CN109987650B - Nickel cobalt lithium manganate positive electrode material, preparation method and application thereof - Google Patents
Nickel cobalt lithium manganate positive electrode material, preparation method and application thereof Download PDFInfo
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Abstract
A preparation method of a nickel cobalt lithium manganate positive electrode material comprises the following steps: preparing a mixed solution comprising a nickel source, a cobalt source and a manganese source, a strong alkali solution and an ammonium ion-containing inorganic salt solution, simultaneously mixing the mixed solution, the strong alkali solution and the ammonium ion-containing inorganic salt solution to perform a rapid coprecipitation reaction, controlling the pH value of the rapid coprecipitation reaction to be 10-12 to obtain a first suspension, and separating the first suspension to obtain a precipitate; preparing the precipitate into a second suspension, and carrying out ball milling on the second suspension; spray drying the ball-milled second suspension to obtain precursor powder; mixing the precursor powder with a lithium source to obtain a mixture; and calcining the mixture to obtain the nickel cobalt lithium manganate cathode material. The invention also provides a nickel cobalt lithium manganate positive electrode material, a positive electrode plate and a lithium ion battery.
Description
Technical Field
The invention relates to the field of batteries, in particular to a nickel cobalt lithium manganate positive electrode material, and a preparation method and application thereof.
Background
With the development of society, energy and environmental problems are increasingly prominent, and the electric vehicle is used as an effective means to relieve the energy and environmental problems brought by the traditional fuel vehicle. Lithium ion battery is as the energy supply core part of electric motor car, and the development bottleneck of its performance mainly lies in positive pole material, and what use more to lithium ion power battery positive pole material at present is lithium iron phosphate, spinel lithium manganate and nickel cobalt lithium manganate, because the requirement to electric motor car continuation of the journey mileage is higher and higher, so nickel cobalt lithium manganate positive pole material that has high energy density and higher compaction density has received people's favor. The nickel cobalt lithium manganate positive electrode material integrates the good cycle performance of lithium cobaltate, the high specific capacity of lithium nickelate and the high safety and low cost of lithium manganate through the synergistic effect of three elements of Ni-Co-Mn.
Currently, the research on the preparation method of the nickel cobalt lithium manganate cathode material is more than that of a hydrothermal method, a sol-gel method, a molten salt method, a spray pyrolysis method and the like. However, these methods are not suitable for mass production, mainly because of low yield, expensive raw materials, and difficult control of the synthesis process. Therefore, a coprecipitation method is widely adopted at present, firstly a ternary precipitate precursor is synthesized through coprecipitation, then the precursor is mixed with a lithium source, and finally the ternary cathode material is obtained through high-temperature calcination. However, the traditional coprecipitation method has long process time for synthesizing the precursor, and the requirement on the morphology of the precursor is high, so that the synthesis conditions need to be strictly controlled in the synthesis process, and the obtained precursor needs to be dried for a long time.
Disclosure of Invention
In view of the above, there is a need to provide a method for preparing a lithium nickel cobalt manganese oxide positive electrode material with a relatively simple synthesis process, so as to solve the above problems.
In addition, a nickel cobalt lithium manganate positive electrode material is also needed to be provided.
In addition, a positive plate and a lithium ion battery comprising the nickel cobalt lithium manganate positive electrode material are also necessarily provided.
A preparation method of a nickel cobalt lithium manganate positive electrode material comprises the following steps:
preparing a mixed solution comprising a nickel source, a cobalt source and a manganese source, a strong alkali solution and an ammonium ion-containing inorganic salt solution, simultaneously mixing the mixed solution, the strong alkali solution and the ammonium ion-containing inorganic salt solution to perform a rapid coprecipitation reaction, controlling the pH value of the rapid coprecipitation reaction to be 10-12 to obtain a first suspension, and separating the first suspension to obtain a precipitate;
preparing the precipitate into a second suspension, and carrying out ball milling on the second suspension;
spray drying the ball-milled second suspension to obtain precursor powder;
mixing the precursor powder with a lithium source to obtain a mixture; and
and calcining the mixture to obtain the nickel cobalt lithium manganate cathode material.
