CN114014383A - High-tap-density positive electrode material and preparation method of positive electrode piece - Google Patents
High-tap-density positive electrode material and preparation method of positive electrode piece Download PDFInfo
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- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/00—Electrodes
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The application belongs to the technical field of positive electrode materials, and particularly relates to a high-tap-density positive electrode material and a preparation method of a positive electrode piece, wherein a metal mixed salt solution, a precipitator solution and a complexing agent solution are independently fed into a liquid in a protective atmosphere, are continuously mixed with a base solution in a reaction container, and are subjected to precipitation reaction; carrying out solid-liquid separation treatment on the overflowing reaction feed liquid and returning the obtained filter residue to the reaction container for at least one reaction growth treatment; stopping feeding when the precipitate reaches a preset granularity and a preset radial distance, aging the reaction liquid in the reaction container, then performing solid-liquid separation to obtain a high-tap precursor, mixing the high-tap precursor with lithium salt, and then performing sintering treatment to obtain a high-tap anode material; the positive pole piece is obtained by mixing the high-tap positive pole material with the conductive agent, the aluminum powder and the low-melting-point metal powder and then performing hot pressure processing.
Description
Technical Field
The application belongs to the technical field of battery materials, and particularly relates to a high-tap positive electrode material and a preparation method of a positive electrode piece.
Background
In recent years, international society is gradually reducing the dependence on fossil energy to achieve the goal of carbon neutralization, and new energy electric vehicles are gradually coming into the visual field of people and are also increasingly appearing on the city street. As one of the most important parts of a new energy automobile, a battery has been receiving attention from various fields. The compaction also determines the energy density of the anode material to a certain extent, but the high-compaction material is generally obtained by a large-diameter-distance precursor obtained by a continuous method or a series of growth process conditions at present, the conventional continuous method cannot realize the consistent growth cycle of large and small particles, so that the consistency of the material is poor, and the high-compaction material obtained by optimizing the process conditions sometimes does not have the required morphology, or physicochemical indexes, productivity and the like cannot well meet the requirements; the performance of electrochemical performance and evaluation thereof can be directly influenced by the quality of coating, and the performance of the material is often influenced by the problems of moisture absorption, viscosity and the like of the material in the process of coating the positive electrode, the conductive agent and the binder on the positive electrode current collector in a pulping mode in the existing process.
Generally, the yield of the high-tap positive electrode precursor material prepared by the conventional continuous method is large but difficult to control, the radial distance is generally 1.0-1.4 and cannot be automatically adjusted, in addition, the high tap density has influence on the capacity and internal resistance of the battery and the polarization effect in the charging and discharging processes, and the positive electrode material with the proper and relatively high tap density can reduce the internal resistance of the battery, reduce the polarization loss, prolong the cycle life of the battery and improve the utilization rate of the lithium ion battery.
Generally speaking, the ultimate purpose of pulping and coating is to combine the positive electrode with the current collector, and the normal positive electrode manufacturing step is to prepare a slurry which can just flow by adjusting the viscosity of the positive electrode, a conductive agent and a binder by a manual or mechanical method and coating the slurry on an aluminum foil, wherein the method comprises the following steps: the preparation method comprises the steps of pulping, coating, rolling and cutting, wherein organic matters are introduced in the process to reduce the conductivity of the material, and the preparation steps are more, so that the material is easy to absorb moisture and the loss in the preparation process is larger.
Disclosure of Invention
The application aims to provide a preparation method of a high-tap positive electrode material and a positive electrode piece, and aims to solve the problems of low tap, poor consistency, poor conductivity of the positive electrode piece and large loss in the preparation process of the positive electrode material prepared by the conventional preparation method to a certain extent.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
the application provides a preparation method of a high-tap positive electrode material, which comprises the following steps:
in a protective atmosphere, continuously mixing a metal mixed salt solution, a precipitator solution and a complexing agent solution with a base solution in a reaction container in a continuous feeding mode respectively, and carrying out precipitation reaction;
after the overflowing reaction feed liquid after the precipitation reaction is subjected to first solid-liquid separation treatment, returning the obtained filter residue to the reaction container for at least one reaction growth treatment;
stopping feeding the metal mixed salt solution, the precipitator solution and the complexing agent solution when the precipitate reaches the preset granularity and the preset diameter distance; aging the reaction liquid in the reaction container, and then carrying out second solid-liquid separation to obtain a high-tap precursor;
and carrying out second mixing treatment on the high-tap precursor and lithium salt, and sintering treatment to obtain the high-tap positive electrode material.
Further, the metal ion concentration of the metal mixed salt solution is 0.5-2.5mol/L, and the flow rate is 0.001L/h-500L/h;
the concentration of the precipitant solution is 4-14mol/L, and the flow rate is 0.0001L/h-375L/h;
the concentration of the complexing agent solution is 0.2-14mol/L, and the flow rate is 0.0001L/h-375L/h.
Furthermore, the metal mixed salt solution, the precipitator solution and the complexing agent solution are fed independently.
Further, the protective gas in the protective atmosphere is continuously introduced into the reaction container in a gas flow mode, and the protective gas is independently introduced.
Further, the general formula of the high tap precursor is (Ni)xCoyMnzQd)LeWherein x is more than or equal to 0 and less than or equal to 1-d, y is more than or equal to 0 and less than or equal to 1-d, z is more than or equal to 0 and less than or equal to 1-d, d is more than or equal to 0 and less than or equal to 0.5, and x + y + z + d is equal to 1; q is one or more of Fe, Mg, Ca, Al, Y, Ti, Zn, Zr, Nb, Mo or W, L is hydroxyl or carbonate, the diameter distance S of the high tap precursor is 0.8-2.0, and the granularity D50 is 5.0-20.0 μm.
Further, the metals in the metal mixed salt solution include Ni, Co, Mn, and Q; wherein Q is one or more of Fe, Mg, Ca, Al, Y, Ti, Zn, Zr, Nb, Mo or W; and/or
The salt in the metal mixed salt solution comprises one or more of sulfate, chloride, nitrate, acetate or alkoxide; and/or
The complexing agent solution comprises one or more of EDTA solution, ammonia water solution, ammonium chloride solution, ammonium sulfate solution and ammonium nitrate solution; and/or
The precipitant solution comprises one or more of ammonia water solution, sodium hydroxide solution, potassium hydroxide solution and sodium carbonate solution.
Further, the concentration of ammonium radical in the base solution is 0.1-20mol/L, and the pH value is 7-14; and/or
The protective gas is one or more of nitrogen or rare gas; and/or
The lithium salt is one or more of lithium carbonate, lithium hydroxide and lithium titanate.
