CN110002515B - Preparation method of high-capacity single-crystal ternary cathode material - Google Patents
Preparation method of high-capacity single-crystal ternary cathode material Download PDFInfo
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Abstract
A preparation method of a high-capacity single crystal type ternary cathode material comprises the following steps: firstly, preparing a nickel-cobalt-manganese hydroxide precursor with a core-shell structure by adopting a coprecipitation method, intermittently introducing quantitative bicarbonate to prepare a loose and porous core at the initial stage of core formation, preparing a loose and porous flaky shell by greatly reducing the rotating speed and improving the pH value after the core formation is finished, and adding a dispersing agent to effectively prevent the shell from agglomerating due to the reduction of the rotating speed at the core-shell conversion stage; and secondly, mixing the prepared precursor with lithium salt, and calcining at high temperature for one time in an oxygen-rich atmosphere to obtain the single crystal ternary cathode material. The battery prepared from the ternary cathode material has high lithium ion transmission efficiency, reduced anisotropy in the crystal, high capacity and good safety performance. The problem of poor material capacity exertion caused by low lithium ion transmission efficiency of the single crystal ternary material is effectively solved. Meanwhile, the single crystal ternary cathode material is prepared by one-time sintering, the preparation process is simple, and the production cost is low.
Description
Technical Field
The invention relates to the field of lithium ion battery materials, in particular to a preparation method of a high-capacity single-crystal ternary cathode material.
Background
The explosive development of new energy automobiles drives the explosive growth of the demand of lithium ion batteries, and the lithium battery industry chain faces significant challenges and opportunities from top to bottom.
With the requirement of new energy automobiles on the endurance mileage becoming higher and higher, the ternary cathode material with high nickel content and low cobalt content gradually becomes one of the main development directions of the cathode material of the lithium ion battery. Meanwhile, the high safety performance of the new energy automobile is a pursuit which is unchangeable over the ancient times, so that the single crystallization of the ternary anode material also can be another main development direction of the anode material of the lithium ion battery.
At present, the ternary cathode material is mainly secondary spherical particles formed by agglomeration of primary nanoparticles, the volume of the lithium ion-releasing cathode material of the battery can contract and expand to a certain degree in the charging and discharging processes, and the volume change of the material can be aggravated along with the aggravation of the charging and discharging degree and the increase of the cycle number, so that the following problems are caused: firstly, because crystal boundaries exist among primary nano particles, cracks can appear between the crystal boundaries in the charging and discharging processes, and the performance of the electrical property of the material is seriously influenced; secondly, in the manufacturing process of the battery, the secondary ball particles are easily crushed, so that the interface reaction between the material and the electrolyte is aggravated, and the electrical property and the safety performance of the material are seriously worsened.
Compared with the prior art, the single crystal type cathode material can avoid the generation of cracks between crystal boundaries, reduce side reactions with electrolyte and well improve the cycle performance and safety performance of the material. However, compared with secondary spherical particles, the single crystal ternary material is slightly deficient in capacity exertion, mainly because the lithium ion transmission distance of the single crystal particles is greater than that of the primary nanoparticles, and the nanocrystallization of the single crystal particles sacrifices the volume energy density of the battery, so that the method has very important research significance on how to improve the capacity of the single crystal material. Meanwhile, the traditional preparation process of the single crystal material needs higher sintering requirements, so that the production process is complicated and the production cost is high, and therefore the problem needs to be solved.
For example: the existing preparation of the single crystal ternary material is mainly realized by sectional sintering and addition of an auxiliary agent, and the lithium ion transmission performance of the single crystal ternary material cannot be fundamentally improved by regulating and controlling the energy consumption and the productivity through a sintering means. The monocrystal ternary cathode material prepared by the patent CN104979546A has the advantages that the BET of the prepared flower cluster type precursor particles is too high, the filling during sintering is not facilitated, the productivity is low, the final monocrystal ternary cathode material is obtained by the method through pre-sintering, secondary sintering and third sintering, the sintering process is complicated, and the production cost is high.
