CN112687870A - Positive electrode material precursor and preparation method thereof, and positive electrode material and application thereof - Google Patents
Positive electrode material precursor and preparation method thereof, and positive electrode material and application thereof Download PDFInfo
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Abstract
The invention relates to the field of lithium batteries, and discloses a positive electrode material precursor, a preparation method thereof, a positive electrode material and application thereof. The positive electrode material precursor contains flaky single crystal agglomerates and polyhedral single crystal particles; in an XRD pattern of the precursor of the cathode material, the following relations are satisfied among I (001), I (100) and I (101): i (001)/I (100) is not less than 1.5, and I (001)/I (101) is not less than 1.2. The positive electrode material precursor is prepared by intermittent dropwise addition, so that the exposed area of the 001 surface in the positive electrode material precursor is increased. The discharge capacity and the first-week efficiency of the anode material prepared by the anode material precursor and the anode of the lithium battery are improved.
Description
Technical Field
The invention relates to the field of lithium batteries, and discloses a positive electrode material precursor and a preparation method thereof, a positive electrode material and application thereof.
Background
The lithium battery has the advantages of high energy density, high output voltage, small self-discharge, excellent cycle performance, no memory effect and the like, and is widely applied to the fields of portable electronic products, electric tools, electric automobiles and the like. In particular, in recent years, new energy vehicles released by governments are upgraded continuously, and explosive development of power lithium batteries is promoted.
The anode material is a key core component of the lithium battery, not only determines key core indexes such as energy density of the lithium battery, but also accounts for about 40% of the cost of the whole battery. With the continuous improvement of the requirement of people on the endurance mileage of electric vehicles, ternary cathode materials with higher energy density gradually become mainstream cathode materials for passenger vehicles.
The morphology of the lithium battery anode material has important influence on the electrochemical performance of the lithium battery anode material. For ternary cathode materials, the morphology is essentially determined by their precursors. The morphology of the current commercialized ternary cathode material precursor is mainly secondary micron polycrystalline spherical aggregate particles composed of nanoscale or submicron-sized primary particles, and for example, patent CN 107915263a discloses a secondary micron polycrystalline spherical aggregate precursor material with a size of 3.5-4.0 μm. In the charging and discharging process, fine primary particles can contact and react with electrolyte, so that the capacity and first-cycle efficiency of the polycrystalline material are not high, and the actual application requirement in a power battery is difficult to meet.
Disclosure of Invention
The invention aims to solve the problem that the electrochemical performance of polycrystalline spherical aggregates is poor in the charging and discharging processes, and provides a positive electrode material precursor, a preparation method thereof, a positive electrode material and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a positive electrode material precursor containing flaky single crystal agglomerates and polyhedral single crystal particles;
wherein in the XRD pattern of the precursor of the cathode material, the following relations are satisfied among I (001), I (100) and I (101): i (001)/I (100) is not less than 1.5, and I (001)/I (101) is not less than 1.2;
wherein the chemical formula of the precursor of the positive electrode material is NixCoyMz(OH)2M is at least one selected from Fe, Cr, Cu, Ti, Mg, W, Mo, Nb, Zn, Sn, Zr, Ga, Mn and Al;
wherein x is more than or equal to 0.3 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.5, and z is more than or equal to 0 and less than or equal to 0.3.
The second aspect of the present invention provides a method for preparing a precursor of a positive electrode material, the method comprising:
(1) intermittently dropwise adding a metal salt solution, a precipitator solution and an optional complexing agent solution, mixing and reacting;
(2) and (2) carrying out solid-liquid separation and drying treatment on the product obtained in the step (1) to obtain the precursor of the positive electrode material.
Preferably, in the step (1), the intermittent dropwise adding process comprises (1) simultaneously dropwise adding the metal salt solution, the precipitant solution and the optional complexing agent solution into a reaction kettle under reaction conditions;
(2) after the three solutions are simultaneously dripped for 2-12h each time, stopping feeding the metal salt solution for 0.5-4 h;
(3) and (3) repeating the intermittent dropwise adding process in the step (2) until the reaction is finished.
The third aspect of the present invention provides the positive electrode material precursor prepared by the preparation method described above.
A fourth aspect of the invention provides a positive electrode material containing the positive electrode material precursor as described above and a lithium element.
The invention provides a positive electrode material precursor or application of the positive electrode material precursor in a lithium battery.
The invention provides a novel precursor of a positive electrode material, which is different from a polycrystalline spherical precursor and contains sheet-shaped single crystal agglomerates and polyhedral single crystal particles, wherein the exposed area of the 001 surface of the precursor is more, for example, XRD (X-ray diffraction) patterns in figures 2 and 3 show that the intensity of the diffraction peak of the 001 surface of the precursor is obviously higher compared with that of the traditional spherical precursor, which indicates that the 001 surface is more exposed, and the morphology endows the precursor of the positive electrode material with better electrochemical performance.
The discharge capacity and the first-week efficiency of the anode material and the anode of the lithium battery prepared by adopting the anode material precursor can be improved. Under the 0.1C multiplying power, the discharge capacity of the lithium battery can exceed 200mAh at most, and the first-week efficiency can reach 92%.
Drawings
Fig. 1A is an SEM image of a precursor of the positive electrode material prepared in example 1 of the present invention;
fig. 1B is an SEM image of the positive electrode material precursor prepared in example 1 of the present invention;
fig. 2 is an XRD pattern of the precursor of the positive electrode material prepared in example 1 of the present invention;
fig. 3 is an XRD pattern of the precursor of the positive electrode material prepared in comparative example 1 of the present invention;
fig. 4 is a charge-discharge curve of a lithium battery assembled by the positive electrode material of example 1 of the present invention.
