickel source solution is (0.4-0.6): 1.
further, the molar ratio of hydroxyl in the second alkali liquor to the nickel source in the nickel source solution is (1.5-2.5): 1.
further, in the nickel source solution, the nickel source is selected from: at least one of nickel sulfate, nickel chloride and nickel nitrate.
Further, in the cobalt source solution, the cobalt source is selected from: at least one of cobalt sulfate, cobalt chloride and cobalt nitrate.
Further, in the manganese source solution, the manganese source is selected from: at least one of manganese sulfate, manganese chloride and manganese nitrate.
In a second aspect, the present application provides a ternary precursor composite material comprising a ternary precursor core and Al (OH) coated on an outer surface of the core3And (4) shell layer.
Further, in the ternary precursor composite material, the coating content of the aluminum element is 0.3-1 wt%.
Further, in the ternary precursor composite material, Al (OH)3The thickness of the shell layer is 0.2-0.3 μm.
Further, the particle size D50 of the ternary precursor composite material is 9-13 μm.
Further, the tap density of the ternary precursor composite material is 1.5-2.5 g/cm3。
In a third aspect, the present application provides a ternary material, wherein the ternary material is prepared by mixing and sintering the above ternary precursor composite material and lithium salt.
In a fourth aspect, the present application provides a secondary battery, wherein the positive electrode sheet of the secondary battery comprises the ternary material.
According to the preparation method of the ternary precursor composite material provided by the first aspect of the application, metaaluminate is used as a raw material of a coating material, and can directly react with hydroxide ions in alkali liquor to generate Al (OH)3Forming Al (OH) on the surface of the ternary precursor by a liquid phase coating process under the condition of not using a complexing agent3And (4) coating. The preparation process is simple, easy to operate, mild in reaction condition and suitable for industrial large-scale production and application. And prepared to be coated with Al (OH)3Ternary precursor composite for shell layer, Al (OH)3The shell layer can effectively inhibit the dissolution of transition metal ions in the ternary precursor material, and the structural stability of the ternary precursor composite material is improved, so that the structural stability and the safety of the ternary cathode material are improved.
The ternary precursor composite material provided by the second aspect of the application comprises a ternary precursor inner core and Al (OH) coated on the outer surface of the inner core3Shell layer of Al (OH)3The shell layer can effectively inhibit the dissolution of transition metal ions in the ternary precursor material, and improve the structural stability of the ternary precursor composite material, thereby improving the structural stability and safety of the ternary cathode material.
The ternary material provided by the third aspect of the application is prepared by mixing and sintering the ternary precursor composite material and lithium salt, wherein the ternary precursor composite material is coated with Al (OH)3The shell layer effectively inhibits the dissolution of transition metal ions in the ternary precursor material, improves the structural stability of the ternary precursor composite material, and has the advantages of regular product morphology, low tap density and increased active specific surface area. The ternary material prepared by mixing the lithium salt with the lithium salt and sintering the mixture has better propertyThe structural stability and the safety of the ternary material are improved, and the electrochemical performance of the ternary material is improved.
The positive plate of the secondary battery provided by the fourth aspect of the application comprises the ternary material, and the ternary material has better structural stability and safety, so that the electrochemical performances of the secondary battery such as cycle stability, safety, service life and the like are improved.
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 schematic flow chart of a method for preparing a ternary precursor composite material provided in an embodiment of the present application;
FIG. 2 is a scanning electron microscope image of the ternary precursor composite material provided in embodiments 1-3 of the present application;
fig. 3 is a scanning electron microscope image of the ternary precursor composite material provided in embodiments 1, 4, and 5 of the present application;
FIG. 4 is a scanning electron micrograph of a ternary precursor composite provided in example 6 of the present application;
FIG. 5 is a scanning electron micrograph of a ternary precursor composite provided in example 1 of the present application;
fig. 6 is a scanning electron microscope image of the ternary precursor composite provided in example 7 of the present application.
Detailed Description
In order to make the technical problems, technical solutions and advantageous 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 (one) of a, b, or c," or "at least one (one) of 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 description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass in the description of the embodiments of the present application may be in units of mass known in the chemical industry, such as μ g, mg, g, and kg.
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.