Further, the nickel source, the cobalt source and the manganese source are all water-soluble salts, the water-soluble salts comprise at least one of sulfate, nitrate, chloride and acetate, and the strong base comprises at least one of potassium hydroxide, sodium hydroxide and lithium hydroxide; the inorganic salt containing ammonium ions comprises at least one of ammonia water, ammonium sulfate, ammonium chloride and ammonium fluoride, and the lithium source is at least one of lithium hydroxide, lithium carbonate, lithium nitrate and lithium acetate.
Furthermore, the total mole number of the nickel element, the cobalt element and the manganese element in the precursor powder is x, the mole number of the lithium element in the lithium source is y, and the x: y is 1: 1.03-1: 1.1.
Further, the calcination comprises a first calcination stage and a second calcination stage, wherein the first calcination stage is to pre-calcine the mixture at 450-500 ℃ for 2-5 h at a temperature rise rate of 5-10 ℃/min, the second calcination stage is to heat the mixture to 750-1000 ℃ at a temperature rise rate of 1-3 ℃/min, and the temperature is kept for 9-18 h at the temperature.
Further, in the second calcining stage, when the mole number of the nickel element is less than or equal to 50% of the total mole number of the nickel element, the cobalt element and the manganese element, calcining the mixture in an air atmosphere; when the mole number of the nickel element is more than 50% of the total mole number, the mixture is calcined under an oxygen atmosphere.
Further, the conditions of the rapid coprecipitation reaction include a stirring speed of 500-1000r/min, a reaction temperature of 40-60 ℃, a feeding speed of 12.5-30 mL/min, and a reaction time of 0.5-2 h.
The lithium nickel cobalt manganese oxide positive electrode material has a chemical general formula of LiNiaCobMn1-a-bO20 to said<a<1，0<b<1, a: b ═ 1:1 to 8: 1; the nickel cobalt lithium manganate positive electrode material is composed of secondary particles formed by agglomerating nanoscale primary particles, the particle size of the primary particles is 100nm-500nm, the secondary particles are approximately spherical, and the particle size of the secondary particles is 1 mu m-30 mu m.
Furthermore, the particle diameter D50 of the secondary particles of the nickel cobalt lithium manganate positive electrode material is 12-13 μm, D10 is 4.0-5.0 μm, D90 is 30-32 μm, and the particle diameter distribution curve is in normal distribution.
The utility model provides a positive plate, positive plate include the mass flow body and set up in the coating material on mass flow body surface, coating material includes nickel cobalt lithium manganate cathode material, conducting material and binder.
A lithium ion battery comprises a positive plate, a negative plate, a diaphragm arranged between the positive plate and the negative plate and electrolyte.
The preparation method of the lithium nickel cobalt manganese oxide positive electrode material provided by the invention is based on the rapid coprecipitation combined spray drying technology to obtain the lithium nickel cobalt manganese oxide positive electrode material with high sphericity and uniform particle size distribution, and the preparation method is beneficial to shortening the synthesis time of the lithium nickel cobalt manganese oxide precursor, and has the advantages of short reaction time in the rapid coprecipitation process, simple process, low cost, suitability for mass production and huge industrialized production value. Meanwhile, according to the preparation method provided by the invention, the nickel cobalt lithium manganate anode materials with different properties can be prepared according to the difference of the composition proportions of the nickel, the cobalt and the manganese. The nickel cobalt lithium manganate positive electrode material provided by the invention has high charge-discharge specific capacity, high voltage and high temperature cycling stability and good rate capability.
Drawings
Fig. 1 is a flow chart of a preparation method of a lithium nickel cobalt manganese oxide positive electrode material provided by an embodiment of the invention.
Fig. 2 is an X-ray diffraction pattern (XRD) of the lithium nickel cobalt manganese oxide positive electrode material prepared in example 1 of the present invention.
Fig. 3A, fig. 3B and fig. 3C are scanning electron microscope test charts of the lithium nickel cobalt manganese oxide positive electrode material prepared in example 1 of the present invention under different magnifications, respectively.