Reference numerals
A sheet-shaped single crystal agglomerate and B polyhedral single crystal grains
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a positive electrode material precursor, which comprises a flaky single crystal agglomerate and polyhedral single crystal particles;
wherein in the XRD pattern of the precursor of the cathode material, the following relations are satisfied among I (001), I (100) and I (101): i (001)/I (100) is not less than 1.5, and I (001)/I (101) is not less than 1.2;
wherein the chemical formula of the precursor of the positive electrode material is NixCoyMz(OH)2M is at least one selected from Fe, Cr, Cu, Ti, Mg, W, Mo, Nb, Zn, Sn, Zr, Ga, Mn and Al;
wherein x is more than or equal to 0.3 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.5, and z is more than or equal to 0 and less than or equal to 0.3. Preferably, 0.6. ltoreq. x.ltoreq.0.95, 0.05. ltoreq. y.ltoreq.0.2, 0.05. ltoreq. z.ltoreq.0.2.
Preferably, M is selected from Mn and/or Al. That is, preferably, the chemical formula of the positive electrode material precursor is NixCoyMnz(OH)2Or NixCoyAlz(OH)2。
It should be understood that x + y + z is 1.
In a preferred embodiment of the present invention, SEM images of the positive electrode material precursor are shown in fig. 1A and 1B. As can be seen from fig. 1A and 1B, the positive electrode material precursor according to the present invention contains flaky single crystal agglomerates and polyhedral single crystal particles. As can be seen from fig. 2, the positive electrode material precursor contains at least three diffraction peaks, including a (001) diffraction peak at an angle of 2 θ of 19.6 °, a (100) diffraction peak at an angle of 2 θ of 33.4 °, and a (101) diffraction peak at an angle of 2 θ of 38.8 °. The diffraction peak of the precursor of the cathode material is sharp, which shows that the crystal structure is well developed, and the intensity of the diffraction peak of the (001) crystal face is more obvious, which shows that the (001) crystal face in the precursor is more fully exposed. The difference between the precursor of the cathode material and the existing polycrystalline spherical aggregate is obvious, the appearance of the existing polycrystalline spherical aggregate is spherical or spheroidal, and the intensity of a diffraction peak (especially the intensity of a 001 surface) is also obviously lower than that of the precursor material.
Wherein, the positive electrode material precursor, I (001), I (100) and I (101) satisfy the following relations: i (001)/I (100) is not less than 1.5, and I (001)/I (101) is not less than 1.2.
Wherein I (001) is the diffraction peak intensity of the (001) crystal plane, and the intensity is measured as the height of the diffraction peak.
Wherein I (100) is the diffraction peak intensity of the (100) crystal plane, and the intensity is measured as the height of the diffraction peak.
Wherein I (101) is the diffraction peak intensity of the (101) crystal plane, and the intensity is measured as the height of the diffraction peak.
The flaky single crystal agglomerate refers to an agglomerate formed by agglomeration of flaky single crystals in a primary appearance and the flaky single crystals in a secondary appearance.
The polyhedral single crystal particles refer to single crystal particles with polyhedral morphology.
In the present invention, the scanning electron microscope image (SEM) was obtained by a scanning electron microscope of ZEISS Merlin model of ZEISS, Germany.
In the present invention, the XRD pattern was measured by an X-ray diffractometer model D8 Advance SS from Bruker, Germany.
In the present invention, the particle size of the positive electrode material precursor is preferably 2 to 8 μm, and the method for measuring the particle size is a dynamic light scattering technique.
The inventor of the invention unexpectedly finds that in the process of preparing the precursor of the cathode material, the morphological characteristics of the precursor obtained in the mode of continuously dropwise adding the raw materials basically accord with the polycrystalline spherical aggregate, and when the precursor is prepared in the mode of intermittently dropwise adding, the precursor containing flaky single crystal aggregates and polyhedral single crystal particles can be obtained, and the precursor with the special morphology has better electrochemical performance.
The second aspect of the present invention provides a method for preparing a precursor of a positive electrode material, the method comprising:
(1) intermittently dripping a metal salt solution, a precipitator solution and an optional complexing agent solution, mixing and reacting;
(2) carrying out solid-liquid separation and drying treatment on the product obtained in the step (1) to obtain the precursor of the positive electrode material;
the metal salt solution contains metal elements Ni, Co and M, wherein M is at least one selected from Fe, Cr, Cu, Ti, Mg, W, Mo, Nb, Zn, Sn, Zr, Ga, Mn and Al;
wherein the molar usage ratio of the Ni element, the Co element and the M element is (0.3-1): (0-0.5): (0-0.3).
The invention has wide selection range of the usage of Ni, Co and M elements, and the molar usage ratio of the Ni element, the Co element and the M element is preferably (0.6-0.95): (0.05-0.2): (0.05-0.2).
In the present invention, the metal salt solution may be a metal salt solution conventionally used in the art, and preferably, the metal salt solution contains a metal element of a combination of Ni, Co and Mn or a combination of Ni, Co and Al.
In the present invention, the kind of the metal salt contained in the metal salt solution may not be particularly limited, and preferably, the metal salt solution contains at least one metal salt selected from the group consisting of metal sulfate, metal nitrate, metal acetate, and metal oxalate. For example, the nickel salt may be at least one of nickel sulfate, nickel nitrate, nickel acetate, nickel oxalate, and nickel chloride; the cobalt salt can be at least one of cobalt nitrate, cobalt chloride, cobalt acetate and cobalt sulfate; the manganese salt can be at least one of manganese sulfate, manganese nitrate, manganese acetate and manganese chloride; the aluminum salt may be at least one of aluminum nitrate, aluminum chloride, aluminum acetate, and aluminum sulfate.