As shown in fig. 1, a first aspect of the embodiments of the present application provides a method for preparing a ternary precursor composite material, including the following steps:
s10, preparing a nickel-cobalt-manganese ternary precursor;
s20, mixing the nickel-cobalt-manganese ternary precursor with meta-aluminate and alkali liquor for reaction to obtain the product coated with Al (OH)3Ternary precursor composite material of shell layer.
In the preparation method of the ternary precursor composite material provided in the first aspect of the embodiment of the present application, after the nickel-cobalt-manganese ternary precursor is prepared, the nickel-cobalt-manganese ternary precursor, the meta-aluminate and the alkali solution are mixed and dissolved, in the mixing reaction process, the meta-aluminate can ionize metal aluminum ions, and the metal aluminum ions can be combined with hydroxide in the alkali solution to form al (oh)3Depositing on the surface of the nickel-cobalt-manganese ternary precursor to form Al (OH)3And obtaining a shell layer to obtain the ternary precursor composite material with the core-shell structure. In the preparation method of the ternary precursor composite material in the embodiment of the application, metaaluminate is used as the raw material of the coating material, and can directly participate in the reaction with hydroxide ions in alkali liquor to generate Al (OH)3Forming Al (OH) on the surface of the ternary precursor by a liquid phase coating process under the condition of not using a complexing agent3And (4) coating. The preparation process is simple, easy to operate, mild in reaction condition and suitable for industrial large-scale production and application. And prepared to be coated with Al (OH)3Ternary precursor composite for shell layer, Al (OH)3The shell layer can effectively inhibit the dissolution of transition metal ions in the ternary precursor material, and the structural stability of the ternary precursor composite material is improved, so that the structural stability and the safety of the ternary cathode material are improved. In addition, Al (OH)3The ionization degree is higher, the number of movable ions in the system is more, and the conductivity of the coating material can be obviously improved, so that the low level of the coating material is improvedMild rate capability.
In some embodiments, in step S10, the step of preparing the nickel-cobalt-manganese ternary precursor includes: mixing and reacting a nickel source solution, a cobalt source solution, a manganese source solution, a second alkali liquor and ammonia water, carrying out a complex reaction on metal raw materials such as a nickel source, a cobalt source, a manganese source and the like and the ammonia water in the reaction process, and then carrying out a coprecipitation reaction on the metal raw materials and the alkali liquor to generate a nickel-cobalt-manganese ternary precursor compound and form crystal grains to obtain the nickel-cobalt-manganese ternary precursor.
In some embodiments, the step of mixing the nickel source solution, the cobalt source solution, the manganese source solution, the second alkali solution, and the ammonia water comprises: in order to prevent metal raw materials such as a nickel source, a cobalt source, a manganese source and the like from being oxidized and improve the stability and the utilization rate of the raw materials, a nickel source solution, a cobalt source solution and a manganese source solution are respectively added into reaction systems such as a reaction kettle and the like under inert atmosphere such as nitrogen, argon, helium and the like; then adding ammonia water and a second alkali liquor to adjust the concentration and the pH value of ammonium ions in the reaction kettle. In some specific embodiments, after a nickel source, a cobalt source and a manganese source are respectively prepared into 1-2 mol/L solutions, the nickel source solution, the cobalt source solution, the manganese source solution and other raw materials are respectively injected into a reaction kettle at the flow rate of 100-130L/h through a variable frequency metering pump, and nitrogen is introduced to serve as a protective atmosphere to prevent metal elements in the raw materials from being oxidized; then, adding ammonia water and an alkaline solution of NaOH to adjust the concentration of ammonium ions and the pH value in the reaction kettle.
In some embodiments, a nickel source solution, a cobalt source solution, a manganese source solution, a second alkali solution and ammonia water are mixed and then react at a temperature of 50-55 ℃ and a pH value of 11.5-12, a metal raw material substance undergoes a complex reaction with the ammonia water and a coprecipitation reaction with the alkali solution to generate a nickel-cobalt-manganese ternary precursor compound, crystal grains are formed, and the crystal grains gradually grow until the particle size D50 of the precursor reaches a target value, so that the nickel-cobalt-manganese ternary precursor is obtained.