Therefore, how to solve the above-mentioned deficiencies of the prior art is a problem to be solved by the present invention.
Disclosure of Invention
The invention aims to provide a preparation method of a high-capacity single-crystal ternary cathode material.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a high-capacity single-crystal ternary cathode material; the method sequentially comprises the following steps:
step one, adding pure water and a complexing agent into a reaction kettle to serve as a base solution; continuously introducing inert gas to ensure that the oxygen concentration of the whole reaction system in the reaction kettle is kept to be less than or equal to 200ppm, the time of introducing the inert gas is more than or equal to 6 hours, and the reaction temperature is controlled to be 40-60 ℃;
then, starting stirring, and adding a salt solution of nickel, cobalt and manganese, an alkali solution and ammonia water into the reaction kettle to start reaction;
adding the alkali solution to control the pH value of the reaction solution to be 11.0-12.0;
introducing the ammonia water in the reaction process to maintain the ammonia concentration in the reaction solution at 0.3-0.8 mol/L;
adding 1-4 mol/L bicarbonate solution every 40-120 min in the reaction process, wherein the adding amount of each time accounts for 0.1-1% of the volume ratio of the reaction solution in the reaction kettle, so as to prepare a porous inner core, the diameter of the inner core is 1-4 mu m, and the specific surface area is 10-30 m2/g；
Step two, stopping adding liquid and suspending reaction after reacting for 4-10 hours, adding a dispersing agent into the reaction kettle, wherein the adding amount accounts for 0.1-1% of the volume ratio of the reaction solution in the reaction kettle, and then aging for 1-2 hours;
after the aging is finished, adjusting the rotation speed of 50-100 rpm on the basis of the rotation speed of the first step, then continuously adding the salt solution of nickel, cobalt and manganese, the alkali solution and the ammonia water to continuously react, continuously adding the alkali solution to control the pH of the reaction solution to be 12.0-13.0, and continuously adding the ammonia water to enable the ammonia concentration in the reaction solution to be 0.3-1.0 mol/L, thereby preparing a loose flaky shell;
step four, aging, washing and drying the product obtained in the step three to obtain a nickel-cobalt-manganese hydroxide precursor with a porous core and a loose and flaky shell;
step five, mixing the precursor obtained in the step four with lithium salt according to a molar ratio of 1: (1.0-1.2), then enabling the oxygen content of a sintering system to be more than 90% in an oxygen-rich atmosphere, calcining at the high temperature of 600-1000 ℃ for 6-20 h to obtain a single crystal lithium nickel cobalt manganese oxide, and then performing coarse crushing, fine crushing and sieving to remove iron to obtain a finished product of the single crystal lithium nickel cobalt manganese oxide.
The relevant content in the above technical solution is explained as follows:
1. in the scheme, ammonia water is preferably selected as the complexing agent in the step one, so that the ammonia concentration of the base solution is controlled to be 0.05-1.0 mol/L.
2. In the scheme, the inert gas in the step one is used as a protective gas and comprises nitrogen or argon or helium, and the gas flow is controlled to be 2-6 m3/h。
3. In the above scheme, the bicarbonate in the bicarbonate solution in the first step is at least one of ammonia bicarbonate, potassium bicarbonate, sodium bicarbonate, calcium bicarbonate and magnesium bicarbonate.
4. In the scheme, the salt solution of nickel, cobalt and manganese in the first step and the third step is at least one of sulfate, nitrate and chloride of nickel, cobalt and manganese, and the concentration of the salt solution is 2-4 mol/L;
the concentration of the alkali solution in the first step and the third step is 20-50%, and the concentration of the ammonia water is 2-5 mol/L.
5. In the above scheme, the dispersant in the second step is at least one of polyethylene glycol, sodium pyrophosphate, potassium citrate and sodium silicate.
6. In the scheme, the total reaction time of the first step to the third step is 40-100 h.
7. In the scheme, the general formula of the nickel-cobalt-manganese hydroxide obtained in the fourth step is NiXCoYMnZ(OH)2Wherein X is more than or equal to 0.3 and less than or equal to 0.8, and X + Y + Z = 1.