Fig. 4A is a cycle performance test chart of a button cell assembled by the lithium nickel cobalt manganese oxide positive electrode material prepared in example 1 of the invention at 25 ℃, and fig. 4B is a cycle performance test chart of a button cell assembled by the lithium nickel cobalt manganese oxide positive electrode material prepared in example 1 of the invention at 60 ℃.
Fig. 5A is a rate performance test chart of a button cell assembled by the lithium nickel cobalt manganese oxide positive electrode material prepared in example 1 of the invention at 25 ℃, and fig. 5B is a rate performance test chart of a button cell assembled by the lithium nickel cobalt manganese oxide positive electrode material prepared in example 1 of the invention at 60 ℃.
The following detailed description will further illustrate the invention in conjunction with the above-described figures.
Detailed Description
So that the manner in which the above recited objects, features and advantages of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to the embodiments thereof which are illustrated in the appended drawings. In addition, the embodiments and features of the embodiments of the present application may be combined with each other without conflict. In the following description, numerous specific details are set forth to provide a thorough understanding of the present invention, and the described embodiments are merely a subset of the embodiments of the present invention, rather than a complete embodiment. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes all and any combination of one or more of the associated listed items.
Referring to fig. 1, an embodiment of the present invention provides a method for preparing a lithium nickel cobalt manganese oxide positive electrode material, including the following steps:
step S1: preparing a mixed solution comprising a nickel source, a cobalt source and a manganese source, a strong alkali solution and an ammonium ion-containing inorganic salt solution, simultaneously mixing the mixed solution, the strong alkali solution and the ammonium ion-containing inorganic salt solution to perform a rapid coprecipitation reaction, controlling the pH value of the rapid coprecipitation reaction to be 10-12 to obtain a first suspension, and separating the first suspension to obtain a precipitate;
step S2: preparing the precipitate into a second suspension, and carrying out ball milling on the second suspension;
step S3: spray drying the ball-milled second suspension to obtain precursor powder;
step S4: mixing the precursor powder with a lithium source to obtain a mixture;
step S5: and calcining the mixture to obtain the nickel cobalt lithium manganate cathode material.
In step S1, the nickel source, the cobalt source and the manganese source are all water-soluble salts, and the water-soluble salts include at least one of sulfate, nitrate, chloride and acetate; the alkali comprises at least one of potassium hydroxide, sodium hydroxide and lithium hydroxide; the inorganic salt containing ammonium ions comprises at least one of ammonia water, ammonium sulfate, ammonium chloride and ammonium fluoride, and the ammonium ions are used as complexing agents to carry out rapid coprecipitation reaction on the nickel source, the cobalt source and the manganese source in an alkaline environment.
Further, the rapid coprecipitation reaction is carried out in a protective atmosphere, wherein the protective atmosphere is an argon atmosphere or a nitrogen atmosphere; the total molar concentration of nickel, cobalt and manganese metal ions contained in the mixed solution is 2-4 mol/L, the concentration of the alkali solution is 4-16 mol/L, and the concentration of the inorganic salt solution containing ammonium ions is 0.1-0.5 times of the molar concentration of the metal ions.
Further, the rapid coprecipitation reaction is carried out under the conditions that the stirring speed is 500-1000r/min, the reaction temperature is 40-60 ℃, the feeding speed is 12.5-30 mL/min, and the reaction time is 0.5-2 h, so as to obtain the precipitate.
Specifically, the mixed solution nucleates and gradually grows into secondary particles in an alkaline environment containing ammonium ions.
Further, in the process of the rapid coprecipitation reaction, since hydroxide ions are continuously consumed, an alkali solution needs to be continuously added to maintain the pH value during the rapid coprecipitation reaction, so that the rapid coprecipitation reaction can be continuously and stably performed.