In some embodiments, a nickel source solution, a cobalt source solution, a manganese source solution, a second alkali solution and ammonia water are mixed and then react at a temperature of 50-55 ℃ and a pH value of 11.5-12, a nickel-cobalt-manganese ternary precursor compound is generated through a complexation reaction of a metal raw material substance and the ammonia water and a coprecipitation reaction of the metal raw material substance and the alkali solution, crystal grains are formed, the reaction is stopped after the crystal grains gradually grow until the particle size D50 of the precursor reaches 11.8-12 μm, the feed liquid is transferred to a centrifuge, and water is used for washing until the pH value of effluent is less than 9, so that the nickel-cobalt-manganese ternary precursor is obtained. The target value of the particle size D50 in the embodiment of the application ensures the reactivity and the capacity of the ternary precursor material.
In some embodiments, by NixCoyMnz(OH)2Adding a nickel source solution, a cobalt source solution and a manganese source solution into a reaction system according to the stoichiometric ratio of nickel, cobalt and manganese in the ternary precursor, wherein x + y + z is 1, x is more than or equal to 0.6 and less than or equal to 0.8, y is more than or equal to 0.1 and less than or equal to 0.2, and z is more than or equal to 0.2 and less than or equal to 0.3. The nickel source, cobalt source and manganese source of the embodiments of the present application are Ni as described abovexCoyMnz(OH)2The prepared ternary precursor material is a high-nickel ternary precursor material with the Ni content of 0.6-0.8, and the x content is 0.6-0.8, so that the high-nickel ternary cathode material can be obtained, the higher the nickel content is, the higher the actual specific discharge capacity of the ternary material is, but the thermal stability and the capacity retention rate can be reduced, and the high-nickel ternary cathode material with the Ni content of 0.6-0.8 has the characteristics of larger discharge capacity, good structural stability, good cycle performance and the like. In addition, in the ternary precursor material, the content of cobalt can influence the ionic conductivity of the ternary cathode material, and the content of cobalt is more than or equal to 0.1 and less than or equal to 0.2, so that the ternary cathode material has better charge-discharge rate performance. Mn during the charging and discharging process of the battery4+The valence state is unchanged, the manganese content can influence the structural stability of the ternary cathode material, and z is more than or equal to 0.2 and less than or equal to 0.3, so that the structure is stabilized. In some embodiments, the chemical formula of the ternary precursor material prepared includes, but is not limited to, Ni0.67Co0.13Mn0.20(OH)2、Ni0.80Co0.10Mn0.10(OH)2、Ni0.94Co0.03Mn0.03(OH)2、Ni0.60Co0.20Mn0.20(OH)2And the like.
In some embodiments, the molar ratio of ammonia to nickel source in the nickel source solution is (0.4-0.6): 1; the addition proportion of ammonia water in the reaction system can influence the complex reaction between metal raw material substances, and the metal raw material substances and ammonium ions can be fully complexed by the proportion. In some embodiments, the molar ratio of ammonia to nickel source in the nickel source solution includes, but is not limited to, 0.4:1, 0.5:1, 0.6:1, and the like.
In some embodiments, the molar ratio of hydroxide in the second alkaline solution to the nickel source in the nickel source solution is (1.5-2.5): 1, the proportion of hydroxide ions in a reaction system can influence the coprecipitation effect of a ternary precursor, and if the proportion of the hydroxide ions is too low, the ternary precursor compound is not beneficial to being fully precipitated; if the proportion of hydroxyl is too high, too much cation is introduced, so that the content of impurity elements in the ternary precursor is increased, and the electrochemical performance of the ternary precursor material is reduced. In some embodiments, the molar ratio of hydroxide in the second alkaline solution to nickel source in the nickel source solution includes, but is not limited to, 1.5:1, 2:1, 2.5:1, and the like.
In some embodiments, the alkaline substance in the second alkaline solution is sodium hydroxide, and the solvent is water, wherein the sodium hydroxide can provide abundant hydroxide ions, which is beneficial to precipitation of the ternary precursor compound; the water has good dissolving effect on components such as a nickel source, a cobalt source, a manganese source, ammonia water and the like, is beneficial to full reaction of the components, improves the utilization rate of raw materials, and simultaneously improves the preparation efficiency of the nickel-cobalt-manganese ternary precursor.