Further, the reaction growth treatment process is accompanied with a first stirring treatment, and the first stirring rate is gradually slowed down from 350rpm at 300-; and/or
The temperature in the reaction vessel is maintained at 30-90 ℃; and/or
The aging treatment is specifically a second stirring treatment which is carried out continuously after the alkali is added, and the speed of the second stirring treatment is 25-50 rpm.
The second aspect of the present application provides a method for preparing a positive electrode plate, comprising the following steps:
and mixing the high-tap positive electrode material prepared by the preparation method with a conductive agent, aluminum powder and low-melting-point metal powder, and then carrying out hot-pressing processing to obtain the positive electrode piece.
Further, the temperature of the hot pressure processing treatment is 20-400 ℃, and the pressure is 0.1MPa-30 MPa; and/or
The conductive agent is one or more of conductive carbon black, superfine conductive carbon black, acetylene carbon black, graphene, carbon fiber and carbon nano tube; and/or
The low-melting-point metal powder is one or more of tin powder, bismuth powder, lead powder, cadmium powder and indium powder.
According to the preparation method of the high-tap anode material, the method of step-type continuous mixing reaction is adopted, the overflowing reaction material liquid is subjected to first solid-liquid separation treatment and then fed back to the reaction container in the reaction process, the steps are repeated, so that the particle size of a precursor in the reaction is different, the radial distance is controllable, the prepared anode material is high in tap, and the precursor material is prepared in the same reaction container under the same condition, so that the obtained anode material is good in consistency.
According to the preparation method of the anode piece provided by the second aspect of the application, the uniformity of the raw materials is guaranteed through solid-phase mixing, the mixed raw materials are directly pressed and formed in a hot pressure processing mode, a complex pulping process is avoided, the adhesive force among the high-compaction anode material, the conductive agent and the metal powder is enhanced, meanwhile, the deformation resistance of the anode is reduced, and the prepared anode piece has higher density and better conductivity.
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 process flow diagram for preparing a high tap positive electrode material provided in an embodiment of the present application;
fig. 2 is a relationship between the cycle number and specific capacity of the button cell battery provided by the embodiment of the application;
fig. 3 is a particle size distribution diagram of a cathode material provided in an example of the present application;
fig. 4 is a scanning electron microscope image of the cathode material provided in the embodiment 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 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 method for preparing a high-tap cathode material, where a process flow is shown in fig. 1, and the method includes the following steps:
s01: in a protective atmosphere, continuously mixing a metal mixed salt solution, a precipitator solution and a complexing agent solution with a base solution in a reaction container in a continuous feeding mode respectively, and carrying out precipitation reaction;
s02: after carrying out first solid-liquid separation treatment on the overflowed reaction feed liquid, returning the obtained filter residue to the reaction container for carrying out at least one reaction growth treatment;
s03: stopping feeding the metal mixed salt solution, the precipitator solution and the complexing agent solution when the precipitate reaches the preset granularity and the preset diameter distance; aging the reaction liquid in the reaction container, and then carrying out second solid-liquid separation to obtain a high-tap precursor;
s04: and carrying out second mixing treatment on the high-tap precursor and lithium salt, and sintering treatment to obtain the high-tap positive electrode material.
It should be noted that, at present, high-tap materials are generally obtained by large-diameter-distance precursors obtained by a continuous method or a series of growth process conditions, the conventional continuous method cannot achieve the consistent growth cycle of large and small particles, so that the consistency of the materials is poor, and the high-tap materials obtained by optimizing the process conditions sometimes do not have the required morphology, or physicochemical indexes, productivity and the like cannot well meet the requirements. The method for preparing the high-tap positive electrode material provided by this embodiment adopts a staged continuous mixing reaction mode, and adds part of the precursor in the reaction liquid back to the reaction vessel at a certain frequency after the first solid-liquid separation treatment in the reaction process to continue to grow, and repeats this step, so that the particle size of the prepared precursor is different, the diameter distance is large and controllable, and the prepared positive electrode material has high tap.
In step S01, the metal mixed salt solution, the precipitant solution, and the complexing agent solution are continuously added in a continuous addition manner, so that the precipitation reaction is continuously performed, a new precursor is generated by continuous reaction, and the generated precursor maintains a certain particle size growth rate.
In the examples, the metal mixed salt solution was fed at a concentration of 0.5 to 2.5mol/L and at a flow rate of 0.001L/h to 500L/h. In other examples, the precipitant solution is controlled to have a concentration of 4 to 14mol/L and is fed at a flow rate of 0.0001L/h to 375L/h. In still other embodiments, the complexing agent solution has a concentration of 0.2 to 14mol/L and is fed at a flow rate of 0.0001L/h to 375L/h. The reaction rates of the three are controlled by simultaneously controlling the feeding rates of the three or respectively controlling the feeding rates of the three, so that the precursor is continuously generated within a certain rate range and the particle size is increased.
In particular embodiments, the metals in the metal mixed salt solution include Ni, Co, Mn, and Q; q is one or more of Fe, Mg, Ca, Al, Y, Ti, Zn, Zr, Nb, Mo or W, the salt in the metal mixed salt solution comprises one or more of sulfate, chlorate, nitrate, acetate or alkoxide, and the molar ratio of metal ions such as nickel ions, cobalt ions, manganese ions, Q element ions and the like in the solvent is controlled to ensure that the required precursor is obtained by precipitation reaction; the complexing agent solution can comprise one or more of EDTA solution, ammonia water solution, ammonium chloride solution, ammonium sulfate solution and ammonium nitrate solution, achieves the purpose of coprecipitation through complexation and is assisted with the improvement of the crystal morphology; the precipitant solution may include one or more of ammonia solution, sodium hydroxide solution, potassium hydroxide solution and sodium carbonate solution, and the precipitant solution can ensure the precipitation reaction to be smoothly carried out by reaching a certain pH value.
In the embodiment, the concentration of ammonium radicals in the base solution is 0.1-20mol/L, the pH value is 7-14, the pH value in the base solution is controlled to slowly carry out the precipitation reaction, and a compact, stable and uniform precursor is generated;
the protective gas is one or more of nitrogen or rare gas, the rare gas comprises helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe) and radon (Rn), and other gases in the air are prevented from generating side reaction with the raw materials in the reaction process.
In addition, the process of the precipitation reaction is accompanied with a first stirring treatment, the first stirring speed is gradually reduced from 300-350rpm to 120-160rpm along with the reaction process, and the stirring speed is gradually reduced along with the increase of the precursor particle size, so as to relieve the extrusion and collision among precursor particles caused by centripetal force, thereby reducing the fragmentation among the precursor particles caused by extrusion collision, enabling the precursor particles to form stable growth and maintaining the structural integrity;
in the process of precipitation reaction, the temperature in the reaction container is kept at 30-90 ℃, the temperature in the reaction container is properly increased, the reaction activity of each raw material in the reaction container is facilitated, the higher reaction rate is kept, and products with different shapes and structures can be obtained by adjusting the reaction temperature.