In the present invention, the metal salt solution preferably has a molar concentration of 0.01 to 5mol/L, for example, 0.01mol/L, 0.1mol/L, 0.5mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L and any range of composition between any two values, more preferably 0.5 to 3mol/L, and still more preferably 1 to 2mol/L, in terms of the metal element.
In the present invention, the kind of the precipitant may not be particularly limited, and preferably, the precipitant is selected from at least one of NaOH, KOH, and LiOH.
In the present invention, the concentration of the precipitant solution is not particularly limited, and preferably, the concentration of the precipitant solution is 0.02 to 10mol/L, and for example, may be 0.02mol/L, 0.1mol/L, 0.5mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L, 10mol/L, and any range of composition between any two values, more preferably 2 to 8mol/L, and further preferably 2 to 6 mol/L.
In the present invention, the kind of the complexing agent may not be particularly limited, and is a compound capable of forming a complex with Ni, Co and M in an aqueous solution; preferably, the complexing agent is selected from at least one of ammonium ion donors, ethanolamine-based complexing agents, aminocarboxylic acid-based complexing agents, hydroxyaminocarboxylic acid-based complexing agents, and carboxylate-based complexing agents.
Among them, the ammonium ion donor is preferably at least one selected from the group consisting of aqueous ammonia, ammonium oxalate, ammonium carbonate and ammonium hydroxide.
Among them, the ethanolamine-based complexing agent is preferably diethanolamine.
Among them, the aminocarboxylic acid-based complexing agent is preferably at least one selected from sodium Nitrilotriacetate (NTA), ethylenediaminetetraacetic acid and salts thereof (EDTA), and diethylenetriaminepentaacetic acid (DTPA).
Among them, the hydroxyaminocarboxylic acid-based complexing agent is preferably at least one selected from the group consisting of hydroxyethylenediaminetetraacetic acid (HEDTA), ethyleneglycol bis (. beta. -diaminoethyl) ethyl ether-N, N' -tetraacetic acid (EGTA) and salts thereof, and dihydroxyglycine and salts thereof.
Among them, the carboxylate-based complexing agent is preferably at least one selected from oxalic acid and its salts, tartaric acid and its salts, citric acid and its salts, gluconic acid and its salts, carboxymethylhydroxymalonic acid (CMOM) and its salts, carboxymethylhydroxysuccinic acid (CMOS) and its salts, and hydroxyethylglycine (DHEG) and its salts.
In the present invention, the concentration of the complexing agent solution is not particularly limited, and preferably, the concentration of the complexing agent solution is 0.01 to 15mol/L, for example, 0.01mol/L, 0.1mol/L, 0.5mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L, 10mol/L, 11mol/L, 12mol/L, 13mol/L, 14mol/L, 15mol/L, and any range of the composition between any two values, more preferably 2 to 10mol/L, and still more preferably 2 to 6 mol/L.
In the present invention, preferably, in step (1), the intermittent dropwise addition process comprises:
(1) dripping the metal salt solution, the precipitant solution and the optional complexing agent solution into a reaction kettle simultaneously under the reaction condition;
(2) after the three solutions are simultaneously dripped for 2-12h each time, stopping feeding the metal salt solution for 0.5-4 h;
(3) and (3) repeating the intermittent dropwise adding process in the step (2) until the reaction is finished.
In the present invention, the pH of the reaction system is 9 to 12. As a preferable technical scheme, the pH value of the reaction system is 10-11.5. It is understood that, in the reaction process of the intermittent dropping, stopping the dropping of the metal salt solution raises the pH of the solution, and when the dropping of the metal salt solution is resumed, the pH of the solution needs to be adjusted to a set value by adjusting the dropping rate of the metal salt solution.
According to the invention, the dropping speed of the materials is selected in a wide range, and the dropping speed is only required to meet the requirement that the pH value of the materials simultaneously dropped into the reaction kettle in the step (1) can reach the range, preferably, the dropping speed of the metal salt solution is 10-200mL/h based on the total amount of 1L of the metal salt solution. Preferably, the dropping speed of the precipitant solution is 10-200mL/h based on the total amount of 1L of the precipitant solution. Preferably, the dropping speed of the complexing agent solution is 10-200mL/h based on 1L of the total amount of the complexing agent solution. The dropping flow rate can be controlled by those skilled in the art according to the need of pH.
It should be noted that, in the present invention, the total amount of 1L of the metal salt solution is taken as a reference, and the dropping speed of the metal salt solution is 10 to 200mL/h, which means that when the total amount of the metal salt solution is 1L, the dropping speed of the metal salt solution is 10 to 200mL/h, and correspondingly, when the total amount of the metal salt solution is 0.5L, the dropping speed of the metal salt solution is 5 to 100 mL/h; correspondingly, when the total amount of the metal salt solution is 5L, the dropping speed of the metal salt solution is 50-1000 mL/h.
In the step (1), the reaction conditions preferably include: the temperature is 30-70 ℃, preferably 45-60 ℃; the time is not less than 10h, preferably 24-72 h. By controlling the temperature and/or time of the reaction, the growth of the precursor crystal can be controlled.
Preferably, the mixing is carried out under stirring conditions, more preferably, the stirring speed is 50-1000r/min, such as 50r/min, 80r/min, 100r/min, 200r/min, 300r/min, 400r/min, 500r/min, 600r/min, 700r/min, 800r/min, 900r/min, 1000r/min, and more preferably 600-1000r/min, and any value in the range of any two of these values.