In some embodiments, the nickel source solution comprises a nickel source selected from the group consisting of: at least one of nickel sulfate, nickel chloride and nickel nitrate. In some embodiments, the cobalt source solution comprises a cobalt source selected from the group consisting of: at least one of cobalt sulfate, cobalt chloride and cobalt nitrate. In some embodiments, the manganese source in the manganese source solution is selected from the group consisting of: at least one of manganese sulfate, manganese chloride and manganese nitrate. The metal salts selected in the embodiments of the present application have good solubility, and are favorable for reacting with alkali liquor and ammonia water in a reaction system to generate a ternary precursor compound, and when the crystal grain of the chemical substance grows to an expected grain size D50, a nickel-cobalt-manganese ternary precursor is obtained.
In some embodiments, in step S20, the nickel-cobalt-manganese ternary precursor is mixed with meta-aluminate and alkali solutionAfter the mixing, carrying out mixing reaction for 1-3 hours under the conditions that the pH value is 8.5-9.5 and the stirring speed is 100-140 r/min, wherein no complexing agent is added in the mixing reaction process, the metaaluminate can ionize metal aluminum ions, and the metal aluminum ions are combined with hydroxide radicals in alkali liquor to form Al (OH)3Depositing on the surface of the nickel-cobalt-manganese ternary precursor to form Al (OH)3And obtaining a shell layer to obtain the ternary precursor composite material with the core-shell structure. Known solubility product Ksp [ Al (OH) ]3]＝1.9×10-33Complete formation of Al (OH)3The pH of the precipitate is about 6, and Al3+The ions meet OH-A large amount of Al (OH) is formed3Flocculent precipitate, but due to Al (OH)3Being amphoteric, higher acidity or basicity results in Al (OH)3Redissolving, so that the preferable pH value of the embodiment of the application is 8.5-9.5, and the Al (OH) is effectively ensured3Stability of (2), in favor of Al (OH)3Growing Al (OH) attached to the surface of the nickel-cobalt-manganese ternary precursor3And coating the shell layer. The pH value of the mixing reaction in the embodiment of the present application can be adjusted by additionally adding an alkaline substance such as sodium hydroxide.
In addition, the stirring speed is 100-140 r/min, preferably 110-130 r/min, preferably 120r/min, and within the stirring speed range of the embodiment of the application, with the increase of the stirring strength, not only can independent nucleation caused by local over-concentration of the material be effectively reduced, but also the mass transfer of the reaction ions in the system is enhanced, so that the reaction ions can be fully diffused; meanwhile, along with the increase of the stirring strength, the collision and friction probability among the particles is increased, so that the coating is more uniform and compact, and the particle surface tends to be smooth. However, when the stirring intensity is too high, the particles may be broken. In addition, the length of the reaction time also has an influence on the coating effect, and as the reaction time is prolonged, the uniformity of the coating layer of the composite material is improved, and the roughness of the surface is reduced, so that the surface of the composite material is more uniform and smooth. However, if the reaction time is too long, the cladding layer in the ternary precursor composite material is too thick, so that the gram volume of the composite material is reduced.
In some embodiments, the molar ratio of hydroxide ions in the meta-aluminate to the alkaline solution is 1:(6-7); the proportion not only fully ensures that aluminum ions in the aluminum metaaluminate and hydroxide ions in the alkali liquor react to generate Al (OH)3Precipitating; and a slight excess of hydroxide ions prevents the precipitation of aluminum. If the proportion of the meta-aluminate is too high or too low, the reaction by-products are increased, and the control of Al (OH) is not facilitated3And the thickness of the coating layer. In some embodiments, the molar ratio of hydroxide ions in the meta-aluminate and the lye may be 1:6, 1:6.5, 1:7, and the like.
In some embodiments, the meta-aluminate is selected from: at least one of aluminum sulfate, sodium metaaluminate and potassium metaaluminate; these meta-aluminates all contain meta-aluminates and can react directly with hydroxide ions to form Al (OH)3And a complexing agent is not added in the reaction process of the coating layer, so that the reaction efficiency is high.
In some embodiments, the lye comprises sodium hydroxide and the solvent, including but not limited to water, facilitates the reaction of the hydroxide ions with the meta-aluminate to form Al (OH)3And (4) coating.