It should also be noted that the reaction vessel for feeding the three reactants can be a reaction kettle commonly used in the current production, and the size of the reaction vessel can be 2L-40m3The method can also be an improved reaction kettle, for example, the reaction kettle is provided with respective feed inlets of three solutions of a metal mixed salt solution, a precipitator solution and a complexing agent solution, the feed inlets of the three solutions and an air inlet of a protective gas are independently arranged, an overflow port with a piston is arranged at a position slightly below the air inlet, in the specific embodiment of the application, part of precursor feed liquid subjected to filtering treatment directly overflows from the overflow port of the reaction container to a filtering device, the manner of taking out the precursor solution is simple and easy to operate, and does not interfere the reaction in the reaction container, meanwhile, the metal mixed salt solution, the precipitator solution and the complexing agent solution are independently fed, the three solutions are not contacted before reaching the reaction container, the phenomenon that the reaction feed liquid reacts in advance to generate impurities when not reaching the reaction container due to the mixed feed is avoided, further, the protective gas is continuously introduced into the reaction kettle in an air flow manner, and protective gas independently admits air, reaction vessel has certain leakproofness, can make inside certain malleation of formation of reaction vessel stop the admission of outside air behind the continuous protective gas that lets in, prevent that the reaction feed liquid in the reaction vessel from contacting with the air and then being oxidized, in the embodiment of this application, the inlet pipe of metal mixed salt solution, complexing agent solution, precipitant solution and protective gas's intake pipe dispersion arrange, can arrange with 3 o ' clock directions, 6 o ' clock directions, 9 o ' clock directions and 12 o ' clock directions of clock direction respectively, and the direction of admitting air of metal mixed salt solution, complexing agent solution, precipitant solution all is perpendicular to the liquid level downwards and the export all is below the liquid level.
In step S02, after performing a first solid-liquid separation treatment on the overflowing reaction feed liquid, returning the obtained filter residue to the reaction container for at least one reaction growth treatment, where the filter residue after the first solid-liquid separation treatment is left to stand for a t time and then returned to the reaction container for the reaction growth treatment, and the reaction container reacts to generate a very small amount of new precursor particles within the t time period of standing, and meanwhile, the particle size of the generated precursor also increases with the reaction progress to form a certain particle size difference with the filtered precursor.
In step S03, the predetermined particle size is 5.0 μm or less, D50 or less, 20.0 μm or less, D50 represents the particle size corresponding to the cumulative particle size distribution percentage of a sample reaching 50%, the predetermined diameter distance S (also referred to as the particle size distribution span) is in the range of 0.8 to 2.0, and the diameter distance S is (D90-D10)/D50, which is a measure of the width of the particle size distribution of the sample, the smaller S is the narrower the particle size distribution, and conversely, the wider the particle size distribution is, the more the particles in the prepared precursor are filled with each other, the smaller the voids are, so that the higher the tap of the prepared cathode material is, as shown in fig. 3, the schematic diagram of the diameter distance and the particle size distribution of the high tap cathode material prepared in this example, specifically, the morphology of the high tap cathode material prepared in this example under an electron microscope is shown in fig. 4, wherein the particle sizes of the high tap electrode material are different, and the gaps between the particles are smaller, the tap is high.
In the embodiment of the application, the aging treatment is specifically a second stirring treatment which is performed continuously after the alkali is added, wherein the speed of the second stirring treatment is 25-50rpm, so that metal ions dissociated in the feed liquid are fully reacted to a certain extent, and the surface morphology of the precursor is optimized.
Further, the aging treatment time is 2-24h, the added alkali can be sodium hydroxide or potassium hydroxide and is used for reacting with metal ions which are not completely reacted, the metal utilization rate is improved, the alkali concentration is 0.1-12mol/L, the volume is determined according to the volume of a reaction container and the reaction characteristics, in the specific embodiment of the application, the volume of the added alkali solution is 10ml-100L, the aging treatment can ensure that the free metal ions on the surface of the precursor have sufficient time for reaction and growth, and can optimize the morphology of the precursor and improve the sphericity of precursor particles.
It should be noted that, in the following description,the general formula of the high-tap precursor prepared by the preparation method provided by the embodiment of the application is (Ni)xCoyMnzQd)LeWherein x is more than or equal to 0 and less than or equal to 1-d, y is more than or equal to 0 and less than or equal to 1-d, z is more than or equal to 0 and less than or equal to 1-d, d is more than or equal to 0 and less than or equal to 0.1, and x + y + z + d is equal to 1; q is one or more of Fe, Mg, Ca, Al, Y, Ti, Zn, Zr, Nb, Mo or W, L is hydroxyl or carbonate, and the preparation of each metal ion in the metal mixed salt solution can be (Ni) according to the general formula of the precursorxCoyMnzQm)LnThe element ratio in the precursor is used for preparing a metal mixed salt solution, and the target precursor is accurately and efficiently generated.
In step S03, the lithium salt is one or more of lithium carbonate, lithium hydroxide, and lithium titanate, and further, the mass ratio of the high-tap positive electrode material precursor to the lithium salt is 1: 0.8-1.2.
In the embodiment of the application, after the aging treatment, deionized water washing is needed, and then a second solid-liquid separation treatment is carried out, wherein the washing is carried out for filtering to remove impurities such as residual alkali, and the washed sample is dried and then sintered; the sintering treatment temperature is 600-1000 ℃, and the sintering time is 4-72h, in the specific embodiment of the application, the sintering treatment comprises preheating treatment and heat treatment, the preheating treatment temperature is 300-600 ℃, the preheating time is 2-8h, the heat treatment temperature (namely, the sintering temperature) is 600-1000 ℃, and the sintering time is 4-72h, and the sintering condition can meet and complete the ion migration and lattice recombination in the process of synthesizing the precursor into the cathode material.
The second aspect of the present application provides a method for preparing a positive electrode plate, comprising the following steps:
and mixing the high-tap positive electrode material prepared by the preparation method with a conductive agent, aluminum powder and low-melting-point metal powder, and then carrying out hot-pressing processing to obtain the positive electrode piece.
It should be noted that, in the normal manufacturing process of the positive electrode plate at present, the positive electrode, the conductive agent, the binder and the solvent are adjusted in viscosity by hand or mechanically to prepare a slurry which can just flow, and the slurry is coated on the aluminum foil, and the method flow is as follows: the preparation method of the anode provided by the embodiment of the application adopts a hot-pressing processing mode to directly press and form the mixed raw materials, avoids the complicated pulping process, enhances the adhesive force between the high-compaction anode material and the conductive agent and metal powder, relieves the deformation resistance of the anode in the heat treatment process, enables the prepared anode to have higher compactness and be more durable, and tests show that the anode prepared by the method provided by the embodiment can enable the high-compaction anode material to be utilized by 100 percent, and can be applied to button batteries and laminated batteries, the battery prepared by the positive electrode has better conductivity, the first charge-discharge efficiency can reach 97%, and the first charge-discharge efficiency is only 89% under the conventional method of the same material.