8. In the scheme, the stirring speed in the first step is 150-300 rpm, and the stirring speed in the third step is 50-200 rpm.
9. In the foregoing scheme, the lithium salt in the fifth step is lithium carbonate, lithium nitrate, or lithium hydroxide.
The working principle and the advantages of the invention are as follows:
according to the invention, the precursor with the core-shell structure is used, the core is loose and porous, and the infiltration and storage of the electrolyte can be increased, so that the transmission of lithium ions is facilitated, the conduction of the lithium ions is improved, and the rate capability of the single crystal material is improved. Firstly, preparing a loose and porous inner core, adding bicarbonate solution to manufacture pores, stopping adding the bicarbonate after the inner core grows to a certain size, and reducing the rotating speed and increasing the pH value to form a loose flaky shell. The nickel-cobalt-manganese hydroxide prepared in the way has reduced anisotropy of crystal structure, is beneficial to radial diffusion of lithium ions, shortens the transmission distance of the lithium ions, and improves the capacity exertion and safety performance of the material. Meanwhile, a dispersing agent is added before the core-shell conversion, so that the surface charge of the material is changed, and the problem of agglomeration between shells in the rotation speed down regulation process is effectively solved.
Secondly, the specific surface area of the precursor particles prepared by the method is 10-30 m2The/g is close to that of the conventional secondary spherical particles, so the filling amount is unchanged after lithium mixing, and the productivity is higher.
And thirdly, the single crystal ternary cathode material is prepared by one-step sintering after lithium mixing, the production process is simple, and the production cost can be reduced.
Drawings
FIG. 1 is a SEM photograph of a cross section of Ni-Co-Mn hydroxide according to an embodiment of the present invention;
FIG. 2 is a 10000 times SEM photograph of Ni-Co-Mn hydroxide according to an embodiment of the invention;
FIG. 3 is a graph of particle size distribution of nickel cobalt manganese hydroxide according to an embodiment of the present invention;
FIG. 4 is a 10000 times SEM photograph of Li-Ni-Co-Mn oxide in accordance with an embodiment of the present invention;
FIG. 5 is a graph (0.1C/0.1C; 3.0-4.3V) showing the first charge and discharge of a button cell assembled by lithium nickel cobalt manganese oxide and a commercial signal single crystal NCM523 ternary cathode material according to an embodiment of the present invention.
Detailed Description
The invention is further described below with reference to the following examples:
example (b): referring to the attached drawings 1-5, a preparation method of a high-capacity single-crystal ternary positive electrode material is disclosed; the method sequentially comprises the following steps:
step one, reaction preparation, namely, adding the mixture into a reaction kettle (6 m)3) Adding pure water (1500L) and complexing agent as base solution; continuously introducing inert gas to ensure that the oxygen concentration of the whole reaction system in the reaction kettle is kept to be less than or equal to 200ppm, the time of introducing the inert gas is more than or equal to 6 hours, and the reaction temperature is controlled to be 40-60 ℃, preferably 50 ℃; the complexing agent is preferably ammonia water, so that the ammonia concentration of the base solution is controlled to be 0.05-1.0 mol/L. The inert gas is used as protective gas, nitrogen, argon, helium and the like can be selected, and the gas flow is controlled to be 2-6 m3/h。
Then, starting the reaction, starting stirring, and pumping the salt solution of nickel, cobalt and manganese, the alkali solution and the ammonia water into the reaction kettle through a metering pump.
Adding the alkali solution to control the pH of the reaction solution to be 11.0-12.0, preferably 11.5 +/-0.1; the first step is a nucleation stage, the pH is controlled to be 11.0-12.0 because the initial reaction stage is a crystal nucleus preparation process, if the pH is less than 11.0, the nickel, cobalt and manganese ions in the system are incompletely precipitated, the proportion of the nickel, cobalt and manganese ions in the prepared product deviates, and the ion distribution is not uniform; if the pH value is more than 12.0, the nucleation speed is too fast to be higher than the growth speed of crystals, so that micro powder is easy to appear in a system, and the prepared product has poor sphericity, poor compaction and other performance defects.
