CN114477312B - Method for preparing ternary positive electrode material precursor by layered doping - Google Patents
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Abstract
The invention discloses a method for preparing ternary positive electrode material precursors by layered doping, which comprises the steps of adding a metal salt solution, a precipitator solution, a complexing agent solution and a rubidium salt solution into a reaction kettle bottom solution, performing coprecipitation reaction, suspending feeding when the particle size in the reaction kettle grows to be smaller than the target particle size of 0.5-3 mu m, adding deionized water, and concentrating and displacing feed liquid containing rubidium ions in the reaction kettle; then continuing the coprecipitation reaction, adding molybdenum salt solution at the same time to perform the coprecipitation reaction until the average particle size of the particles grows to the target particle size, and stopping feeding to obtain a solution containing precursor materials; and (3) stirring the obtained solution containing the precursor material, aging, washing, drying, screening and removing iron to obtain the ternary positive electrode material precursor with the core-shell structure. The invention can prevent crack generation in the process of nucleation of the ternary positive electrode material precursor, and improve the conductivity and capacity retention rate of the lithium ion battery while improving the high-temperature cycle performance and the multiplying power of the ternary positive electrode material.
Description
Technical Field
The invention relates to a ternary positive electrode material precursor, in particular to a method for preparing the ternary positive electrode material precursor by layered doping.
Background
The nickel-cobalt-manganese ternary positive electrode material precursor is the most important raw material for preparing the positive electrode material of the lithium ion battery, and the ternary precursor is mainly prepared by simultaneously adding nickel-cobalt-manganese metal salt solution, liquid alkali and ammonia water into a reaction kettle for coprecipitation reaction, wherein microcracks usually occur in the nucleation process of the coprecipitation reaction due to the limitations of equipment and process conditions. In order to better exert the excellent performance of the ternary cathode material, the preparation of the precursor is important to the production of the ternary cathode material, because the quality (morphology, particle size distribution, specific surface area, impurity content, tap density and the like) of the precursor directly determines the physicochemical index of the final sintered product, the electrical performance of the ternary cathode material formed by sintering is general, the cycle performance and the specific capacity are poor, and in order to solve the defects, the preparation process of the ternary precursor adopts a method of doping other metal elements or coating the surface of the ternary precursor at present, and the doping or coating can improve the high-temperature cycle performance and the multiplying power of the ternary cathode material, but the conductivity and the capacity retention of the lithium ion battery prepared by the precursor are poor, so that the requirements cannot be met.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing a ternary positive electrode material precursor by layered doping, which can prevent crack generation in the nucleation process of the ternary positive electrode material precursor, improve the high-temperature cycle performance and the multiplying power of the ternary positive electrode material, and improve the conductivity and the capacity retention rate of the lithium ion battery.
The technical scheme adopted for solving the technical problems is as follows: a method for preparing a ternary positive electrode material precursor by layered doping comprises the following steps:
(1) Preparing a metal salt solution, a precipitator solution, a complexing agent solution, a rubidium salt solution and a molybdenum salt solution;
(2) Adding water, complexing agent solution and precipitant solution into a reaction kettle, stirring and keeping the temperature constant to prepare reaction kettle bottom solution;
(3) Adding a metal salt solution, a precipitator solution, a complexing agent solution and a rubidium salt solution into the bottom solution of the reaction kettle, performing coprecipitation reaction, suspending feeding when the particle size in the reaction kettle grows to be smaller than the target particle size of 0.5-3 mu m, adding deionized water, and concentrating and displacing feed liquid containing rubidium ions in the reaction kettle;
(4) Then continuously adding a metal salt solution, a precipitator solution and a complexing agent solution into the reaction kettle, simultaneously adding a molybdenum salt solution for coprecipitation reaction until the average particle size of particles grows to the target particle size, and stopping feeding to obtain a solution containing a precursor material;
(5) And (3) stirring the solution containing the precursor material obtained in the step (4) for ageing, washing, drying, screening and removing iron to obtain the ternary positive electrode material precursor with the core-shell structure.
Further, the metal salt solution is an aqueous solution containing nickel salt, cobalt salt and manganese salt, the molar ratio of the nickel salt to the cobalt salt to the manganese salt is 60-90:5-20:10-30, the total concentration of metal ions in the metal salt solution is 1-2 mol/L, and the nickel salt, the cobalt salt and the manganese salt are at least one of sulfate, nitrate and halogen salt.