In the embodiment of the application, the temperature of the hot-pressing processing is 20-400 ℃, the pressure is 0.1-30 MPa, the positive electrode is easy to be pressed and formed under the condition, and the preparation efficiency of the positive electrode is improved under the condition that the performance of each raw material is not influenced.
In the embodiment of the application, the conductive agent is one or more of conductive carbon black, ultrafine conductive carbon black, acetylene black, graphene, carbon fiber and carbon nano tube, the conductive agent has good conductivity, a grid structure is formed through hot pressure processing, and the grid structure is inlaid with a high-tap positive electrode material, so that the conductive agent has better conductivity, a more stable and more uniform structure and longer charge-discharge cycle life.
In the embodiment of the application, the low-melting-point metal powder is one or more of tin powder, bismuth powder, lead powder, cadmium powder and indium powder, and the active material is mixed with the low-melting-point metal, so that the positive electrode can be more easily pressed and formed, and the conductivity of the positive electrode piece is improved.
In order to make the above implementation details and operations of the present application clearly understood by those skilled in the art, and to make the progress of the high tap cathode material and the preparation method of the cathode obviously apparent in the examples of the present application, the above technical solutions are illustrated by a plurality of examples below.
Example one
The base solution was adjusted to 1L in a 2L reactor, having a certain pH of 10.8, 2.5g/L ammonium radical, temperature of 55 deg.C, rotation speed of 260rpm and continuous nitrogen flow for a certain period of time. Firstly, dissolving nickel sulfate, cobalt sulfate and manganese sulfate according to a metal molar ratio of 5:2:3 to obtain a metal mixed salt solution of 2 mol/L; mixing sodium hydroxide and an ammonia water solution according to a molar ratio of 6: 1 to obtain a precipitant solution with hydroxyl of 8 mol/L; dissolving ammonium chloride and an ammonia water solution according to a molar ratio of 1:1 to obtain a complexing agent solution with ammonium groups of 8 mol/L; then three solutions of metal mixed salt solution, precipitator solution and complexing agent solution are injected into a reaction kettle from respective feed inlets through a peristaltic pump, the three solutions enter pipelines of the reaction kettle and are dispersedly arranged to form four different directions with an air inlet, an overflow port is arranged at the position slightly lower than the air inlet, the temperature is controlled to be 55 ℃, the pH value is 10.8, the ammonium radical is 2.5g/L, the flow rate of the metal salt solution is kept to be 20ml/h, the precipitator solution is 10ml/h and the complexing agent solution is 2ml/h before the reaction period, the relative constant flow rate of the feed liquid is kept on the basis of keeping the pH value and the ammonium radical stable (mainly related to the flow rate stability of the peristaltic pump and needing to carry out flow rate fine adjustment to ensure the stability of the ammonium radical and the pH value), the temperature is gradually increased and kept to be 75 ℃ after the feed is carried out for 30 minutes, the pH value is 9.5, the ammonium radical is 2.0g/L, keeping relatively constant feed liquid flow, controlling the stirring rotation speed to reduce along with the growth of the granularity, reducing the stirring rotation speed to 220rpm at 5 microns, reducing the stirring rotation speed to 200rpm at 6 microns, reducing the stirring rotation speed to 180rpm at 7 microns, reducing the stirring rotation speed to 160rpm at 8 microns, reducing the stirring rotation speed to 140rpm at 9 microns, finally reducing the rotation speed to 140rpm at 10 microns, introducing nitrogen all the time, along with the reaction, when the feed liquid in the reaction kettle reaches the full kettle, overflowing the feed liquid to a filtering device outside the reaction kettle after the kettle is full, pumping the feed liquid into the reaction kettle again through a peristaltic pump after most of mother liquid is filtered, pumping the feed liquid into the reaction kettle within 3 minutes every 180 minutes through the peristaltic pump, continuously feeding, growing and pulling the radial distance by mixing the inside and the outside, stopping feeding when the granularity reaches 10 microns, and controlling the radial distance to be 1.2 at the moment.
After the feeding is stopped, the rotating speed of the reaction kettle is reduced to 30rpm, and 10ml of 8mol/L solution is added after stirring for 4 hoursThe sodium hydroxide solution is continuously stirred at a low speed, the sodium hydroxide solution is washed and filtered after being aged for 12 hours, the obtained filter cake is dried at 120 ℃, the filter cake is weighed and mixed with lithium carbonate after 18 hours, wherein Li/M is 1.1, the mixture is uniformly mixed and then put into a tubular furnace for sintering, the sintering preheating temperature is 550 ℃, the heat preservation time is 2 hours, the heat treatment temperature is 850 ℃, the heat preservation time is 16 hours, and the sodium hydroxide solution with the size of 10 micrometers, the radial distance of 1.2 and the tap compaction time of 2.3g/cm is finally obtained after sintering3The positive electrode material LNCM 523.
Crushing and grinding the obtained cathode material LNCM523, drying at 120 ℃ for 8h, and mixing with a conductive agent sp, wherein the mass ratio of the conductive agent sp to the positive electrode material LNCM523 is 10: 1, mixing with aluminum powder, wherein the mass ratio is 2: 1, finally mixing the powder with tin powder, wherein the mass ratio of the powder to the tin powder is 8: and 1, finally, carrying out hot-pressing processing on the mixed powder at 232 ℃ to obtain a positive pole piece, and cutting to obtain the positive pole piece applicable to button batteries and laminated batteries.
By using the obtained positive electrode plate and a lithium plate as a counter electrode to assemble a half cell, as shown in fig. 2, the capacity after 10 times of circulation at a current density of 0.1C in a blue test system can reach 169mAh/g, and the obtained first effect is 97%.