The alkali solution can be selected from soluble alkali solution such as sodium hydroxide and potassium hydroxide.
Introducing the ammonia water in the reaction process to maintain the ammonia concentration in the reaction solution at 0.3-0.8 mol/L, preferably 0.6 mol/L; ammonia water as a complexing agent reaches a balance relationship with the pH, and the ammonia concentration affects the primary morphology of the particles and the formation of loose flakes of the shell.
Adding bicarbonate solution with the concentration of 1-4 mol/L (preferably 2 mol/L) every 40-120 min (preferably 60 min) in the reaction process, wherein the adding amount of each time accounts for 0.1-1% of the volume ratio of the reaction solution in the reaction kettle, so as to prepare the porous inner core. The particle size is monitored in real time during the reaction process, the reaction is stopped when the particle size (diameter) of the core reaches 1-4 μm (preferably 3.5-4.0 μm), and the specific surface area is 10-30 m2(ii) in terms of/g. The bicarbonate in the bicarbonate solution is at least one of ammonia bicarbonate, potassium bicarbonate, sodium bicarbonate, calcium bicarbonate and magnesium bicarbonate.
Step two, calculating from the beginning of the reaction, stopping adding liquid (namely stopping adding the salt solution of nickel, cobalt and manganese, the alkali solution and the ammonia water) after reacting for 4-10 h, adding a dispersing agent (10 kg) into the reaction kettle, wherein the adding amount accounts for 0.1-1% of the volume ratio of the reaction solution in the reaction kettle, and then aging for 1-2 h; the dispersing agent is at least one of polyethylene glycol, sodium pyrophosphate, potassium citrate and sodium silicate. If no dispersing agent is added, the prepared inner core can be agglomerated together after the rotating speed is greatly reduced, and the subsequent loose slice shell is not beneficial to wrapping the inner core. The aging effect is to make the dispersant dissolved better and to make the non-stable particles in the system grow continuously to reach the stability of the system.
And step three, after the aging is finished, adjusting the rotation speed of 50-100 rpm on the basis of the rotation speed of the step one, then continuously adding the nickel-cobalt-manganese salt solution, the alkali solution and the ammonia water through a metering pump, continuously adding the alkali solution to control the pH value of the reaction solution to be 12.0-13.0, and continuously adding the ammonia water to enable the ammonia concentration in the reaction solution to be 0.3-1.0 mol/L, thereby preparing the loose flaky shell. And D (50) monitoring the material process in real time in the reaction process, and stopping the reaction when the reaction reaches 5.5-6.0 mu m.
The third step is a shell making stage, the pH is controlled to be 12.0-13.0 because the reaction enters a growth stage, if the pH is less than 12.0, the growth speed of crystals is greater than the nucleation speed of crystal nuclei, primary particles are more and more compact along with the reaction, and loose sheets cannot be formed, so that the pH needs to be controlled to be more than 12.0, the nucleation speed of the crystal nuclei is accelerated, and the particles are loose; if the pH is >13.0, a large number of crystal nuclei are formed, and a large amount of fine powder is generated to limit the crystal growth rate.
Step four, aging the product obtained in the step three for 2 hours, centrifugally washing until the material is neutral, and finally completely drying at 150 ℃ to obtain a nickel-cobalt-manganese hydroxide precursor with a porous inner core and a loose and flaky outer shell; the obtained nickel-cobalt-manganese hydroxide has the general formula of NiXCoYMnZ(OH)2Wherein X is more than or equal to 0.3 and less than or equal to 0.8, and X + Y + Z = 1. The aging time, the washing mode and requirement, and the drying temperature and time are standard practice in the industry, and can be known by those skilled in the art, and are not the invention point of the present invention, so that the detailed description is omitted.