In step S2, the solid content in the second suspension is 20% to 35%, the second suspension is placed in a ball milling jar and ball milled for 2h to 5h at a rotation speed of 200r/min to 500r/min, wherein the material of the ball milling jar is at least one of zirconia or agate, the material of the ball milling jar is nylon, polytetrafluoroethylene or agate, and the material-ball ratio (i.e., the mass ratio of the second suspension to the ball milling) is 1:10 to 15.
In step S3, the ball-milled second suspension is spray-dried in a spray dryer at an inlet temperature of 200 ℃ to 300 ℃, an air blowing efficiency of 50% to 70%, and an air pressure of 0.1MPa to 0.5MPa, to obtain the precursor powder. Because the precipitate particles after ball milling are nano particles, in the spray drying process, the second turbid liquid is atomized in a spray dryer to form fog drops, the fog drops contain the precipitate of the nano particles, under the action of hot air, the fog drops quickly lose moisture, the precipitate of the nano particles in the fog drops is recombined to form large secondary particles, the secondary particles are spherical, the secondary particles are precursor powder, and therefore the particle recombination and the pelletizing in the spray drying process are realized, and meanwhile, the drying of the precursor powder is also completed.
Furthermore, in the spray drying process, the nanoscale primary particles are gathered into micron-sized secondary particles, so that the compaction density of the nickel cobalt lithium manganate anode material prepared by calcination is increased, and the volume energy density of the nickel cobalt lithium manganate anode material as a lithium ion battery electrode material is increased.
In step S4, the precursor powder is mixed with a lithium source in a proportion to obtain a mixture, the lithium source is at least one of lithium hydroxide, lithium carbonate, lithium nitrate and lithium acetate, and when two or more lithium sources are selected, the proportion of the lithium sources is any proportion. The precursor powder contains three metal elements of nickel element, cobalt element and manganese element, the total mole number of the nickel element, the cobalt element and the manganese element is x, the mole number of the lithium element contained in the lithium source is y, and the x: y is 1: 1.03-1: 1.1.
In step S5, the calcination includes a first calcination stage and a second calcination stage, the first calcination stage is to pre-calcine the mixture at 450-500 ℃ for 2-5 h with a temperature rise rate of 5-10 ℃/min, the second calcination stage is to heat up to 750-1000 ℃ with a temperature rise rate of 1-3 ℃/min, and the temperature is kept at this temperature for 9-18 h.
Further, the calcination also comprises a cooling stage, and the mixture after the second calcination stage is cooled to room temperature at the speed of 5-10 ℃/min.
Further, in the second calcination stage, when the number of moles of the nickel element is less than or equal to 50% of the total number of moles of the three elements, the mixture is calcined under an air atmosphere; when the number of moles of the nickel element is more than 50% of the total number of moles of the three elements, the mixture is calcined under an oxygen atmosphere.
And further, sieving the calcined product by a 300-mesh sieve to obtain the nickel cobalt lithium manganate positive electrode material.
The invention also provides a lithium nickel cobalt manganese oxide positive electrode material prepared by the preparation method, wherein the chemical general formula of the lithium nickel cobalt manganese oxide positive electrode material is LiNiaCobMn1-a-bO20 to said<a<1，0<b<1, a: b ═ 1:1 to 8: 1; the nickel cobalt lithium manganate positive electrode material is formed by agglomerating nanoscale primary particlesThe particle size of the primary particles is 100nm-500nm, the secondary particles are approximately spherical, and the particle size of the secondary particles is 1 μm-30 μm.
Furthermore, the particle diameter D50 of the secondary particles of the nickel cobalt lithium manganate positive electrode material is 12-13 μm (namely the particle diameter of the secondary particles is smaller than 12-13 μm and accounts for 50 percent of the total), D10 is 4.0-5.0 μm, D90 is 30-32 μm, and the particle diameter distribution curve is in normal distribution.
In one embodiment, the D50 is 12.3 μm, the D10 is 4.8 μm, and the D90 is 30.9 μm.
Furthermore, the valence state of the nickel element in the nickel cobalt lithium manganate positive electrode material is +2 and/or + 3.
Specifically, the nickel element with the valence of +3 in the nickel cobalt lithium manganate cathode material is increased along with the increase of the content of the nickel element.