Example two
The bottom liquid is prepared in a 2L reaction kettle, the volume of the bottom liquid is 1L, the pH value is 13.1, the ammonium radical is 18g/L, the temperature is 68 ℃, the rotating speed of 330rpm is kept, and argon gas is continuously introduced for a certain time. Firstly, dissolving nickel acetate, cobalt acetate, manganese acetate and ferric chloride according to the metal molar ratio of 90:4:4:2 to obtain 1.5mol/L metal mixed salt solution; preparing a solution with the concentration of 11mol/L of sodium hydroxide as a precipitant solution; EDTA and an ammonia solution are mixed according to a molar ratio of 1: 2 mixing to obtain a complexing agent solution with 4mol/L of ammonium radicals; then three solutions of metal mixed salt solution, precipitator solution and complexing agent solution are injected into a reaction kettle from respective feed inlets through a peristaltic pump, pipelines of the three solutions entering the reaction kettle are arranged in a dispersing way to form four different directions with an air inlet, an overflow port is arranged at the position slightly below the air inlet, the temperature is controlled to be 68 ℃, the pH value is 13.1, the ammonium radical is 18g/L, the flow rate of the metal salt solution is kept to be 40ml/h, the precipitator solution is 11ml/h and the complexing agent solution is 6ml/h in the front of the reaction period for 10 minutes, the flow rate of the material liquid is kept relatively constant on the basis of keeping the pH value and the ammonium radical stable, the temperature is kept unchanged after feeding for 10 minutes, the pH value is 9.8, the ammonium radical is 2.3g/L, the relatively constant flow rate of the material liquid is kept, the stirring speed is controlled to be reduced along with the growth of the granularity, the 5 mu m is reduced to 280rpm, the 6 mu m is reduced to 230rpm, 7 μm down to 170rpm, 8 μm down to 120rpm, 9 μm down to 100rpm, 10 μm down to 85rpm, 11 μm down to 60rpm, and finally 16 μm at 60rpm, and argon was passed through. After the material liquid in the reaction kettle is full of the material liquid, the material liquid overflows to a filtering device outside the reaction kettle, most mother liquid is filtered, and then the material is pumped into the reaction kettle through a peristaltic pump again, the material is pumped into the reaction kettle through the peristaltic pump within 3 minutes every 120min, the material is continuously fed, the material is grown through the inner material mixing and the outer material mixing, the radial distance is pulled, the feeding is stopped when the granularity reaches 16 micrometers, and the radial distance is 1.0 at the moment.
After feeding is stopped, the rotating speed of the reaction kettle is reduced to 30rpm, 20ml of 4mol/L sodium hydroxide solution is added after stirring for 4 hours, low-speed stirring is continued, washing and filtering are carried out after aging for 12 hours, the obtained filter cake is dried at 130 ℃, the filter cake is weighed and mixed with lithium hydroxide after 18 hours, wherein Li/M is 1.05, the mixture is uniformly mixed and then put into a tube furnace for sintering, the sintering preheating temperature is 500 ℃, the heat preservation time is 8 hours, the heat treatment temperature is 700 ℃, the heat preservation time is 18 hours, and finally the anode material LNCMF90442 which is 16 micrometers in size, 1.0 in diameter distance and 2.3g/cm3 in tap is obtained after sintering.
Crushing and grinding the obtained cathode material LNCMF90442, drying at 120 ℃ for 8 hours, and mixing with a conductive agent graphene, wherein the mass ratio of the conductive agent graphene to the conductive agent graphene is 10: 1, mixing with aluminum powder, wherein the mass ratio is 5: and 1, finally mixing the alloy with BiSnPd alloy (53% of Bi, 15% of Sn and 32% of Pd) in a mass ratio of 4: and 1, finally, carrying out hot-pressing processing on the mixed powder at 100 ℃ to obtain a positive pole piece, and cutting to obtain the positive pole piece applicable to button batteries and laminated batteries.
The obtained positive pole piece is utilized, a lithium piece is taken as a counter electrode to assemble a half cell, the capacity after 20 times of circulation in a blue test system at the current density of 0.1C can reach 207mAh/g, and the obtained first effect is 92%.
Example three
The bottom liquid was adjusted in a 20L reactor to a volume of 10L, with a certain pH of 7.8, ammonium groups of 0.2g/L, temperature of 40 ℃, 300rpm speed and nitrogen gas continuously passed for a certain period of time. Firstly, nickel nitrate: manganese nitrate according to a metal molar ratio of 80: dissolving at the ratio of 20 to obtain 2.5mol/L metal mixed salt solution; preparing a solution with the concentration of sodium carbonate of 7.5mol/L as a precipitator solution; preparing an ammonia water solution into a complexing agent solution of 0.2 mol/L; then three solutions of metal mixed salt solution, precipitator solution and complexing agent solution are injected into a reaction kettle from respective feed inlets through a peristaltic pump, pipelines of the three solutions entering the reaction kettle are arranged in a dispersed manner to form four different directions with an air inlet, an overflow port is arranged at the position slightly below the air inlet, the temperature is controlled to be 40 ℃, the pH value is 7.8, the ammonium radical is 0.2g/L, the flow rate of the metal salt solution is kept to be 1L/h, the precipitator solution is 0.34L/h and the complexing agent solution is 0.16L/h before the reaction period is carried out for 120 minutes, the relative constant of the flow rate of the feed liquid is kept on the basis of keeping the pH value and the ammonium radical stable, after the feed is carried out for 120 minutes, the temperature is gradually increased and kept to be 40 ℃, the pH value is 7.5, the ammonium radical is 3.5g/L, the relative constant of the flow rate of the feed liquid is kept, the stirring speed is controlled to be reduced along with the growing granularity, and the 5 mu m is reduced to 220rpm, 6 μm down to 200rpm, 7 μm down to 180rpm, 8 μm down to 160rpm, 9 μm down to 140rpm, and finally at 10 μm at 140rpm, and once with nitrogen. After the feed liquid in the reaction kettle is full of the feed liquid, the feed liquid overflows to a filtering device outside the reaction kettle, most of the mother liquid is filtered, and then the feed liquid is pumped into the reaction kettle through a peristaltic pump again, the feed liquid is pumped into the reaction kettle through the peristaltic pump every 450 minutes within 3 minutes, the feed liquid grows and the radial distance is pulled open through continuous feeding and internal and external mixing, the feed is stopped when the granularity reaches 10 micrometers, and the radial distance is 1.9 at the moment.
After feeding is stopped, reducing the rotating speed of the reaction kettle to 30rpm, stirring for 4h, adding 200ml of 2mol/L sodium carbonate solution, continuously stirring at a low speed, aging for 12h, washing and filtering, drying the obtained filter cake at 130 ℃, weighing the filter cake after 18h, mixing the filter cake with lithium titanate, wherein Li/M is 1.08, uniformly mixing, putting the mixture into a tube furnace for sintering, sintering at a preheating temperature of 500 ℃, keeping the temperature for 4h, keeping the heat treatment temperature at 760 ℃, keeping the temperature for 20h, sinteringFinally obtaining the product with the size of 10 microns, the diameter distance of 1.9 and the tap of 2.3g/cm3The cathode material LNM 8020.
The obtained cathode material LNM8020 is crushed and ground, dried at 120 ℃ for 8 hours, and then mixed with a mixture of carbon fibers and conductive carbon black (the mass ratio of the carbon fibers to the conductive carbon black is 1: 1), wherein the mass ratio is 10: 1, mixing with aluminum powder, wherein the mass ratio is 8: and 1, finally mixing the powder with BiPb powder (Bi accounts for 50 percent, Pb accounts for 50 percent) in a mass ratio of 2: and 1, finally, carrying out hot-pressing processing on the mixed powder at 160 ℃ to obtain a positive pole piece, and cutting to obtain the positive pole piece applicable to button batteries and laminated batteries.