In the present invention, it is preferable that the product obtained in step (1) is subjected to a cooling treatment before being subjected to solid-liquid separation. After the cooling treatment, the temperature of the product is preferably reduced to room temperature, which may be 25 ℃.
In the present invention, the solid-liquid separation in the step (2) is not particularly limited as long as the produced precursor is separated, and for example, a filtration or centrifugation method may be employed.
In the present invention, it is preferable that the product obtained by the solid-liquid separation is subjected to a washing treatment.
In the present invention, the drying method may be a method conventional in the art, and may be, for example, vacuum drying, air drying, freeze drying or oven drying. The present invention has a wide selection range of drying conditions, such as: the temperature is 70-150 ℃ and the time is 4-16 h.
The third aspect of the present invention provides the positive electrode material precursor prepared by the preparation method described above.
The properties of the positive electrode material precursor are described in detail in the first aspect, and the description is not repeated here.
A fourth aspect of the invention provides a positive electrode material containing the positive electrode material precursor as described above and a lithium element.
Preferably, the molar ratio of the lithium element to the battery positive electrode material precursor is 0.9 to 1.2:1, for example, 0.9, 0.95, 1.00, 1.05, 1.10, 1.15, 1.20, and any value in the range of any two of these values, in terms of the metal element.
The lithium element in the present invention may be present in the form of a lithium salt, and the lithium salt is preferably at least one selected from the group consisting of lithium nitrate, lithium chloride, lithium carbonate, lithium hydroxide and lithium acetate.
Methods for preparing the cathode material using the cathode material precursor are well known in the art and will not be described herein.
The invention provides a positive electrode material precursor or application of the positive electrode material precursor in a lithium battery.
According to the application provided by the invention, the battery positive electrode material, the conductive agent and the binder are mixed, coated and sliced to be used as the battery positive electrode. The conductive agent and the binder can be various conductive agents and binders which are conventionally used in the field, and the description of the invention is omitted. The amount of the conductive agent and the binder may be the amount conventionally used in the art, for example, the mass content of the positive electrode material may be 50 to 98%, the mass content of the conductive agent may be 1 to 25%, and the mass content of the binder may be 1 to 25% based on the total amount of the positive electrode.
Methods for preparing lithium batteries using the positive electrode material precursor or the positive electrode material are well known in the art and will not be described herein.
The present invention will be described in detail below by way of examples.
Scanning Electron Micrographs (SEM) were obtained by scanning electron microscopy of ZEISS Merlin model, ZEISS company, germany.
The XRD pattern was measured by an X-ray diffractometer model D8 Advance SS from Bruker, Germany.
In the following examples and comparative examples, the metal salt solution is a sulfate solution of Ni, Mn, and Co elements.
Example 1
This example is for explaining the method for preparing and evaluating the precursor of the positive electrode material and the positive electrode material according to the present invention
(1) Preparation of positive electrode material precursor
Preparing a metal salt solution with the concentration of 2mol/L of metal ions (wherein the molar ratio of nickel, cobalt and manganese elements is 8:1: 1); preparing NaOH solution with the concentration of 4 mol/L; preparing ammonia water solution with the concentration of 6 mol/L.
And dropwise adding the prepared metal salt solution, NaOH solution and ammonia water solution into the reaction kettle simultaneously under the stirring state to perform precipitation reaction. The dropping speed of the metal salt solution is 60 mL/h; the dropping speed of the ammonia solution is 60mL/h, and the pH value of the reaction system is 11 by controlling the dropping speed of the NaOH solution. And after the three solutions are simultaneously dripped for 6 hours, stopping feeding the metal salt solution for 1 hour, keeping feeding of NaOH and the ammonia water solution, and repeating the process.
In the reaction process, the stirring speed is controlled to be 600rpm, the reaction temperature is controlled to be 55 ℃, and the reaction time is controlled to be 48 h. And (3) naturally cooling, then terminating the precipitation reaction, carrying out vacuum filtration on the slurry, washing the slurry for 3 times by using deionized water, and then drying and dehydrating the slurry in a vacuum drying oven at 120 ℃ for 12 hours to obtain the precursor of the cathode material.
(2) Evaluation of Positive electrode Material precursor
The SEM images of the precursor of the cathode material are shown in fig. 1A and fig. 1B, and it can be seen from the SEM images that the shape of the precursor of the cathode material is obviously different from that of the traditional polycrystalline spherical aggregate, and the precursor of the cathode material consists of sheet-shaped single crystal agglomerates and polyhedral single crystal particles.
The XRD (X-ray diffraction) spectrum of the precursor of the cathode material is shown in figure 2, the diffraction peak of the precursor of the cathode material is very sharp, the crystal structure of the precursor of the cathode material is well developed, the intensity of the diffraction peak corresponding to the (001) crystal face is obviously stronger than the intensity of other diffraction peaks, the (001) crystal face of the precursor of the cathode material is fully exposed, the intensity ratio of I (001)/I (100) is 2.5, and the intensity ratio of I (001)/I (101) is 1.5.
(3) Preparation and evaluation of cathode Material
Taking 10g of the precursor of the positive electrode material obtained in the step (1), and adding a lithium source LiOH & H2And O, enabling the molar ratio of Li (Ni + Co + Mn) to be 1.05:1, fully and uniformly mixing the two, and carrying out solid-phase reaction to obtain the cathode material.
And taking 10g of the positive electrode material, adding 1.25g of acetylene black and 12.5g of 10 mass percent polyvinylidene fluoride solution, uniformly mixing, coating, slicing and filling into a glove box to obtain the lithium battery.
Electrochemical performance at 0.1C rate was measured, and a charge-discharge curve thereof is shown in fig. 4, and specific results of discharge capacity and first-cycle efficiency are shown in table 1.