Further, the crystal form of the nickel cobalt lithium manganate positive electrode material is a hexagonal phase, the nickel cobalt lithium manganate positive electrode material is of a layered structure, and the space group is
The embodiment of the invention also provides a positive plate, which comprises a current collector and a coating material arranged on the surface of the current collector, wherein the coating material comprises the nickel cobalt lithium manganate positive electrode material, a conductive material and a binder, the nickel cobalt lithium manganate positive electrode material, the conductive material and the binder are dispersed in a solvent according to a proportion and are uniformly mixed to obtain a dispersion solution, and then the dispersion solution is coated on the current collector, dried and sliced to obtain the positive plate.
The embodiment of the invention also provides a lithium ion battery, which comprises the positive plate, the negative plate, a diaphragm arranged between the positive plate and the negative plate and electrolyte.
The present invention will be specifically described below with reference to examples.
Example 1
Respectively taking nickel sulfate, cobalt sulfate and manganese sulfate as a nickel source, a cobalt source and a manganese source, wherein the molar ratio of the nickel sulfate to the cobalt sulfate to the manganese sulfate is 8:1:1, and preparing the nickel sulfate, the cobalt sulfate and the manganese sulfate into a mixed solution, wherein the total molar amount is 2 mol/L; sodium hydroxide is strong base and is prepared into 10mol/L sodium hydroxide solution; ammonia water is taken as a complexing agent, 0.5mol/L ammonia water solution is prepared, 1L deionized water is added into a reaction kettle, and a proper amount of sodium hydroxide solution and ammonia water are added; under the conditions that the stirring speed is 600r/min, the reaction temperature is 50 ℃ and high-purity nitrogen is continuously introduced, a mixed solution containing nickel sulfate, cobalt sulfate and manganese sulfate, a sodium hydroxide solution and an ammonia water solution are simultaneously added into a reaction kettle to obtain a rapid coprecipitation reaction, a first suspension is obtained, the pH value in the rapid coprecipitation reaction process is kept to be 11.5, the feeding speed is 15mL/min, and the reaction is carried out for 1h to obtain a precipitate.
Washing and filtering the precipitate; and then preparing the precipitate into a second suspension with the solid content of 25%, placing the second suspension in a ball milling tank, adding agate balls, wherein the mass ratio of the precipitate to the agate balls in the second suspension is 1:10, and then ball milling the second suspension for 3 hours at the speed of 400 r/min.
And carrying out spray drying on the ball-milled second suspension, wherein the inlet temperature of the spray drying is 250 ℃, the blowing efficiency is 60%, and the air pressure is 0.3MPa, and carrying out spray drying to obtain precursor powder.
And mixing the precursor powder and lithium hydroxide according to a ratio to obtain a mixture, wherein x: y is 1: 1.05. Heating the mixture to 500 ℃ at a heating rate of 10 ℃/min and preserving the heat for 5h in the atmosphere of high-purity oxygen; then heating to 780 ℃ at the heating rate of 3 ℃/min and preserving heat for 11 h; and then cooling to room temperature at a cooling rate of 5 ℃/min to finally obtain the nickel cobalt lithium manganate cathode material.
Example 2
In contrast to the examples: the nickel source, the cobalt source and the manganese source in this example are nickel chloride, cobalt chloride and manganese chloride, respectively, the molar ratio of nickel chloride, cobalt chloride and manganese chloride is 7:1.5:1.5, the pH value of the rapid coprecipitation reaction is 11.2, and the temperature in the second calcination stage is 820 ℃.
The other steps are the same as in example 1 and are not repeated here.
Example 3
In contrast to the examples: the nickel source, the cobalt source, and the manganese source in this example are nickel nitrate, cobalt nitrate, and manganese nitrate, respectively, the molar ratio of nickel nitrate, cobalt nitrate, and manganese nitrate is 6:2:2, the pH value at which the rapid coprecipitation reaction occurs is 11.0, and the temperature at the second calcination stage is 850 ℃.
The other steps are the same as in example 1 and are not repeated here.