In some embodiments, a method of making a ternary precursor composite comprises the steps of:
s11, pressing NixCoyMnz(OH)2Adding a nickel source solution, a cobalt source solution and a manganese source solution into a reaction system according to the stoichiometric ratio of nickel, cobalt and manganese in the ternary precursor, wherein x + y + z is 1, x is more than or equal to 0.6 and less than or equal to 0.8, y is more than or equal to 0.1 and less than or equal to 0.2, and z is more than or equal to 0.2 and less than or equal to 0.3; and then adding ammonia water and a second alkali liquor to adjust the pH value in the reaction kettle to 11.5-12, reacting at the temperature of 50-55 ℃ until the particle size D50 of the precursor reaches 11.8-12 mu m, stopping the reaction, transferring the feed liquid into a centrifuge, and washing with water until the pH value of effluent is less than 9 to obtain the nickel-cobalt-manganese ternary precursor.
S21, mixing the nickel-cobalt-manganese ternary precursor with meta-aluminate and alkali liquor, wherein the molar ratio of hydroxide ions in the meta-aluminate to the alkali liquor is 1: (6-7), then adding an alkaline substance to adjust the pH value to 8.5-9.5, carrying out mixing reaction for 1-3 hours under the condition that the stirring speed is 100-140 r/min, putting the feed liquid into a centrifugal machine, and washing the feed liquid with pure water to obtain the product coated with Al (OH)3Ternary precursor composition of shell layerA material.
The second aspect of the embodiment of the application provides a ternary precursor composite material, which comprises a ternary precursor core and Al (OH) coated on the outer surface of the core3And (4) shell layer.
The ternary precursor composite material provided by the second aspect of the embodiment of the application comprises a ternary precursor inner core and Al (OH) coated on the outer surface of the inner core3Shell layer of Al (OH)3The shell layer can effectively inhibit the dissolution of transition metal ions in the ternary precursor material, and the structural stability of the ternary precursor composite material is improved, so that the structural stability and the safety of the ternary cathode material are improved.
In some embodiments, the ternary precursor composite material comprises 0.3 to 1 wt% of the aluminum element, further 0.3 to 0.8 wt%, and further 0.3 to 0.5 wt%. In some embodiments, the ternary precursor composite material comprises Al (OH)3The thickness of the shell layer is 0.2 to 0.3 μm, specifically 0.2 μm, 0.25 μm, 0.3 μm, or the like. The coating content/thickness can effectively inhibit the dissolution of transition metal ions in the ternary precursor material, and improve the structural stability and safety of the ternary precursor composite material and the ternary cathode material. If the coating amount of the aluminum element is too high or the thickness of the coating layer is too thick, the gram capacity of the composite material is reduced, the precursor composite material and a lithium source are influenced to be sintered to prepare the ternary cathode material, lithium ion diffusion is influenced, and the electrochemical performance of the ternary cathode material is reduced. If the coating amount of the aluminum element is too low or the thickness of the coating layer is too low, the dissolution of transition metal ions in the ternary precursor material is difficult to be effectively inhibited, and the improvement effect on the structural stability and the safety performance of the ternary precursor composite material and the ternary cathode material is poor.
The particle size D50 of the ternary precursor composite material in the embodiment of the application can be regulated and controlled in the preparation process according to the actual application requirements, and the particle size D50 of the ternary precursor is regulated and controlled by controlling the grain growth time, the material concentration, the reaction conditions and other factors. In some embodiments, the particle size D50 of the ternary precursor composite material is 9-12 μm, is small and uniform, and is beneficial to the subsequent preparation of the ternary cathode material, so that the prepared ternary cathode material has a larger specific surface area, is beneficial to lithium ion deintercalation, and improves the electrochemical performance of the ternary cathode material. In some embodiments, the particle size D50 of the ternary precursor composite includes, but is not limited to, 9 μm, 10 μm, 11 μm, 12 μm, and the like.
In some embodiments, the tap density of the ternary precursor composite is 1.5-2.5 g/cm3. The ternary precursor composite material in the embodiment of the application has relatively small tap density and large active specific surface area, and is favorable for reacting with lithium salt to generate the ternary material. In some embodiments, the tap density of the ternary precursor composite includes, but is not limited to, 1.5g/cm3、2g/cm3、2.5g/cm3And the like.
In a third aspect of the embodiments of the present application, a ternary material is provided, which is obtained by mixing and sintering the above ternary precursor composite material and a lithium salt.
The ternary material provided by the third aspect of the embodiments of the present application is prepared by mixing and sintering the ternary precursor composite material with lithium salt, wherein the ternary precursor composite material is coated with al (oh)3The shell layer effectively inhibits the dissolution of transition metal ions in the ternary precursor material, improves the structural stability of the ternary precursor composite material, and has the advantages of regular product morphology, low tap density and increased active specific surface area. The ternary material prepared by mixing the lithium salt with the lithium salt and sintering the mixture has good structural stability and safety, and the electrochemical performance of the ternary material is improved.