Further, the precipitant solution is a sodium hydroxide solution with the concentration of 5-12 mol/L, the complexing agent solution is an ammonia water solution with the mass concentration of 12% -24%, the concentration of rubidium ions in the rubidium salt solution is 0.1-1 mol/L, and the concentration of molybdenum ions in the molybdenum salt solution is 0.1-1 mol/L.
Further, in the step (3) and the step (4), the reaction temperature is controlled to be 40-70 ℃, the pH value is controlled to be 11.5-13, the ammonia concentration is controlled to be 2-16 g/L, and the stirring rotating speed is controlled to be 300-600 rpm.
Further, the feeding amount of the metal salt solution is 20-500L/h, the feeding amount ratio of the rubidium salt solution to the metal salt solution is 1:200-10000, and the feeding amount ratio of the molybdenum salt solution to the metal salt solution is 1:200-10000.
Further, the average particle diameter of the particles in the step (3) is a particle size distribution D50 value, and the target particle diameter is 3-13 mu m.
Further, the molecular formula of the prepared ternary positive electrode material precursor is as follows: ni (Ni) x Co y Mn 1-x-y (OH) 2 [Rb] m [Mo] n M and n are doping amounts, wherein x is more than or equal to 0.50 and less than or equal to 0.90, y is more than or equal to 0.05 and less than or equal to 0.30, 1-x-y is more than or equal to 0.05 and less than or equal to 0.30, m is more than or equal to 0.0001 and less than or equal to 0.005, and n is more than or equal to 0.0001 and less than or equal to 0.005.
In the step (3), the feed liquid containing rubidium ions in the reaction kettle is replaced by concentration.
The ternary positive electrode material is prepared by the method for preparing the ternary positive electrode material precursor through layered doping.
A lithium ion battery comprising the ternary cathode material described above.
The beneficial effects of the invention are as follows: the method for preparing the ternary positive electrode material precursor by layered doping prevents crack generation in the nucleation process of the ternary positive electrode material precursor, improves the high-temperature cycle performance and multiplying power of the ternary positive electrode material, and improves the conductivity and capacity retention rate of the lithium ion battery, wherein the maximum capacity of the 1C multiplying power cycle 100 times is 192.5mah/g, and the maximum conductivity is 9.7 multiplied by 10 -3 The capacity retention rate is 92.68% at most after 100 cycles.
Detailed Description
The invention is further illustrated below with reference to examples.
Example 1:
adding pure water into a reaction kettle, heating to 60 ℃, then adjusting the pH of the prepared liquid-alkali solution to 12.0, adding ammonia water solution, preparing the base solution to 4.5g/L, and running stirring blades in the reaction kettle at a rotating speed of 260r/min to prepare the base solution for the coprecipitation reaction. Then, a nickel cobalt manganese solution (molar ratio of nickel to cobalt to manganese: 67:13:20) was added at a rate of 300L/h, a 32% aqueous alkali solution was added at a rate of 185L/h, a 21% aqueous ammonia solution was added at a rate of 30L/h, a rubidium salt solution was added at a rate of 100ml/min by using a peristaltic pump, ph was reduced to 11.60 at a rate of 0.05/h and maintained after the reaction, nitrogen gas having a purity of 99.99% was introduced at a rate of 3000L/h for 7 hours before the reaction, and compressed air was introduced at a rate of 500L/h for 8 hours. After 30 hours of coprecipitation reaction in the reaction kettle, the particle size D50 grows to 3 mu m, the feeding is stopped, deionized water is added, residual rubidium ions are replaced by concentrating the supernatant, the feeding is continued after waiting for 2 hours, the rubidium salt solution is changed into molybdenum salt solution, the flow is unchanged, the feeding is stopped when the particle D50 grows to 4 mu m, and the total reaction time is 75 hours. And washing impurities, filtering, dehydrating and drying the ternary positive electrode material precursor liquid to obtain the layered doped ternary positive electrode material precursor.