The obtained positive pole piece and the lithium piece are used as counter electrodes to assemble a half cell, the capacity can reach 187mAh/g after 5 times of circulation in a blue test system at a current density of 0.1C, and the obtained first effect is 96%.
Example four
The base solution was prepared in a 2000L reactor in a volume of 1000L with a certain pH of 12.4, ammonium radicals of 4.5g/L, a temperature of 30 ℃ and a rotation speed of 300rpm with a continuous flow of nitrogen for a certain period of time, during which time the temperature was reduced by cooling water. Firstly, nickel sulfate: cobalt sulfate: manganese sulfate according to the metal molar ratio of 65: 25: dissolving the mixture according to the proportion of 10 to obtain a metal mixed salt solution with the concentration of 2.2 mol/L; preparing a sodium hydroxide solution with the hydroxide ion concentration of 10mol/L as a precipitator solution; preparing an ammonia water solution into a complexing agent solution of 8 mol/L; then three solutions of metal mixed salt solution, precipitator solution and complexing agent solution are injected into a reaction kettle from respective feed inlets through a peristaltic pump, pipelines of the three solutions entering the reaction kettle are arranged in a dispersing way to form four different directions with an air inlet, an overflow port is arranged at the position slightly below the air inlet, the temperature is controlled at 30 ℃, the pH value is 12.4, the ammonium radical is 4.5g/L, the flow rate of the metal salt solution is kept at 150L/h, the precipitator solution is 66L/h and the complexing agent solution is 20L/h in the first 30 minutes of the reaction period, the flow rate of the feed liquid is kept relatively constant on the basis of keeping the pH value and the ammonium radical stable, the temperature is gradually increased and kept at 70 ℃, the pH value is 11.2, the ammonium radical is 3.2g/L, the relatively constant flow rate of the feed liquid is kept, the stirring speed is controlled to be reduced along with the particle size, the 5 mu m is reduced to 200rpm, the final 6 μm was run at 200rpm with nitrogen passing through. After the feed liquid in reation kettle is full of the cauldron, overflow the feed liquid to the outer filter equipment of reation kettle in, squeeze into reation kettle through the peristaltic pump with the material again after filtering most mother liquor in, squeeze into reation kettle in 3 minutes through the diaphragm pump every 240 minutes, grow and pull open the footpath apart from through constantly feeding reaction growth, inside and outside compounding, the granularity reaches 6 microns and then stops the feeding, and the footpath is 1.6 this moment.
After feeding is stopped, the rotating speed of the reaction kettle is reduced to 50rpm, the reaction kettle is stirred for 4 hours, 200ml of 2mol/L sodium carbonate solution is added to be continuously stirred at a low speed, the obtained filter cake is washed and filtered after being aged for 12 hours, the obtained filter cake is dried at 130 ℃, the filter cake is weighed and mixed with lithium titanate after 18 hours, wherein Li/M is 1.08, the obtained mixture is uniformly mixed and then put into a tubular furnace to be sintered, the sintering preheating temperature is 500 ℃, the heat preservation time is 4 hours, the heat treatment temperature is 850 ℃, the heat preservation time is 20 hours, and the sintered product is finally obtained, wherein the size is 6 micrometers, the radial distance is 1.6, and the tap is 2.3g/cm3LNCM 652510.
The obtained cathode material LNCM652510 is crushed and ground, dried at 120 ℃ for 8h, and then mixed with a mixture of carbon fiber and conductive carbon black (the mass ratio of the carbon fiber to the conductive carbon black is 2: 1), wherein the mass ratio is 9: 1, mixing with aluminum powder, wherein the mass ratio is 8: and 1, finally mixing the powder with BiPb powder (Bi accounts for 40% and Pb accounts for 60%) in a mass ratio of 2: and 1, finally, carrying out hot-pressing processing on the mixed powder at 180 ℃ to obtain a positive pole piece, and cutting to obtain the positive pole piece applicable to button batteries and laminated batteries.
The obtained positive pole piece and the lithium piece are used as counter electrodes to assemble a half cell, the capacity of the half cell after 10 times of circulation in a blue test system at the current density of 0.2C can reach 171mAh/g, and the obtained first effect is 94%.
Comparative example 1
The base solution was adjusted to 1L in a 2L reactor, having a certain pH of 10.8, 2.5g/L ammonium radical, temperature of 55 deg.C, rotation speed of 260rpm and continuous nitrogen flow for a certain period of time. Firstly, dissolving nickel sulfate, cobalt sulfate and manganese sulfate according to a metal molar ratio of 5:2:3 to obtain a metal mixed salt solution of 2 mol/L; mixing sodium hydroxide and an ammonia water solution according to a molar ratio of 6: 1 to obtain a precipitant solution with hydroxyl of 8 mol/L; mixing ammonium chloride and an ammonia water solution according to a molar ratio of 1:1 dissolving to obtain complexing agent solution with 8mol/L of ammonium radical; then three solutions of metal mixed salt solution, precipitator solution and complexing agent solution are injected into a reaction kettle from respective feed inlets through a peristaltic pump, pipelines of the three solutions entering the reaction kettle are arranged in a dispersing way to form four different directions with an air inlet, an overflow port is arranged at the position slightly below the air inlet, the temperature is controlled to be 55 ℃, the pH value is 10.8, the ammonium radical is 2.5g/L, the flow rate of the metal salt solution is kept to be 20ml/h, the precipitator solution is 10ml/h and the complexing agent solution is 2ml/h in the first 30 minutes of the reaction period, the relative constant flow rate of the feed liquid is kept on the basis of keeping the pH value and the ammonium radical stable (mainly related to the flow rate stability of the peristaltic pump, if unstable, flow rate fine adjustment is needed to ensure the stability of the ammonium radical and the pH value), after feeding for 30 minutes, the temperature is gradually increased and kept to be 75 ℃, the pH value is 9.5, the ammonium radical is 2.0g/L, keeping relatively constant feed liquid flow, controlling the stirring rotating speed to reduce along with the growth of the granularity, reducing the rotating speed of 5 microns to 220rpm, reducing the rotating speed of 6 microns to 200rpm, reducing the rotating speed of 7 microns to 180rpm, reducing the rotating speed of 8 microns to 160rpm, reducing the rotating speed of 9 microns to 140rpm, finally reducing the rotating speed of 140rpm when the particle size of 10 microns, and introducing nitrogen all the time, along with the reaction, when the feed liquid in the reaction kettle reaches the full kettle, the feed liquid overflows to the outside of the reaction kettle and carries out waste recovery after the full kettle, stopping feeding when the granularity in the reaction kettle reaches 10 microns, and at the moment, the radial distance is 0.6.