In some embodiments, the lithium salt is selected from one or more of lithium hydroxide, lithium chloride, lithium carbonate, lithium acetate, lithium nitrate, and lithium oxalate, and each of the lithium salts can be sintered with the ternary precursor composite material at a high temperature to form the ternary cathode material.
In some embodiments, the molar ratio of the metal ions to the lithium salt in the ternary precursor composite material is (1-1.1): 1, and the ratio is favorable for the ternary precursor composite material to fully react with the lithium salt to generate the nickel-cobalt-manganese ternary cathode material.
In some embodiments, the ternary precursor composite is mixed with a lithium salt at a sintering temperature of 450 ℃ and a sintering time of 600 ℃3-8h, the sintering condition can ensure that the ternary precursor composite material fully reacts with lithium salt to generate NixCoyMnzAnd (3) O ternary cathode material, wherein x + y + z is 1.
The fourth aspect of the embodiments of the present application also provides a secondary battery, in which a positive electrode sheet of the secondary battery contains the ternary material described above.
The positive plate of the secondary battery provided by the fourth aspect of the embodiment of the present application comprises the ternary material in the above embodiments, and the ternary material has good structural stability and safety, so that the electrochemical properties of the secondary battery, such as cycle stability, safety, service life, and the like, are improved.
In some embodiments, the positive plate comprises a current collector and an active material layer, wherein the current collector and the active material layer are arranged in a lamination mode, and the active material layer comprises a ternary material, a conductive agent, a binder and the like.
In some embodiments, the process for preparing the positive electrode material into the positive electrode sheet comprises the following steps: mixing the ternary positive electrode material, the conductive agent and the binder to obtain electrode slurry, coating the electrode slurry on a current collector, and drying, rolling, die cutting and the like to obtain the positive electrode plate.
In some embodiments, the positive electrode current collector includes, but is not limited to, any one of a copper foil, an aluminum foil.
In some embodiments, the binder is present in the electrode slurry in an amount of 2 wt% to 4 wt%. In particular embodiments, the binder may be present in an amount of 2 wt%, 3 wt%, 4 wt%, and the like, which are typical and not limiting. In a specific embodiment, the binder comprises one or more of polyvinylidene chloride, soluble polytetrafluoroethylene, styrene butadiene rubber, hydroxypropyl methylcellulose, carboxymethylcellulose, polyvinyl alcohol, acrylonitrile copolymer, sodium alginate, chitosan, and chitosan derivatives. In some embodiments, the conductive agent is present in the electrode slurry in an amount of 3 wt% to 5 wt%. In specific embodiments, the content of the conductive agent may be 3 wt%, 4 wt%, 5 wt%, and the like, which are typical but not limiting contents. In particular embodiments, the conductive agent includes one or more of graphite, carbon black, acetylene black, graphene, carbon fibers, C60, and carbon nanotubes.
The secondary battery in the embodiment of the present application may be a lithium ion battery or a lithium metal battery or the like.
The negative electrode sheet, the electrolyte, the diaphragm and the like in the secondary battery of the embodiment are not particularly limited, and can be applied to any battery system.
In order to make the details and operations of the embodiments of the present invention clearly understood by those skilled in the art, and to make the advanced performances of the ternary precursor composite material and the preparation method thereof, the cathode material, and the secondary battery of the embodiments of the present invention obviously manifest, the embodiments are exemplified below by a plurality of examples.
Example 1
A ternary precursor composite, the preparation of which comprises the steps of:
1.1 reagents and apparatus
Reagent: NiSO4·6H2O、CoSO4·7H2O、MnSO4·H2O、Al2(SO4)318H2O, NaOH solution, aqueous ammonia solution;
equipment: a 100L reaction kettle (a whole set), a pH meter, an A3 atomic absorption instrument (Beijing Pujingyou Co., Ltd.), ICP-optima 5300DV (American PE company), a RISE-2006 particle size analyzer and a TSM-6301F scanning electron microscope.