Example 2:
adding pure water into a reaction kettle, heating to 60 ℃, then adjusting the pH of the prepared liquid-alkali solution to 11.95, adding ammonia water solution, preparing the base solution to 5g/L, and running stirring blades in the reaction kettle at a rotating speed of 260r/min to prepare the base solution for the coprecipitation reaction. Then, 1.98mol/L of nickel cobalt manganese solution was added at a flow rate of 300L/h, 32% aqueous alkali solution was added at a flow rate of 185L/h, 21% aqueous ammonia solution was added at a flow rate of 30L/h, 0.5mol/L of rubidium salt solution was added at a flow rate of 200ml/min by using a peristaltic pump, ph was reduced to 11.60 at a rate of 0.05/h and maintained after the reaction, nitrogen gas having a purity of 99.99% was introduced at a flow rate of 3000L/h for 6 hours before the reaction, and compressed air was introduced at a flow rate of 500L/h for 7 hours. After a coprecipitation reaction for 27 hours in the reaction kettle, the particle size D50 grows to 3 mu m, feeding is stopped, deionized water is added, residual rubidium ions are replaced by concentrating, feeding is continued after waiting for 2 hours, feeding is continued after waiting for 3 hours, the rubidium salt solution is changed into molybdenum salt solution, the flow is unchanged, stopping the reaction when the particle size continues to grow to 3.6-3.7 mu m, and the total reaction time is 68 hours. And washing impurities, filtering, dehydrating and drying the ternary precursor slurry to obtain the layered doped ternary precursor.
Example 3:
adding pure water into a reaction kettle, heating to 60 ℃, regulating the pH value of the prepared aqueous alkali solution to 11.55, adding ammonia water solution, preparing the base solution to 6.5g/L, and running the stirring blades in the reaction kettle at the rotating speed of 260r/min to prepare the base solution for the coprecipitation reaction. Then, a nickel cobalt manganese solution of 1.98mol/L (ratio: 83:7:10) was added at a flow rate of 360L/h, a 32% aqueous alkali solution was added at a flow rate of 135L/h, a 21% aqueous ammonia solution was added at a flow rate of 25L/h, a rubidium salt solution of 0.5mol/L was added at a flow rate of 150ml/min by using a peristaltic pump, and after the reaction time was 2 hours, ph was reduced to 11.40 at a rate of 0.05/h and maintained, and 3000L/h of nitrogen gas with a purity of 99.99% was introduced throughout the reaction time. After 60 hours of coprecipitation reaction in the reaction kettle, stopping feeding when the D50 value of the particles grows to 8 mu m, adding deionized water, replacing residual rubidium ions by concentrating, continuing feeding after waiting for 2 hours, changing rubidium salt solution into 0.5mol/L molybdenum salt solution, keeping the flow unchanged, stopping feeding when the D50 value of the particles in the reaction kettle grows to 10 mu m, and keeping the total reaction time to be 80 hours. And washing impurities, filtering, dehydrating and drying the ternary precursor slurry to obtain the layered doped ternary precursor.
Comparative example 1: (not doped with rubidium molybdenum, otherwise the same as in example 1)
Adding pure water into a reaction kettle, heating to 60 ℃, then adjusting the pH of the prepared liquid-alkali solution to 12.0, adding ammonia water solution, preparing the base solution to 4.5g/L, and running stirring blades in the reaction kettle at a rotating speed of 260r/min to prepare the base solution for the coprecipitation reaction. Then, 1.98mol/L of nickel cobalt manganese solution was added at a flow rate of 300L/h, 32% of aqueous alkali solution was added at a flow rate of 185L/h, and 21% of aqueous ammonia solution was added at a flow rate of 30L/h, and during the reaction, ph was reduced to 11.60 at a rate of 0.05/h and maintained after the reaction, nitrogen gas having a purity of 99.99% was introduced at a flow rate of 3000L/h for 7 hours before the reaction, and compressed air was introduced at a flow rate of 500L/h for 8 hours. After 98h coprecipitation reaction in the reaction kettle, stopping when the granularity grows to 3.6 um. And washing impurities, filtering, dehydrating and drying the ternary precursor slurry to obtain the ternary precursor.
Comparative example 2: (otherwise, the same as in example 1, the concentration replacement was not performed)
Adding pure water into a reaction kettle, heating to 60 ℃, then adjusting the pH of the prepared liquid-alkali solution to 12.0, adding ammonia water solution, preparing the base solution to 4.5g/L, and running stirring blades in the reaction kettle at a rotating speed of 260r/min to prepare the base solution for the coprecipitation reaction. Then, 1.98mol/L of nickel cobalt manganese solution was added at a flow rate of 300L/h, 32% aqueous alkali solution was added at a flow rate of 185L/h, 21% aqueous ammonia solution was added at a flow rate of 30L/h, 0.5mol/L of rubidium salt solution was added at a flow rate of 100ml/min by using a peristaltic pump, ph was reduced to 11.60 at a rate of 0.05/h and maintained after the reaction, nitrogen gas having a purity of 99.99% was introduced at a flow rate of 3000L/h for 7 hours before the reaction, and compressed air was introduced at a flow rate of 500L/h for 8 hours. After 30 hours of coprecipitation reaction in the reaction kettle, the particle size D50 grows to 3 mu m, the rubidium salt solution is stopped, the molybdenum salt solution is introduced at the same flow, the feeding is stopped when the particle D50 value grows to 4 mu m, and the total reaction time is 75 hours. And washing impurities, filtering, dehydrating and drying the ternary positive electrode material precursor liquid to obtain the layered doped ternary positive electrode material precursor.