Example 4
In contrast to the examples: the nickel source, the cobalt source and the manganese source in the embodiment are respectively nickel acetate, cobalt acetate and manganese acetate, the molar ratio of the nickel acetate, the cobalt acetate and the manganese acetate is 5:2:3, the pH value of the rapid coprecipitation reaction is 10.8, the temperature in the second calcination stage is 870 ℃, and the calcination atmosphere is air.
The other steps are the same as in example 1 and are not repeated here.
Example 5
In contrast to the examples: the nickel source, the cobalt source and the manganese source in the embodiment are respectively nickel sulfate, cobalt chloride and manganese nitrate, the molar ratio of the nickel sulfate, the cobalt chloride and the manganese nitrate is 1:1:1, the complexing agent is an ammonium chloride solution, the concentration of the ammonium chloride solution is 0.5mol/L, the pH value of the rapid coprecipitation reaction is 10.5, the temperature in the second calcination stage is 900 ℃, and the calcination atmosphere is air.
The other steps are the same as in example 1 and are not repeated here.
Specific treatment conditions for examples 1 to 5 are shown in Table 1.
Table 1 examples 1-5 specific treatment conditions
Referring to fig. 2, XRD test is performed on the lithium nickel cobalt manganese oxide positive electrode material obtained in example 1, since the lithium nickel cobalt manganese oxide positive electrode material does not have a special standard PDF card matching it, and is usually matched with LiNiO2Or LiCoO2Matching with standard PDF card, LiNiO2With LiCoO2Belongs to the same crystal system, so the diffraction peak positions corresponding to the standard PDF cards are the same. The standard PDF card selected in FIG. 2 is LiNiO2The lithium nickel cobalt manganese oxide cathode material and LiNiO prepared in example 12The characteristic peaks of (A) are well matched, and no other impurity peaks exist.
Scanning electron microscope tests are performed on the lithium nickel cobalt manganese oxide positive electrode material prepared in example 1, and the test results are shown in fig. 3A, fig. 3B and fig. 3C, and fig. 3A, fig. 3B and fig. 3C are the test results under different magnifications, wherein the magnifications in fig. 3A, fig. 3B and fig. 3C are sequentially increased, from fig. 3A, the lithium nickel cobalt manganese oxide positive electrode material is approximately spherical, the particle size distribution is uniform, and the particle size of the secondary particles of the lithium nickel cobalt manganese oxide positive electrode material is 1 μm-20 μm; as can be seen from fig. 3B, each spherical lithium nickel cobalt manganese oxide positive electrode material is composed of smaller primary particles; as can be seen from FIG. 3C, the primary particles have a relatively uniform size distribution, ranging from about 100nm to about 500 nm.
The nickel cobalt lithium manganate positive electrode materials prepared in examples 1 to 5 were used as a positive electrode material of a lithium ion battery, and a 2032 type button cell was assembled in a glove box filled with high purity argon gas by using a lithium sheet as a counter electrode. The button cell is tested by using a LANHE CT2001A battery test system to perform electrochemical performance tests at room temperature (25 ℃) and high temperature (60 ℃), wherein the electrochemical performance tests comprise a cycle performance test and a rate performance test. During the cycle performance test, the charge-discharge voltage range at room temperature is 2.8-4.5V, the charge-discharge voltage range at high temperature is 2.8-4.3V, and the current density of the cycle performance test is 1C (180 mA/g); during the multiplying power performance test, the current density is 0.2C, 1C, 2C, 32C, 5C and 10C in sequence, 10 cycles are carried out under each current density, and the discharge voltage range is consistent with that during the cycle performance test.
Examples 1-5 electrochemical performance test the results of the tests at 25 c and 60 c are shown in tables 2 and 3, respectively.