1.2 precursor preparation
Preparing 1.5mol/L solution of Ni sulfate, Co sulfate and Mn sulfate according to the chemical dose ratio of Ni to Co to Mn of 94 to 03, and then mixing the solution with ammonia water and NaOH solution according to the ammonia-nickel ratio: 0.5:1, alkali-nickel ratio: 2:1, controlling the flow rate to be 120g/min, adding the mixture into a 100L reaction kettle, and controlling the reaction temperature: stopping feeding after the precursor D50 is 11.8-12.0 μm at 50-55 deg.C and pH is 11.5-12.0, placing the feed liquid in a centrifuge, washing with pure water until the pH of the effluent is less than 9 to obtain Ni0.94Co0.03Mn0.03(OH)2Precursor, abbreviation: matrix-NCM.
1.3 coating of precursor with Al (OH)3
A certain amount of Ni is added in the step 1.20.94Co0.03Mn0.03(OH)2Adding the precursor into a 100L reaction kettle, adding pure water, and uniformly stirringLast 0.5mol/L Al2(SO4)3Adding the mixture and 3mol/L NaOH solution into a reaction kettle according to the flow ratio of 1:1, adding NaOH to adjust the pH value to 9 after the material liquid is added, reacting for 2 hours under the condition of stirring speed of 120r/min, putting the material liquid into a centrifugal machine, and washing with pure water to obtain the Al (OH) coated solution3Ni of shell layer0.94Co0.03Mn0.03(OH)2Composite precursors, abbreviation: NCM-A2, wherein the theoretical coating amount of aluminum is 0.5 wt%.
Example 2
A ternary precursor composite material differing from example 1 in that: in step 1.3, the pH value is adjusted to 8, and the ternary precursor composite material is prepared by the following steps: NCM-A1.
Example 3
A ternary precursor composite material differing from example 1 in that: in step 1.3, the pH value is adjusted to 10, and the ternary precursor composite material is prepared by the following steps: NCM-A3.
Example 4
A ternary precursor composite material differing from example 1 in that: in the step 1.3, the reaction time is 1 hour, and the prepared ternary precursor composite material is shortened as follows: NCM-A4.
Example 5
A ternary precursor composite material differing from example 1 in that: in the step 1.3, the reaction time is 1.5 hours, and the prepared ternary precursor composite material is shortened as follows: NCM-A5.
Example 6
A ternary precursor composite material differing from example 1 in that: in the step 1.3, the stirring speed is 100r/min, and the ternary precursor composite material is prepared by the following steps: NCM-A6.
Example 7
A ternary precursor composite material differing from example 1 in that: in the step 1.3, the stirring speed is 140r/min, and the ternary precursor composite material is prepared by the following steps: NCM-A7.
Further, in order to verify the advancement of the embodiments of the present application, the following performance tests were respectively performed on the embodiments:
1. the influence of different pH values on the coating result is investigated through examples 1-3
The granularity D50, tap density, aluminum content, morphology and the like of the ternary precursor and the ternary precursor composite material of the embodiment 1-3 are respectively detected, and the test results are shown in the following table 1 and the scanning electron microscope chart of the attached figure 2:
TABLE 1
Figure BDA0003341046230000151
As can be seen from the test results in Table 1 above, as the reaction pH was increased from 8 to 9, the tap density of the coated sample gradually approached that of the substrate, and the coating amount of Al was close to the theoretical design value of 0.5 wt% at pH 9. However, as the PH continued to increase, from 9 to 10, the tap density and Al coating of the sample decreased, and it was likely that the PH was higher and the Al coating on the surface of the particles began to dissolve, causing a decrease in the amount of Al coating and re-agglomeration of the particles.
In addition, as can be seen from the results shown in FIG. 2, as the reaction pH increased from 8 to 9, the dispersibility of the particles gradually changed from sticky agglomerates to smooth-surfaced dispersed particles, and as the reaction pH continued to increase from 9 to 10, re-agglomeration occurred, which is consistent with the results of the tests in Table 1.
2. The influence of different coating times on the coating results was investigated by examples 1 and 4 to 5
The surface appearances of the ternary precursor composite materials of the embodiments 1 and 4-5 are respectively observed, and the test results are shown in a scanning electron microscope diagram of an attached figure 3, so that along with the side length of the coating time, the uniformity of the surface of the ternary precursor composite material is improved, the surface roughness is reduced, and the surface of the ternary precursor composite material coated for 2 hours in the embodiment 1 is more uniform and smooth.