Comparative example 3: (otherwise the same as in example 1, rubidium was doped and molybdenum was not doped)
Adding pure water into a reaction kettle, heating to 60 ℃, then adjusting the pH of the prepared liquid-alkali solution to 12.0, adding ammonia water solution, preparing the base solution to 4.5g/L, and running stirring blades in the reaction kettle at a rotating speed of 260r/min to prepare the base solution for the coprecipitation reaction. Then, 1.98mol/L of nickel cobalt manganese solution was added at a flow rate of 300L/h, 32% aqueous alkali solution was added at a flow rate of 185L/h, 21% aqueous ammonia solution was added at a flow rate of 30L/h, 0.5mol/L of rubidium salt solution was added at a flow rate of 100ml/min by using a peristaltic pump, ph was reduced to 11.60 at a rate of 0.05/h and maintained after the reaction, nitrogen gas having a purity of 99.99% was introduced at a flow rate of 3000L/h for 7 hours before the reaction, and compressed air was introduced at a flow rate of 500L/h for 8 hours. The feed was stopped when the particle D50 had grown to 4. Mu.m, the total reaction time being 75h. And washing impurities, filtering, dehydrating and drying the ternary positive electrode material precursor liquid to obtain the layered doped ternary positive electrode material precursor.
Comparative example 4: other than doping with molybdenum and not doping with rubidium as in example 1)
Adding pure water into a reaction kettle, heating to 60 ℃, then adjusting the pH of the prepared liquid-alkali solution to 12.0, adding ammonia water solution, preparing the base solution to 4.5g/L, and running stirring blades in the reaction kettle at a rotating speed of 260r/min to prepare the base solution for the coprecipitation reaction. Then, a nickel cobalt manganese solution of 1.98mol/L was added at a flow rate of 300L/h, a 32% aqueous alkali solution of 185L/h, a 21% aqueous ammonia solution of 30L/h, a molybdenum salt solution of 0.5mol/L was added at a flow rate of 100ml/min by using a peristaltic pump, ph was reduced to 11.60 at a rate of 0.05/h and maintained after the reaction, nitrogen gas of 99.99% purity was introduced at a flow rate of 3000L/h for 7 hours before the reaction, and compressed air was introduced at a flow rate of 500L/h for 8 hours. The feed was stopped when the particle D50 had grown to 4. Mu.m, the total reaction time being 75h. And washing impurities, filtering, dehydrating and drying the ternary positive electrode material precursor liquid to obtain the layered doped ternary positive electrode material precursor.
The electrochemical performance detection method comprises the following steps:
1. uniformly mixing the precursors prepared in the examples and the comparative examples and lithium hydroxide according to the molar ratio of M (Ni+Co+Mn): M (Li) =1:1.03, presintering for 4 hours at 450 ℃, taking out, grinding, calcining for 20 hours at 750 ℃, taking out, grinding to finally obtain positive electrode materials, namely A1, A2, A3, D1, D2, D3 and D4;
2. the obtained positive electrode material is prepared according to the following steps: conductive carbon: polyvinylidene fluoride (PVDF) =90: 5:5, preparing slurry to prepare a positive electrode plate (the compacted density of the plate is 3.3g/cm < 2 >) and adopting a metal lithium plate as a negative electrode material to assemble the 2025 button cell;
3. at 1m LiPF6 EC: DEC: dmc=1: 1:1 (V%) is an electrolyte, and after three cycles of activation at a 0.2C magnification, the electrolyte is cycled 100 times at a 0.2C magnification, and the discharge capacity at the 1 st cycle and the discharge capacity at the 100 th cycle are measured, respectively, to calculate the 100-cycle capacity retention rate;
4. four wires are sequentially fixed on a glass slide by adopting conductive silver colloid, the positive electrode material of the lithium ion battery in a pasty state is uniformly coated on the glass slide, then vacuum drying is carried out, a film layer is obtained on the glass slide, an ammeter is adopted to measure current I, a voltmeter is adopted to measure voltage U, and then the conductivity sigma of the positive electrode material of the lithium ion battery is calculated according to a formula sigma=IL/US.