After feeding is stopped, reducing the rotating speed of the reaction kettle to 30rpm, stirring for 4 hours, adding 10ml of 8mol/L sodium hydroxide solution, continuously stirring at a low speed, aging for 12 hours, washing and filtering, drying the obtained filter cake at 120 ℃, weighing the filter cake after 18 hours, mixing the filter cake with lithium carbonate, wherein Li/M is 1.1, uniformly mixing, putting the mixture into a tubular furnace for sintering, wherein the sintering preheating temperature is 550 ℃, the heat preservation time is 2 hours, the heat treatment temperature is 850 ℃, the heat preservation time is 16 hours, and finally obtaining the product with the size of 10 micrometers, the radial distance is 0.6, and the tap density is 1.9g/cm3The positive electrode material LNCM 523.
Crushing and grinding the obtained cathode material LNCM523, drying at 120 ℃ for 8h, and taking out, wherein the cathode material is prepared by the following steps: conductive agent sp: the mass ratio of PVDF is 8: 1: dissolving PVDF and a proper amount of NMP to obtain a solvent, mixing the solvent with a conductive agent sp and a positive electrode material, performing ball milling pulping, uniformly coating the prepared slurry on an aluminum foil, drying, and finally cutting to obtain the positive electrode plate applicable to button batteries and laminated batteries.
The obtained positive pole piece and the lithium piece are used as counter electrodes to assemble a half cell, the capacity can reach 158mAh/g after 10 times of circulation in a blue test system at a current density of 0.1C, and the obtained first effect is 89%.
Comparative example No. two
The base solution was adjusted to 1L in a 2L reactor, having a certain pH of 10.8, 2.5g/L ammonium radical, temperature of 55 deg.C, rotation speed of 260rpm and continuous nitrogen flow for a certain period of time. Firstly, dissolving nickel sulfate, cobalt sulfate and manganese sulfate according to a metal molar ratio of 5:2:3 to obtain a metal mixed salt solution of 2 mol/L; mixing sodium hydroxide and an ammonia water solution according to a molar ratio of 6: 1 to obtain a precipitant solution with hydroxyl of 8 mol/L; mixing ammonium chloride and an ammonia water solution according to a molar ratio of 1:1 dissolving to obtain complexing agent solution with 8mol/L of ammonium radical; then three solutions of metal mixed salt solution, precipitator solution and complexing agent solution are injected into a reaction kettle from respective feed inlets through a peristaltic pump, pipelines of the three solutions entering the reaction kettle are arranged in a dispersing way to form four different directions with an air inlet, an overflow port is arranged at the position slightly below the air inlet, the temperature is controlled to be 55 ℃, the pH value is 10.8, the ammonium radical is 2.5g/L, the flow rate of the metal salt solution is kept to be 20ml/h, the precipitator solution is 10ml/h and the complexing agent solution is 2ml/h in the first 30 minutes of the reaction period, the relative constant of the feed liquid flow rate is kept on the basis of keeping the pH value and the ammonium radical stable (mainly related to the flow rate stability of the peristaltic pump and needing to carry out flow rate fine adjustment to ensure the stability of the ammonium radical and the pH value) after feeding for 30 minutes, the temperature is gradually increased and kept to be 75 ℃, the pH value is 9.5, and the ammonium radical is 2.0g/L, keeping relatively constant feed liquid flow, controlling the stirring rotation speed to reduce along with the growth of the granularity, reducing the stirring rotation speed to 220rpm at 5 microns, reducing the stirring rotation speed to 200rpm at 6 microns, reducing the stirring rotation speed to 180rpm at 7 microns, reducing the stirring rotation speed to 160rpm at 8 microns, reducing the stirring rotation speed to 140rpm at 9 microns, finally reducing the rotation speed to 140rpm at 10 microns, introducing nitrogen all the time, filling the mixture into a filter device outside the reaction kettle when the mixture in the reaction kettle reaches the full level along with the reaction, filtering most of the mother liquor, pumping the mixture into the reaction kettle again through a peristaltic pump within 3 minutes every 120min, continuously feeding, growing the mixture inside and outside and pulling the radial distance, stopping feeding when the granularity reaches 10 microns, and controlling the radial distance to be 1.1 at the moment.
After feeding is stopped, reducing the rotating speed of the reaction kettle to 30rpm, stirring for 4 hours, adding 10ml of 8mol/L sodium hydroxide solution, continuously stirring at a low speed, aging for 12 hours, washing and filtering, drying the obtained filter cake at 120 ℃, weighing the filter cake after 18 hours, mixing the filter cake with lithium carbonate, wherein Li/M is 1.1, uniformly mixing, putting the mixture into a tubular furnace for sintering, wherein the sintering preheating temperature is 550 ℃, the heat preservation time is 2 hours, the heat treatment temperature is 850 ℃, the heat preservation time is 16 hours, and finally obtaining the product with the size of 10 micrometers, the radial distance is 1.1, and the tap density is 2.1g/cm3The positive electrode material LNCM 523.
Crushing and grinding the obtained cathode material LNCM523, drying at 120 ℃ for 8h, and taking out, wherein the cathode material is prepared by the following steps: conductive agent sp: the mass ratio of PVDF is 8: 1: dissolving PVDF and a proper amount of NMP to obtain a solvent, mixing the solvent with a conductive agent sp and a positive electrode material, performing ball milling pulping, uniformly coating the prepared slurry on an aluminum foil, drying, and finally cutting to obtain the positive electrode plate applicable to button batteries and laminated batteries.
The obtained positive pole piece and the lithium piece are used as counter electrodes to assemble a half cell, the capacity can reach 161mAh/g after 10 times of circulation in a blue test system at a current density of 0.1C, and the obtained first effect is 92%.
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. The preparation method of the high-tap positive electrode material is characterized by comprising the following steps:
in a protective atmosphere, continuously mixing a metal mixed salt solution, a precipitator solution and a complexing agent solution with a base solution in a reaction container in a continuous feeding mode respectively, and carrying out precipitation reaction;
after carrying out first solid-liquid separation treatment on the overflowed reaction feed liquid subjected to the precipitation reaction, returning the obtained filter residue to the reaction container for carrying out at least one reaction growth treatment;
stopping feeding the metal mixed salt solution, the precipitator solution and the complexing agent solution when the precipitate reaches the preset granularity and the preset diameter distance; aging the reaction liquid in the reaction container, and then carrying out second solid-liquid separation to obtain a high-tap-density precursor;
and carrying out second mixing treatment on the high-tap precursor and lithium salt, and sintering treatment to obtain the high-tap anode material.