3. The influence of different stirring strengths on the coating results was investigated by examples 1 and 6 to 7
The surface morphologies of the ternary precursor composite materials of examples 1 and 6-7 were respectively observed, and the test results are shown in the scanning electron microscope images of fig. 4 (example 6), 5 (example 1), and 6 (example 7), which shows that with the increase of the stirring strength, not only can the independent nucleation caused by the local over-concentration of the material be effectively reduced, but also the mass transfer of the reactive ions in the system is enhanced, so that the reactive ions can be fully diffused. Meanwhile, the increase of the stirring strength aggravates the collision and friction probability among the particles, so that the coating is more uniform and compact, and the particle surface tends to be smooth. However, too high a stirring intensity may cause particle breakage, as in example 7.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement 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 ternary precursor composite material is characterized by comprising the following steps:
preparing a nickel-cobalt-manganese ternary precursor;
mixing the nickel-cobalt-manganese ternary precursor with meta-aluminate and alkali liquor for reaction to obtain the product coated with Al (OH)3Ternary precursor composite material of shell layer.
2. The method of preparing a ternary precursor composite according to claim 1, wherein the conditions of the mixing reaction comprise: reacting for 1-3 hours under the conditions that the pH value is 8.5-9.5 and the stirring speed is 100-140 r/min;
and/or the molar ratio of metaaluminate ions in the metaaluminate to hydroxide ions in the alkali liquor is 1: (6-7);
and/or, the meta-aluminate is selected from: at least one of aluminum sulfate, sodium metaaluminate and potassium metaaluminate;
and/or the alkali liquor contains sodium hydroxide.
3. The method of preparing the ternary precursor composite of claim 1 or 2, wherein the step of preparing the nickel-cobalt-manganese ternary precursor comprises: and mixing and reacting a nickel source solution, a cobalt source solution, a manganese source solution, a second alkali liquor and ammonia water to obtain the nickel-cobalt-manganese ternary precursor.
4. The method of preparing a ternary precursor composite according to claim 3, wherein the reaction conditions comprise: reacting at the temperature of 50-55 ℃ and the pH value of 11.5-12 until the particle size D50 of the precursor reaches a target value.
5. The method of preparing a ternary precursor composite material according to claim 3, wherein Ni is present as NixCoyMnz(OH)2Adding the nickel source solution, the cobalt source solution and the manganese source solution into a reaction system according to the stoichiometric ratio of nickel, cobalt and manganese in the ternary precursor, wherein x + y + z is 1, x is more than or equal to 0.6 and less than or equal to 0.8, y is more than or equal to 0.1 and less than or equal to 0.2, and z is more than or equal to 0.2 and less than or equal to 0.3;
and/or the molar ratio of the ammonia water to the nickel source in the nickel source solution is (0.4-0.6): 1;
and/or the molar ratio of hydroxide ions in the second alkali liquor to the nickel source in the nickel source solution is (1.5-2.5): 1.
6. the method of preparing a ternary precursor composite according to claim 3, wherein in the nickel source solution, the nickel source is selected from the group consisting of: at least one of nickel sulfate, nickel chloride and nickel nitrate;
and/or, in the cobalt source solution, the cobalt source is selected from: at least one of cobalt sulfate, cobalt chloride and cobalt nitrate;
and/or, in the manganese source solution, the manganese source is selected from: at least one of manganese sulfate, manganese chloride and manganese nitrate.
7. The ternary precursor composite material is characterized by comprising a ternary precursor core and Al (OH) coated on the outer surface of the core3And (4) shell layer.
8. The ternary precursor composite material according to claim 7, wherein the coating content of the aluminum element in the ternary precursor composite material is 0.3 to 1 wt%;
and/or, said Al (OH)3The thickness of the shell layer is 0.2-0.3 μm;
and/or the particle size D50 of the ternary precursor composite material is 9-13 μm;
and/or the tap density of the ternary precursor composite material is 1.5-2.5 g/cm3。
9. A ternary material, wherein the ternary material is prepared by mixing and sintering the ternary precursor composite material as claimed in any one of claims 7 to 8 with a lithium salt.
10. A secondary battery characterized in that a positive electrode sheet of the secondary battery contains the ternary material according to claim 9.
CN202111310528.5A 2021-11-05 2021-11-05 Ternary precursor composite material, preparation method, ternary material and secondary battery Pending CN114084915A (en)

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