Table 1 electrochemical properties of the positive electrode materials obtained in examples and comparative examples
Claims (8)
1. The method for preparing the ternary cathode material precursor by layered doping is characterized by comprising the following steps of:
(1) Preparing a metal salt solution, a precipitator solution, a complexing agent solution, a rubidium salt solution and a molybdenum salt solution;
(2) Adding water, complexing agent solution and precipitant solution into a reaction kettle, stirring and keeping the temperature constant to prepare reaction kettle bottom solution;
(3) Adding a metal salt solution, a precipitator solution, a complexing agent solution and a rubidium salt solution into the bottom solution of the reaction kettle, performing coprecipitation reaction, suspending feeding when the particle size in the reaction kettle grows to be smaller than the target particle size of 0.5-3 mu m, adding deionized water, and concentrating and displacing feed liquid containing rubidium ions in the reaction kettle;
(4) Then continuously adding a metal salt solution, a precipitator solution and a complexing agent solution into the reaction kettle, simultaneously adding a molybdenum salt solution for coprecipitation reaction until the average particle size of particles grows to the target particle size, and stopping feeding to obtain a solution containing a precursor material;
(5) And (3) stirring the solution containing the precursor material obtained in the step (4) for ageing, washing, drying, screening and removing iron to obtain the ternary positive electrode material precursor with the core-shell structure.
2. The method for preparing a ternary cathode material precursor by layered doping according to claim 1, wherein the method comprises the following steps: the metal salt solution is an aqueous solution containing nickel salt, cobalt salt and manganese salt, the molar ratio of the nickel salt to the cobalt salt to the manganese salt is 60-90:5-20:10-30, the total concentration of metal ions in the metal salt solution is 1-2 mol/L, and the nickel salt, the cobalt salt and the manganese salt are at least one of sulfate, nitrate and halogen salt.
3. The method for preparing a ternary cathode material precursor by layered doping according to claim 1, wherein the method comprises the following steps: the precipitant solution is sodium hydroxide solution with the concentration of 5-12 mol/L, the complexing agent solution is ammonia water solution with the mass concentration of 12% -24%, the concentration of rubidium ions in the rubidium salt solution is 0.1-1 mol/L, and the concentration of molybdenum ions in the molybdenum salt solution is 0.1-1 mol/L.
4. The method for preparing a ternary cathode material precursor by layered doping according to claim 1, wherein the method comprises the following steps: in the step (3) and the step (4), the reaction temperature is controlled to be 40-70 ℃, the pH value is controlled to be 11.5-13, the ammonia concentration is controlled to be 2-16 g/L, and the stirring rotating speed is controlled to be 300-600 rpm.
5. The method for preparing a ternary cathode material precursor by layered doping according to claim 1, wherein the method comprises the following steps: the feeding amount of the metal salt solution is 20-500L/h, the feeding amount ratio of the rubidium salt solution to the metal salt solution is 1:200-10000, and the feeding amount ratio of the molybdenum salt solution to the metal salt solution is 1:200-10000.
6. The method for preparing a ternary cathode material precursor by layered doping according to claim 1, wherein the method comprises the following steps: the average particle diameter of the particles in the step (3) is the D50 value of the particle size distribution, and the target particle diameter is 3-13 mu m.
7. The method for preparing a ternary cathode material precursor by layered doping according to claim 1, wherein the method comprises the following steps: the molecular formula of the prepared ternary positive electrode material precursor is as follows: ni (Ni) x Co y Mn 1-x-y (OH) 2 [Rb] m [Mo] n M and n are doping amounts, wherein x is more than or equal to 0.50 and less than or equal to 0.90, y is more than or equal to 0.05 and less than or equal to 0.30, 1-x-y is more than or equal to 0.05 and less than or equal to 0.30, m is more than or equal to 0.0001 and less than or equal to 0.005, and n is more than or equal to 0.0001 and less than or equal to 0.005.
8. The method for preparing a ternary cathode material precursor by layered doping according to claim 1, wherein the method comprises the following steps: in the step (3), the feed liquid containing rubidium ions in the reaction kettle is replaced by concentration.
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