Table 2 results of electrochemical performance test at 25 ℃ for examples 1 to 5
Table 3 results of electrochemical performance test at 60 c for examples 1-5
In table 1, the molar mass of the nickel source in examples 1 to 5 is higher and higher relative to the total molar mass of the nickel source, the cobalt source and the manganese source, that is, the nickel element content of the nickel cobalt lithium manganate positive electrode material prepared in examples 1 to 5 is lower and lower. As can be seen from tables 2 and 3, as the content of the nickel element decreases, the capacity retention rates after 100 cycles at 25 ℃ and 60 ℃ respectively increase gradually, because as the content of the nickel element decreases, the contents of the cobalt element and the manganese element increase, and the stability of the prepared lithium nickel cobalt manganese oxide cathode material becomes higher and higher.
With the reduction of the content of the nickel element, the first reversible capacity and the reversible capacity under 10 ℃ are gradually reduced, because the nickel element in the nickel cobalt lithium manganate positive electrode material is an electrochemically active component, and the capacity is exerted through the oxidation-reduction reaction of the nickel element, the lower the content of the nickel element is, the lower the charge-discharge specific capacity of the nickel cobalt lithium manganate positive electrode material is.
Referring to fig. 4A and 4B, fig. 4A and 4B show cycling performance tests of the button cell assembled with the lithium nickel cobalt manganese oxide positive electrode material prepared in example 1 at 25 ℃ and 60 ℃ for 100 cycles at a current density of 180 mA/g. Referring to fig. 4A, under the test condition of 25 ℃, after the button cell prepared in example 1 is cycled for 100 cycles, the specific discharge capacity is 173mAh/g, and the capacity retention rate is 93.34%; referring to fig. 4B, under the test condition of 60 ℃, the specific discharge capacity is 177mAh/g, and the capacity retention rate is 93.29%; the nickel cobalt lithium manganate cathode material prepared in example 1 has good cycling stability and better high-temperature cycling stability as the lithium ion battery electrode material.
Referring to fig. 5A and 5B, fig. 5A and 5B are respectively a rate performance test of the button cell assembled with the lithium nickel cobalt manganese oxide positive electrode material prepared in example 1 at 25 ℃ and 60 ℃, and after the charge and discharge test at a high rate (10C), the charge and discharge specific capacity returns to the charge and discharge test at a low rate (0.2C), which is still at the same level as that of the original charge and discharge cycle test at a low rate (0.2C), which illustrates that the lithium nickel cobalt manganese oxide positive electrode material prepared in example 1 can withstand the charge and discharge cycle test at a high rate.
The preparation method of the lithium nickel cobalt manganese oxide positive electrode material provided by the invention is based on the rapid coprecipitation combined spray drying technology to obtain the lithium nickel cobalt manganese oxide positive electrode material with high sphericity and uniform particle size distribution, and the preparation method is beneficial to shortening the synthesis time of the lithium nickel cobalt manganese oxide precursor, and has the advantages of short reaction time in the rapid coprecipitation process, simple process, low cost, suitability for mass production and huge industrialized production value. Meanwhile, according to the preparation method provided by the invention, the nickel cobalt lithium manganate anode materials with different properties can be prepared according to the difference of the composition proportions of the nickel, the cobalt and the manganese. The nickel cobalt lithium manganate positive electrode material provided by the invention has high charge-discharge specific capacity, high voltage and high temperature cycling stability and good rate capability.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention.
Claims (8)
1. The preparation method of the nickel cobalt lithium manganate positive electrode material is characterized by comprising the following steps of:
preparing a mixed solution comprising a nickel source, a cobalt source and a manganese source, a strong alkali solution and an ammonium ion-containing inorganic salt solution, simultaneously mixing the mixed solution, the strong alkali solution and the ammonium ion-containing inorganic salt solution to perform a rapid coprecipitation reaction, controlling the pH value of the rapid coprecipitation reaction to be 10.5-12 to obtain a first suspension, and separating the first suspension to obtain a precipitate;
preparing the precipitate into a second suspension, and carrying out ball milling on the second suspension, wherein the solid content in the second suspension is 20-35%, and the material-ball ratio is 1: 10-15;
spray drying the ball-milled second suspension to obtain precursor powder;
mixing the precursor powder with a lithium source to obtain a mixture; and
calcining the mixture to obtain the nickel cobalt lithium manganate positive electrode material;
the calcining comprises a first calcining stage and a second calcining stage, wherein the first calcining stage is to pre-calcine the mixture at 450-500 ℃ for 2-5 h, the heating rate is 5-10 ℃/min, the second calcining stage is to heat up to 750-1000 ℃ at the heating rate of 1-3 ℃/min, and the temperature is kept for 9-18 h at the temperature; in the second calcining stage, when the mole number of the nickel element is less than or equal to 50% of the total mole number of the nickel element, the cobalt element and the manganese element, calcining the mixture in an air atmosphere; when the mole number of the nickel element is more than 50% of the total mole number, the mixture is calcined under an oxygen atmosphere.