Example 2
This example is for explaining the method for preparing and evaluating the precursor of the positive electrode material and the positive electrode material according to the present invention
(1) Preparation of positive electrode material precursor
Preparing a metal salt solution with the concentration of 2mol/L of metal ions (wherein the molar ratio of nickel, cobalt and manganese elements is 18:1: 1); preparing NaOH solution with the concentration of 4 mol/L; preparing ammonia water solution with the concentration of 6 mol/L.
And dropwise adding the prepared metal salt solution, NaOH solution and ammonia water solution into the reaction kettle simultaneously under the stirring state to perform precipitation reaction. The dropping speed of the metal salt solution is 60 mL/h; the dropping speed of the ammonia solution is 60mL/h, and the pH value of the reaction system is 11 by controlling the dropping speed of the NaOH solution. And after the three solutions are simultaneously dripped for 6 hours, stopping feeding the metal salt solution for 1 hour, keeping feeding of NaOH and the ammonia water solution, and repeating the process.
In the reaction process, the stirring speed is controlled to be 600rpm, the reaction temperature is controlled to be 55 ℃, and the reaction time is controlled to be 48 h. And (3) naturally cooling, then terminating the precipitation reaction, carrying out vacuum filtration on the slurry, washing the slurry for 3 times by using deionized water, and then drying and dehydrating the slurry in a vacuum drying oven at 120 ℃ for 12 hours to obtain the precursor of the cathode material.
(2) Evaluation of Positive electrode Material precursor
The SEM image of the positive electrode material precursor is similar to fig. 1A and 1B, and the XRD image is similar to fig. 2.
(3) Preparation and evaluation of cathode Material
Positive electrode material and lithium battery prepared according to the method of example 1
The discharge capacity and first-week efficiency at 0.1C rate were measured, and the specific results are shown in table 1.
Example 3
This example is for explaining the method for preparing and evaluating the precursor of the positive electrode material and the positive electrode material according to the present invention
(1) Preparation of positive electrode material precursor
Preparing a metal salt solution with the concentration of 2mol/L of metal ions (wherein the molar ratio of nickel, cobalt and manganese elements is 3:1: 1); preparing NaOH solution with the concentration of 4 mol/L; preparing ammonia water solution with the concentration of 6 mol/L.
And dropwise adding the prepared metal salt solution, NaOH solution and ammonia water solution into the reaction kettle simultaneously under the stirring state to perform precipitation reaction. The dropping speed of the metal salt solution is 60 mL/h; the dropping speed of the ammonia solution is 60mL/h, and the pH value of the reaction system is 11 by controlling the dropping speed of the NaOH solution. And after the three solutions are simultaneously dripped for 6 hours, stopping feeding the metal salt solution for 1 hour, keeping feeding of NaOH and the ammonia water solution, and repeating the process.
In the reaction process, the stirring speed is controlled to be 600rpm, the reaction temperature is controlled to be 55 ℃, and the reaction time is controlled to be 48 h. And (3) naturally cooling, then terminating the precipitation reaction, carrying out vacuum filtration on the slurry, washing the slurry for 3 times by using deionized water, and then drying and dehydrating the slurry in a vacuum drying oven at 120 ℃ for 12 hours to obtain the precursor of the cathode material.
(2) Evaluation of Positive electrode Material precursor
The SEM image of the positive electrode material precursor is similar to fig. 1A and 1B, and the XRD image is similar to fig. 2.
(3) Preparation and evaluation of cathode Material
Positive electrode material and lithium battery prepared according to the method of example 1
The discharge capacity and first-week efficiency at 0.1C rate were measured, and the specific results are shown in table 1.
Example 4
This example is for explaining the method for preparing and evaluating the precursor of the positive electrode material and the positive electrode material according to the present invention
(1) Preparation of positive electrode material precursor
Preparing a metal salt solution with the concentration of 3mol/L of metal ions (wherein the molar ratio of nickel, cobalt and manganese elements is 8:1: 1); preparing NaOH solution with the concentration of 8 mol/L; preparing an ammonia water solution with the concentration of 10 mol/L.
The operation was carried out in the same manner as in example 1 to obtain a precursor of a positive electrode material.
(2) Evaluation of Positive electrode Material precursor
The SEM image of the positive electrode material precursor is similar to fig. 1A and 1B, and the XRD image is similar to fig. 2.
(3) Preparation and evaluation of cathode Material
Positive electrode material and lithium battery prepared according to the method of example 1
The discharge capacity and first-week efficiency at 0.1C rate were measured, and the specific results are shown in table 1.
Example 5
This example is for explaining the method for preparing and evaluating the precursor of the positive electrode material and the positive electrode material according to the present invention
(1) Preparation of positive electrode material precursor
Preparing a metal salt solution with the concentration of 0.5mol/L of metal ions (wherein the molar ratio of nickel, cobalt and manganese elements is 8:1: 1); preparing NaOH solution with the concentration of 2 mol/L; preparing an ammonia water solution with the concentration of 2 mol/L.
The operation was carried out in the same manner as in example 1 to obtain a precursor of a positive electrode material.
(2) Evaluation of Positive electrode Material precursor
The SEM image of the positive electrode material precursor is similar to fig. 1A and 1B, and the XRD image is similar to fig. 2.
(3) Preparation and evaluation of cathode Material
Positive electrode material and lithium battery prepared according to the method of example 1
The discharge capacity and first-week efficiency at 0.1C rate were measured, and the specific results are shown in table 1.