The obtained nickel-cobalt-manganese ternary precursor particle sample is of a core-shell structure and has a chemical formula of Ni0.5Co0.2Mn0.3(OH)2. The core-shell structure is composed of a core and a shell, the molar ratio of nickel, cobalt and manganese of the core to the shell is consistent, the core is porous and loose, the diameter of the core is 1-4 mu m, and the specific surface area is 10-30 m2(ii)/g; the shell is in a loose flake shape, and the tap density of the particles is 1.64g/cm3The specific surface area is 15.56m2/g。
Step five, the Ni obtained in the step four0.5Co0.2Mn0.3(OH)2The molar ratio of the nickel-cobalt-manganese ternary precursor to the lithium salt is 1: (1.0-1.2), preferably 1: 1.05, then making the oxygen content of the sintering system be more than 90% under the oxygen-rich atmosphere, and calcining for 6-20 h (preferably 10 h) at the high temperature of 600-1000 ℃ (preferably 900 ℃) to obtain the single crystal lithium nickel cobalt manganese oxide (LiNi)0.5Co0.2Mn0.3O2Single crystal ternary cathode material), then obtaining a finished product of the single crystal lithium nickel cobalt manganese oxide after coarse crushing, fine crushing, sieving and iron removal. Wherein the lithium salt is lithium carbonate or lithium nitrate or lithium hydroxide. The modes and requirements of coarse crushing, fine crushing and sieving for removing iron are standard practice in the industry and can be mastered by the technical personnel in the field, and the modes and requirements are not the point of the invention, so the method does not need to be used for removing ironThe description is given.
Step four and step five are post-treatment steps.
Wherein the salt solution of nickel, cobalt and manganese in the first step and the third step is at least one of sulfate, nitrate and chloride of nickel, cobalt and manganese, and the concentration of the salt solution is 2-4 mol/L; the concentration of the alkali solution in the first step and the third step is 20-50%, and the concentration of the ammonia water is 2-5 mol/L. The molar ratio of metal nickel, cobalt and manganese in the nickel-cobalt-manganese salt solution is 5: 2: 3.
the total reaction time of the first to third steps is 40 to 100 hours, preferably 50 hours.
Wherein the stirring speed in the first step is 150-300 rpm, preferably 240 rpm; the stirring speed in the third step is 50-200 rpm, preferably 100 rpm.
Wherein the LiNi prepared in example0.5Co0.2Mn0.3O2The single crystal ternary positive electrode material and a commercially available NCM523 single crystal ternary material with the same model are mixed with a conductive agent and a bonding agent respectively according to a ratio of 8:1:1, a certain amount of bonding agent is added and uniformly mixed to prepare a positive electrode piece, a battery negative electrode adopts a lithium piece and then is assembled into a button battery to be subjected to an electrical performance test on a blue test cabinet, the discharge capacity under different multiplying powers is tested under the voltage of 3.0-4.3V, specific data are shown in Table 1, and it can be seen that the multiplying power performance of the embodiment under different multiplying powers is superior to that of the commercially available material with the same type. Meanwhile, as can be seen from fig. 5, the charge/discharge capacity of the battery assembled by the same type of materials sold in the market at 0.1C is 192.5/171.6mAh/g, and the first effect is 89.14%; the battery assembled by the preparation material of the embodiment has high initial discharge capacity, the 0.1C charge/discharge capacity is 194.9/174.3mAh/g under the voltage of 3.0-4.3V, the first effect is 89.43%, and the initial discharge capacity is improved by 2.7 mAh/g.