2. The production method according to claim 1,
the metal ion concentration of the metal mixed salt solution is 0.5-2.5mol/L, and the flow rate is 0.001-500L/h;
the concentration of the precipitant solution is 4-14mol/L, and the flow rate is 0.0001L/h-375L/h;
the concentration of the complexing agent solution is 0.2-14mol/L, and the flow rate is 0.0001L/h-375L/h.
3. The method of claim 1, wherein the metal mixed salt solution, the precipitant solution, and the complexing agent solution are fed independently.
4. The method according to claims 1, 2 and 3, characterized in that the protective gas in the protective atmosphere is continuously introduced into the reaction vessel in a gas flow, and the protective gas is independently introduced.
5. The method of claim 1, wherein the high tap precursorIs represented by the general formula (Ni)xCoyMnzQd)LeWherein x is more than or equal to 0 and less than or equal to 1-d, y is more than or equal to 0 and less than or equal to 1-d, z is more than or equal to 0 and less than or equal to 1-d, d is more than or equal to 0 and less than or equal to 0.5, and x + y + z + d is equal to 1; q is one or more of Fe, Mg, Ca, Al, Y, Ti, Zn, Zr, Nb, Mo or W, L is hydroxyl or carbonate, the diameter distance S of the high tap precursor is 0.8-2.0, and the granularity D50 is 5.0-20.0 μm.
6. The production method according to any one of claims 1 to 3, wherein the metal in the metal mixed salt solution includes Ni, Co, Mn and Q; wherein Q is one or more of Fe, Mg, Ca, Al, Y, Ti, Zn, Zr, Nb, Mo or W; and/or
The salt in the metal mixed salt solution comprises one or more of sulfate, chloride, nitrate, acetate or alkoxide; and/or
The complexing agent solution comprises one or more of EDTA solution, ammonia water solution, ammonium chloride solution, ammonium sulfate solution and ammonium nitrate solution; and/or
The precipitant solution comprises one or more of ammonia water solution, sodium hydroxide solution, potassium hydroxide solution and sodium carbonate solution.
7. The method according to claim 1, wherein the concentration of ammonium groups in the base solution is 0.1 to 20mol/L, and the pH is 7 to 14; and/or
The protective gas is one or more of nitrogen or rare gas; and/or
The lithium salt is one or more of lithium carbonate, lithium hydroxide and lithium titanate.
8. The method as claimed in claim 1, wherein the reaction growth process is accompanied by a first stirring process, and the first stirring rate is gradually reduced from 350rpm to 160rpm as the reaction progresses from 300-; and/or
The temperature in the reaction vessel is maintained at 30-90 ℃; and/or
The aging treatment is specifically continuous second stirring treatment after adding alkali, and the speed of the second stirring treatment is 25-50 rpm.
9. A preparation method of a positive pole piece is characterized by comprising the following steps:
mixing the high-tap positive electrode material prepared by the preparation method according to any one of claims 1 to 8 with a conductive agent, aluminum powder and low-melting-point metal powder, and then performing hot-pressing processing to obtain the positive electrode piece.
10. The preparation method of the positive pole piece according to claim 9, wherein the temperature of the hot press processing is 20 to 400 ℃, and the pressure is 0.1 to 30 MPa; and/or
The conductive agent is one or more of conductive carbon black, superfine conductive carbon black, acetylene carbon black, graphene, carbon fiber and carbon nano tube; and/or
The low-melting-point metal powder is one or more of tin powder, bismuth powder, lead powder, cadmium powder and indium powder.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140053451A (en) * | 2012-10-25 | 2014-05-08 | 삼성에스디아이 주식회사 | Composite cathode active material, preparation method thereof, and cathode and lithium battery containing the material |
| CN105186043A (en) * | 2015-09-23 | 2015-12-23 | 厦门理工学院 | All-solid-state LiMn2O4-Li4Ti5O12 battery and preparation method thereof |
| CN107331859A (en) * | 2017-07-28 | 2017-11-07 | 荆门市格林美新材料有限公司 | A kind of method of one-pot Fast back-projection algorithm ternary anode material of lithium battery presoma |
| CN108751265A (en) * | 2018-09-04 | 2018-11-06 | 北京当升材料科技股份有限公司 | A kind of preparation method of anode material for lithium-ion batteries and its presoma |
| CN109860581A (en) * | 2018-12-25 | 2019-06-07 | 河南科隆新能源股份有限公司 | A kind of preparation method of the ball-shape nickel hydroxide cobalt manganese presoma of narrow particle diameter distribution |
| CN111540898A (en) * | 2020-05-12 | 2020-08-14 | 宁波容百新能源科技股份有限公司 | Preparation method and application of precursor with good primary particle uniformity |
| CN112420986A (en) * | 2019-08-21 | 2021-02-26 | 南京博驰新能源股份有限公司 | Method for preparing positive and negative pole pieces of lithium battery by dry method |
| CN112687833A (en) * | 2020-12-24 | 2021-04-20 | 蜂巢能源科技有限公司 | Dry method electrode plate preparation method, electrode plate prepared by dry method electrode plate preparation method and application |
-
2021
- 2021-11-05 CN CN202111308686.7A patent/CN114014383A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140053451A (en) * | 2012-10-25 | 2014-05-08 | 삼성에스디아이 주식회사 | Composite cathode active material, preparation method thereof, and cathode and lithium battery containing the material |
| CN105186043A (en) * | 2015-09-23 | 2015-12-23 | 厦门理工学院 | All-solid-state LiMn2O4-Li4Ti5O12 battery and preparation method thereof |
| CN107331859A (en) * | 2017-07-28 | 2017-11-07 | 荆门市格林美新材料有限公司 | A kind of method of one-pot Fast back-projection algorithm ternary anode material of lithium battery presoma |
| CN108751265A (en) * | 2018-09-04 | 2018-11-06 | 北京当升材料科技股份有限公司 | A kind of preparation method of anode material for lithium-ion batteries and its presoma |
| CN109860581A (en) * | 2018-12-25 | 2019-06-07 | 河南科隆新能源股份有限公司 | A kind of preparation method of the ball-shape nickel hydroxide cobalt manganese presoma of narrow particle diameter distribution |
| CN112420986A (en) * | 2019-08-21 | 2021-02-26 | 南京博驰新能源股份有限公司 | Method for preparing positive and negative pole pieces of lithium battery by dry method |
| CN111540898A (en) * | 2020-05-12 | 2020-08-14 | 宁波容百新能源科技股份有限公司 | Preparation method and application of precursor with good primary particle uniformity |
| CN112687833A (en) * | 2020-12-24 | 2021-04-20 | 蜂巢能源科技有限公司 | Dry method electrode plate preparation method, electrode plate prepared by dry method electrode plate preparation method and application |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115924995A (en) * | 2022-12-29 | 2023-04-07 | 合肥综合性国家科学中心能源研究院(安徽省能源实验室) | Preparation method of multi-element anode material with gradient composite structure |
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