Example 6
This example is for explaining the method for preparing and evaluating the precursor of the positive electrode material and the positive electrode material according to the present invention
(1) Preparation of positive electrode material precursor
Preparing a metal salt solution with the concentration of 5mol/L of metal ions (wherein the molar ratio of nickel, cobalt and manganese elements is 8:1: 1); preparing a NaOH solution with the concentration of 10 mol/L; preparing an ammonia water solution with the concentration of 15 mol/L.
The operation was carried out in the same manner as in example 1 to obtain a precursor of a positive electrode material.
(2) Evaluation of Positive electrode Material precursor
The SEM image of the positive electrode material precursor is similar to fig. 1A and 1B, and the XRD image is similar to fig. 2.
(3) Preparation and evaluation of cathode Material
Positive electrode material and lithium battery prepared according to the method of example 1
The discharge capacity and first-week efficiency at 0.1C rate were measured, and the specific results are shown in table 1.
Example 7
This example is for explaining the method for preparing and evaluating the precursor of the positive electrode material and the positive electrode material according to the present invention
(1) Preparation of positive electrode material precursor
Preparing a metal salt solution with the concentration of 0.01mol/L of metal ions (wherein the molar ratio of nickel, cobalt and manganese elements is 8:1: 1); preparing NaOH solution with the concentration of 0.02 mol/L; preparing an ammonia water solution with the concentration of 0.01 mol/L.
The operation was carried out in the same manner as in example 1 to obtain a precursor of a positive electrode material.
(2) Evaluation of Positive electrode Material precursor
The SEM image of the positive electrode material precursor is similar to fig. 1A and 1B, and the XRD image is similar to fig. 2.
(3) Preparation and evaluation of cathode Material
Positive electrode material and lithium battery prepared according to the method of example 1
The discharge capacity and first-week efficiency at 0.1C rate were measured, and the specific results are shown in table 1.
Example 8
This example is for explaining the method for preparing and evaluating the precursor of the positive electrode material and the positive electrode material according to the present invention
(1) Preparation of positive electrode material precursor
The operation was carried out according to the method described in example 1, except that the pH of the system was controlled to 12 by adjusting the dropping rate of the NaOH solution during the dropping process, to obtain a precursor of the positive electrode material.
(2) Evaluation of Positive electrode Material precursor
The SEM image of the positive electrode material precursor is similar to fig. 1A and 1B, and the XRD image is similar to fig. 2.
(3) Preparation and evaluation of cathode Material
Positive electrode material and lithium battery prepared according to the method of example 1
The discharge capacity and first-week efficiency at 0.1C rate were measured, and the specific results are shown in table 1.
Example 9
This example is for explaining the method for preparing and evaluating the precursor of the positive electrode material and the positive electrode material according to the present invention
(1) Preparation of positive electrode material precursor
The operation was carried out according to the method described in example 1, except that the pH of the system was controlled to 9 by adjusting the dropping rate of the NaOH solution during the dropping process, to obtain a precursor of the positive electrode material.
(2) Evaluation of Positive electrode Material precursor
The SEM image of the positive electrode material precursor is similar to fig. 1A and 1B, and the XRD image is similar to fig. 2.
(3) Preparation and evaluation of cathode Material
Positive electrode material and lithium battery prepared according to the method of example 1
The discharge capacity and first-week efficiency at 0.1C rate were measured, and the specific results are shown in table 1.
Example 10
This example is for explaining the method for preparing and evaluating the precursor of the positive electrode material and the positive electrode material according to the present invention
(1) Preparation of positive electrode material precursor
The operation was carried out in the same manner as in example 1, except that the reaction temperature was controlled to 70 ℃ during the dropping to obtain a precursor of a positive electrode material.
(2) Evaluation of Positive electrode Material precursor
The SEM image of the positive electrode material precursor is similar to fig. 1A and 1B, and the XRD image is similar to fig. 2.
(3) Preparation and evaluation of cathode Material
Positive electrode material and lithium battery prepared according to the method of example 1
The discharge capacity and first-week efficiency at 0.1C rate were measured, and the specific results are shown in table 1.
Example 11
This example is for explaining the method for preparing and evaluating the precursor of the positive electrode material and the positive electrode material according to the present invention
(1) Preparation of positive electrode material precursor
The operation was carried out in the same manner as in example 1, except that the reaction temperature was controlled to 30 ℃ during the dropping to obtain a precursor of a positive electrode material.
(2) Evaluation of Positive electrode Material precursor
The SEM image of the positive electrode material precursor is similar to fig. 1A and 1B, and the XRD image is similar to fig. 2.
(3) Preparation and evaluation of cathode Material
Positive electrode material and lithium battery prepared according to the method of example 1
The discharge capacity and first-week efficiency at 0.1C rate were measured, and the specific results are shown in table 1.
Example 12
This example is for explaining the method for preparing and evaluating the precursor of the positive electrode material and the positive electrode material according to the present invention
(1) Preparation of positive electrode material precursor
The operation was carried out in the same manner as in example 1, except that the reaction time was 12 hours, to obtain a precursor of a positive electrode material.
(2) Evaluation of Positive electrode Material precursor
The SEM image of the positive electrode material precursor is similar to fig. 1A and 1B, and the XRD image is similar to fig. 2.
(3) Preparation and evaluation of cathode Material
Positive electrode material and lithium battery prepared according to the method of example 1
The discharge capacity and first-week efficiency at 0.1C rate were measured, and the specific results are shown in table 1.
Example 13
This example is for explaining the method for preparing and evaluating the precursor of the positive electrode material and the positive electrode material according to the present invention
(1) Preparation of positive electrode material precursor
The operation was carried out in the same manner as in example 1 except that the stirring speed was 50r/min, to obtain a precursor of a positive electrode material.