TABLE 1 comparison of the performance at rate of the examples with a commercially available NCM523 single crystal material of the same type
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (9)
1. A preparation method of a high-capacity single-crystal ternary cathode material; the method is characterized in that:
the method sequentially comprises the following steps:
step one, adding pure water and a complexing agent into a reaction kettle to serve as a base solution; continuously introducing nitrogen, argon or helium, keeping the oxygen concentration of the whole reaction system in the reaction kettle to be less than or equal to 200ppm, introducing the inert gas for more than or equal to 6 hours, and controlling the reaction temperature to be 40-60 ℃;
then, starting stirring, and adding a salt solution of nickel, cobalt and manganese, an alkali solution and ammonia water into the reaction kettle to start reaction;
adding the alkali solution to control the pH value of the reaction solution to be 11.0-12.0;
introducing the ammonia water in the reaction process to maintain the ammonia concentration in the reaction solution at 0.3-0.8 mol/L;
adding 1-4 mol/L bicarbonate solution every 40-120 min in the reaction process, wherein the adding amount of each time accounts for 0.1-1% of the volume ratio of the reaction solution in the reaction kettle, so as to prepare a porous inner core, the diameter of the inner core is 1-4 mu m, and the specific surface area is 10-30 m2/g；
Step two, stopping adding liquid and suspending reaction after reacting for 4-10 hours, adding a dispersing agent into the reaction kettle, wherein the adding amount accounts for 0.1-1% of the volume ratio of the reaction solution in the reaction kettle, and then aging for 1-2 hours;
after the aging is finished, adjusting the rotation speed of 50-100 rpm on the basis of the rotation speed of the first step, then continuously adding the salt solution of nickel, cobalt and manganese, the alkali solution and the ammonia water to continuously react, continuously adding the alkali solution to control the pH of the reaction solution to be 12.0-13.0, and continuously adding the ammonia water to enable the ammonia concentration in the reaction solution to be 0.3-1.0 mol/L, thereby preparing a loose flaky shell;
step four, aging, washing and drying the product obtained in the step three to obtain a nickel-cobalt-manganese hydroxide precursor with a porous core and a loose and flaky shell;
step five, mixing the precursor obtained in the step four with lithium carbonate or lithium nitrate or lithium hydroxide according to a molar ratio of 1: (1.0-1.2), then enabling the oxygen content of a sintering system to be more than 90% in an oxygen-rich atmosphere, calcining at the high temperature of 600-1000 ℃ for 6-20 h to obtain a single crystal lithium nickel cobalt manganese oxide, and then performing coarse crushing, fine crushing and sieving to remove iron to obtain a finished product of the single crystal lithium nickel cobalt manganese oxide.
2. The method of claim 1, wherein: and (3) the complexing agent in the first step is ammonia water, and the ammonia concentration of the base solution is controlled to be 0.05-1.0 mol/L.
3. The method of claim 1, wherein: controlling the gas flow of the nitrogen or argon or helium in the first step to be 2-6 m3/h。
4. The method of claim 1, wherein: the bicarbonate in the bicarbonate solution in the step one is at least one of ammonium bicarbonate, potassium bicarbonate, sodium bicarbonate, calcium bicarbonate and magnesium bicarbonate.
5. The method of claim 1, wherein: the salt solution of nickel, cobalt and manganese in the first step and the third step is at least one of sulfate, nitrate and chloride of nickel, cobalt and manganese, and the concentration of the salt solution is 2-4 mol/L;
the concentration of the alkali solution in the first step and the third step is 20-50%, and the concentration of the ammonia water is 2-5 mol/L.
6. The method of claim 1, wherein: and in the second step, the dispersing agent is at least one of polyethylene glycol, sodium pyrophosphate, potassium citrate and sodium silicate.
7. The method of claim 1, wherein: the total reaction time of the first step to the third step is 40-100 h.
8. The method of claim 1, wherein: the general formula of the nickel-cobalt-manganese hydroxide obtained in the fourth step is NiXCoYMnZ(OH)2Wherein X is more than or equal to 0.3 and less than or equal to 0.8, and X + Y + Z = 1.
9. The method of claim 1, wherein: the stirring speed in the first step is 150-300 rpm, and the stirring speed in the third step is 50-200 rpm.
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| CN110589903A (en) * | 2019-07-24 | 2019-12-20 | 南通金通储能动力新材料有限公司 | Large-particle nickel-cobalt-manganese hydroxide and preparation method thereof |
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| CN115710024A (en) * | 2022-10-24 | 2023-02-24 | 天津巴莫科技有限责任公司 | Core-shell structure precursor and preparation method and application thereof |
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