2. The method for preparing the lithium nickel cobalt manganese oxide cathode material according to claim 1, wherein the nickel source, the cobalt source and the manganese source are all water-soluble salts, the water-soluble salts comprise at least one of sulfate, nitrate, chloride and acetate, and the strong base comprises at least one of potassium hydroxide, sodium hydroxide and lithium hydroxide; the inorganic salt containing ammonium ions comprises at least one of ammonia water, ammonium sulfate, ammonium chloride and ammonium fluoride, and the lithium source is at least one of lithium hydroxide, lithium carbonate, lithium nitrate and lithium acetate.
3. The method for preparing the nickel cobalt lithium manganate positive electrode material of claim 1, wherein the total mole number of nickel element, cobalt element and manganese element in the precursor powder is x, the mole number of lithium element in the lithium source is y, and x: y is 1: 1.03-1: 1.1.
4. The method for preparing the nickel cobalt lithium manganate cathode material as set forth in claim 1, wherein the conditions of the rapid coprecipitation reaction include a stirring speed of 500-1000r/min, a reaction temperature of 40-60 ℃, a feeding speed of 12.5-30 mL/min, and a reaction time of 0.5-2 h.
5. The lithium nickel cobalt manganese oxide positive electrode material prepared by the method for preparing the lithium nickel cobalt manganese oxide positive electrode material according to any one of claims 1 to 4, wherein the chemical general formula of the lithium nickel cobalt manganese oxide positive electrode material is LiNiaCobMn1-a-bO20 to said<a<1，0<b<1, a: b ═ 1:1 to 8: 1; the nickel cobalt lithium manganate positive electrode material is composed of secondary particles formed by agglomerating nanoscale primary particles, the particle size of the primary particles is 100nm-500nm, the secondary particles are approximately spherical, and the particle size of the secondary particles is 1 mu m-30 mu m.
6. The lithium nickel cobalt manganese oxide positive electrode material of claim 5, wherein the secondary particle size D50 of the lithium nickel cobalt manganese oxide positive electrode material is 12-13 μm, D10 is 4.0-5.0 μm, D90 is 30-32 μm, and the particle size distribution curve is in a normal distribution.
7. A positive plate, which is characterized by comprising a current collector and a coating material arranged on the surface of the current collector, wherein the coating material comprises the nickel cobalt lithium manganate positive electrode material, a conductive material and a binder according to any one of claims 5 or 6.
8. A lithium ion battery comprising the positive electrode sheet according to claim 7, a negative electrode sheet, a separator provided between the positive electrode sheet and the negative electrode sheet, and an electrolyte.
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| CN113735187B (en) * | 2020-05-29 | 2023-06-09 | 东莞东阳光科研发有限公司 | Preparation method of nickel cobalt lithium manganate precursor |
| CN111908519A (en) * | 2020-07-24 | 2020-11-10 | 四川长虹电器股份有限公司 | High-capacity nickel-rich precursor, positive electrode material and preparation method thereof |
| US11870056B2 (en) * | 2020-08-18 | 2024-01-09 | Wildcat Discovery Technologies, Inc. | Cathode with disordered rocksalt material and method of forming the cathode |
| CN115286055B (en) * | 2022-10-08 | 2023-02-03 | 宜宾锂宝新材料有限公司 | Ternary cathode material, preparation method thereof, cathode and lithium ion battery |
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