(2) Evaluation of Positive electrode Material precursor
The SEM image of the positive electrode material precursor is similar to fig. 1A and 1B, and the XRD image is similar to fig. 2.
(3) Preparation and evaluation of cathode Material
Positive electrode material and lithium battery prepared according to the method of example 1
The discharge capacity and first-week efficiency at 0.1C rate were measured, and the specific results are shown in table 1.
Example 14
This example is for explaining the method for preparing and evaluating the precursor of the positive electrode material and the positive electrode material according to the present invention
(1) Preparation of positive electrode material precursor
The operation was carried out in the same manner as in example 1 except that the stirring speed was 1000r/min, to obtain a precursor of a positive electrode material.
(2) Evaluation of Positive electrode Material precursor
The SEM image of the positive electrode material precursor is similar to fig. 1A and 1B, and the XRD image is similar to fig. 2.
(3) Preparation and evaluation of cathode Material
Positive electrode material and lithium battery prepared according to the method of example 1
The discharge capacity and first-week efficiency at 0.1C rate were measured, and the specific results are shown in table 1.
Comparative example 1
This comparative example is used to illustrate a reference positive electrode material precursor, a method for producing a positive electrode material, and a method for evaluating a positive electrode material
(1) Preparation of positive electrode material precursor
The operation was performed according to the method of example 1, except that the dropping process was a continuous dropping process of the metal solution, the precipitant solution, and the complexing agent solution, and there was no intermittent dropping process of the metal solution, to obtain a positive electrode material precursor.
(2) Evaluation of Positive electrode Material precursor
The SEM image of the precursor of the cathode material shows that the precursor of the cathode material has the morphological characteristics of polycrystalline spherical agglomerates and has better sphericity.
The XRD pattern is shown in FIG. 3, and it can be seen that the difference between the (001) plane, the (100) plane and the (101) plane is small, the intensity ratio of I (001)/I (100) is 1.2, and the intensity ratio of I (001)/I (101) is 1.0.
(3) Preparation and evaluation of cathode Material
Positive electrode material and lithium battery prepared according to the method of example 1
The discharge capacity and first-week efficiency at 0.1C rate were measured, and the specific results are shown in table 1.
TABLE 1
| Numbering | Discharge capacity mAh/g | First week efficiency% |
| Example 1 | 202 | 92 |
| Example 2 | 200.1 | 91.5 |
| Example 3 | 182.7 | 90.4 |
| Example 4 | 199.6 | 91.2 |
| Example 5 | 198.7 | 91.1 |
| Example 6 | 197.6 | 90.7 |
| Example 7 | 197.3 | 90.6 |
| Example 8 | 195.4 | 90.3 |
| Example 9 | 196.5 | 91.3 |
| Example 10 | 198.4 | 90.9 |
| Example 11 | 199.7 | 90.5 |
| Example 12 | 197.8 | 91.4 |
| Example 13 | 194.5 | 91.8 |
| Example 14 | 200.5 | 91.7 |
| Comparative example 1 | 187 | 87 |
From the above results, it can be seen that compared with the comparative example, the method of the present invention produces a novel precursor of a positive electrode material, which is different from the polycrystalline spherical precursor, and contains lamellar single crystal agglomerates and polyhedral single crystal particles, and has a larger exposed area of the 001 plane, and better electrochemical properties, such as higher discharge capacity and first cycle efficiency.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. The precursor of the positive electrode material is characterized by comprising flaky single crystal agglomerates and polyhedral single crystal particles;
wherein in the XRD pattern of the cathode material precursor, the following relations are satisfied among I (001), I (100) and I (101): i (001)/I (100) is not less than 1.5, and I (001)/I (101) is not less than 1.2;
wherein the chemical formula of the precursor of the positive electrode material is NixCoyMz(OH)2M is at least one selected from Fe, Cr, Cu, Ti, Mg, W, Mo, Nb, Zn, Sn, Zr, Ga, Mn and Al;
wherein x is more than or equal to 0.3 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.5, and z is more than or equal to 0 and less than or equal to 0.3.
2. A method for preparing a precursor of a positive electrode material, comprising:
(1) intermittently dropwise adding a metal salt solution, a precipitator solution and an optional complexing agent solution, mixing and reacting;
(2) carrying out solid-liquid separation and drying treatment on the product obtained in the step (1) to obtain the precursor of the positive electrode material;
the metal salt solution contains metal elements Ni, Co and M, wherein M is at least one selected from Fe, Cr, Cu, Ti, Mg, W, Mo, Nb, Zn, Sn, Zr, Ga, Mn and Al;
wherein the molar usage ratio of the Ni element, the Co element and the M element is (0.3-1): (0-0.5): (0-0.3).
3. The production method according to claim 2, wherein the metal salt solution contains a metal element that is a combination of Ni, Co, and Mn or a combination of Ni, Co, and Al;
preferably, the metal salt solution contains at least one metal salt selected from the group consisting of metal sulfate, metal nitrate, metal acetate, and metal oxalate;
preferably, the molar concentration of the metal salt solution is 0.01-5mol/L calculated on the metal element.
4. The production method according to claim 2, wherein the precipitant is selected from at least one of NaOH, KOH, and LiOH;
preferably, the concentration of the precipitant solution is 0.02 to 10 mol/L.
5. The production method according to claim 2, wherein the complexing agent is selected from at least one of an ammonium ion donor, an ethanolamine-based complexing agent, an aminocarboxylic acid-based complexing agent, a hydroxyaminocarboxylic acid-based complexing agent, and a carboxylate-based complexing agent;
preferably, the concentration of the complexing agent solution is 0.01-15 mol/L.
6. The production method according to any one of claims 2 to 5, wherein in the step (1), the intermittent dropwise addition process comprises:
(1) dripping the metal salt solution, the precipitant solution and the optional complexing agent solution into a reaction kettle simultaneously under the reaction condition;
(2) after the three solutions are simultaneously dripped for 2-12h each time, stopping feeding the metal salt solution for 0.5-4 h;
(3) and (3) repeating the intermittent dropwise adding process in the step (2) until the reaction is finished.
7. The production method according to claim 2 or 6, wherein in step (1), the reaction conditions include: the temperature is 30-70 ℃, preferably 45-60 ℃; the time is not less than 10h, preferably 24-72 h;
preferably, the mixing is performed under stirring conditions;
more preferably, the stirring speed is 50-1000 r/min.
8. A precursor of a positive electrode material obtained by the production method according to any one of claims 1 to 7.
9. A positive electrode material, comprising the positive electrode material precursor according to claim 1 or 8 and lithium element;
preferably, the molar ratio of the lithium element to the positive electrode material precursor is 0.9-1.2:1 in terms of metal element.
10. Use of the positive electrode material precursor of claim 1 or 8 or the positive electrode material of claim 9 in a lithium battery.
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| CN201910990467.8A CN112687870B (en) | 2019-10-17 | 2019-10-17 | Positive electrode material precursor and preparation method thereof, and positive electrode material and application thereof |
| US17/754,967 US20220388863A1 (en) | 2019-10-17 | 2020-10-16 | Lithium Battery Positive Electrode Material Precursor, Preparation Method Therefor and Application Thereof |
| JP2022522945A JP2022553217A (en) | 2019-10-17 | 2020-10-16 | Precursor for Lithium Battery Cathode Material, Method for Making the Same, and Application Thereof |
| CA3156276A CA3156276A1 (en) | 2019-10-17 | 2020-10-16 | Lithium battery positive electrode material precursor, preparation method therefor and application thereof |
| PCT/CN2020/121341 WO2021073583A1 (en) | 2019-10-17 | 2020-10-16 | Lithium battery positive electrode material precursor, preparation method therefor and use thereof |
| MX2022004587A MX2022004587A (en) | 2019-10-17 | 2020-10-16 | Lithium battery positive electrode material precursor, preparation method therefor and use thereof. |
| BR112022006646A BR112022006646A2 (en) | 2019-10-17 | 2020-10-16 | LITHIUM BATTERY POSITIVE ELECTRODE MATERIAL PRECURSOR, METHOD OF PREPARING IT AND USE THEREOF |
| AU2020367186A AU2020367186A1 (en) | 2019-10-17 | 2020-10-16 | Lithium battery positive electrode material precursor, preparation method therefor and use thereof |
| KR1020227016598A KR20220084363A (en) | 2019-10-17 | 2020-10-16 | Lithium battery positive active material precursor, manufacturing method and use thereof |
| EP20877356.4A EP4047690A4 (en) | 2019-10-17 | 2020-10-16 | Lithium battery positive electrode material precursor, preparation method therefor and use thereof |
| ZA2022/05597A ZA202205597B (en) | 2019-10-17 | 2022-05-20 | Lithium battery positive electrode material precursor, preparation method therefor and application thereof |
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| CN113582246A (en) * | 2021-06-30 | 2021-11-02 | 南通金通储能动力新材料有限公司 | Preparation method of high-nickel polycrystalline quaternary precursor |
| CN115072804A (en) * | 2022-07-08 | 2022-09-20 | 金驰能源材料有限公司 | Method for regulating and controlling XRD diffraction intensity ratio of crystal faces of precursor (101) and precursor (001) |
| EP4194407A1 (en) * | 2021-12-07 | 2023-06-14 | SK Innovation Co., Ltd. | Cathode active material precursor for lithium secondary battery, cathode active material for lithium secondary battery and lithium secondary battery |
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| CN102244257A (en) * | 2011-06-15 | 2011-11-16 | 清华大学深圳研究生院 | High-temperature manganic acid lithium cathode material and preparation method thereof |
| CN109305699A (en) * | 2018-09-12 | 2019-02-05 | 中伟新材料有限公司 | A kind of preparation method of amorphous monocrystalline oxidation of precursor object |
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| JP2007294119A (en) * | 2006-04-21 | 2007-11-08 | National Institute Of Advanced Industrial & Technology | Single crystal particle of oxide for lithium secondary battery electrode and its manufacturing method, and lithium secondary battery using it |
| CN102244257A (en) * | 2011-06-15 | 2011-11-16 | 清华大学深圳研究生院 | High-temperature manganic acid lithium cathode material and preparation method thereof |
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| CN113582246A (en) * | 2021-06-30 | 2021-11-02 | 南通金通储能动力新材料有限公司 | Preparation method of high-nickel polycrystalline quaternary precursor |
| CN113582246B (en) * | 2021-06-30 | 2023-02-21 | 南通金通储能动力新材料有限公司 | Preparation method of high-nickel polycrystalline quaternary precursor |
| EP4194407A1 (en) * | 2021-12-07 | 2023-06-14 | SK Innovation Co., Ltd. | Cathode active material precursor for lithium secondary battery, cathode active material for lithium secondary battery and lithium secondary battery |
| CN115072804A (en) * | 2022-07-08 | 2022-09-20 | 金驰能源材料有限公司 | Method for regulating and controlling XRD diffraction intensity ratio of crystal faces of precursor (101) and precursor (001) |
| CN115072804B (en) * | 2022-07-08 | 2024-02-02 | 金驰能源材料有限公司 | Method for regulating XRD diffraction intensity ratio of precursor (101) and (001) crystal faces |
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