CN111646520A - Preparation and doping modification method of monocrystal nickel-cobalt lithium aluminate anode material - Google Patents
Preparation and doping modification method of monocrystal nickel-cobalt lithium aluminate anode material Download PDFInfo
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Abstract
A method for preparing a monocrystal nickel cobalt lithium aluminate anode material and doping modification comprises the following steps: (1) in N2In protective gas, carrying out constant-temperature coprecipitation reaction on a mixed solution of soluble nickel salt, cobalt salt, aluminum salt, sodium hydroxide and ammonia water in a reaction kettle, and carrying out aging, solid-liquid separation, filtration, washing and drying on the kettle liquid to obtain a nickel-cobalt lithium aluminate ternary precursor; (2) after presintering the precursor, adding a fluxing agent and a lithium source for primary calcination; (3) after the first-stage calcination, adding a fluorine source for second-stage calcination, and carrying out doping modification on the single crystal material; (4) after ball milling and crushing, washing and sintering are carried out, and finally the doped and modified monocrystal nickel cobalt lithium aluminate ternary positive electrode is obtainedA material.
Description
Technical Field
The invention relates to a lithium ion battery technology, in particular to a preparation technology of a monocrystal nickel cobalt lithium aluminate anode material.
Background
Lithium ion batteries have become a popular choice for mobile and wireless electronic devices, electric tools, hybrid power and electric vehicles (e.g., electric vehicles and electric hybrid vehicles) due to their advantages of long service life, small memory effect, high energy density, small self-discharge degree, environmental protection, and the like. In recent years, with the rise of the electric automobile industry, higher requirements are being placed on the energy density and cycle life of lithium ion batteries. Nickel cobalt lithium aluminate (NCA) cathode materials have been the focus of research because of their high specific energy, good specific power and good cycle life.
Currently, NCA batteries proposed by the combination of panasonic and tesla have been successfully applied to electric vehicles, but further improvements in safety and life are required. The single crystal NCA cathode material has good structural stability, thermal stability and higher compaction density, so that the safety performance and the service life of the NCA material can be effectively improved. In addition, the anion doping replaces oxygen in the material, so that the crystallinity of the material is better, and the stability of the material is further improved.
Chinese patent CN 110620234 a is a high potential lithium ion battery NCA ternary cathode material and its preparation method, which is used to overcome the disadvantage of poor electrochemical cycle performance of high nickel NCA and its derivatives of the lithium ion battery cathode material, especially the disadvantage of poor cycle performance under high cut-off voltage condition. However, the polycrystalline material prepared by the process is easy to generate in charge-discharge cycles compared with a single crystal materialCracks even break secondary particles, leading to severe side reactions of the material, fading of battery capacity, and easily bringing about safety problems. Journal of the Electrochemical Society 2019, 166 th stage 1956-1963, reported a two-step lithiation method for synthesizing single-crystal LiNi0.88Co0.09Al0.03O2The single crystal NCA is prepared only by a solid phase sintering method, and finally prepared materials are poor in dispersibility, low in single crystallization degree and poor in electrochemical performance and are difficult to industrialize.
Disclosure of Invention
The invention aims to improve the service life and the safety performance of an NCA positive electrode material and provides a method for preparing a monocrystal nickel-cobalt lithium aluminate positive electrode material and carrying out anion doping modification, wherein the method is simple in process.
The invention relates to a method for preparing a monocrystal nickel-cobalt lithium aluminate material and doping modification, and monocrystal LiNixCoyAl1-x-yFzO2-zPositive electrode material, formula (II) 0.7<x<0.9，0.1<y<0.2，0.05<z<0.15, comprising the following steps:
preparing sulfate solution from nickel and cobalt sulfate according to the stoichiometric ratio of Ni to Co = x: y, preparing sodium metaaluminate solution containing ammonia water according to the stoichiometric ratio of Co to Al = y:1-x-y, and taking 0.5 mol/L ammonia water solution as reaction kettle bottom liquid;
step (2) starting stirring to adjust the rotation speed of 300-2Under the atmosphere, injecting a sulfate solution and a sodium metaaluminate solution into a reaction kettle containing ammonia water as a base solution through a metering pump; meanwhile, adding 10mol/L NaOH solution into the reaction kettle, and controlling the pH =10-11.5 in the kettle; after the feed is finished, keeping N2Aging for 10-20h under the condition of atmosphere and stirring;
standing and layering the kettle liquid after the reaction in the step (3) to obtain NixCoyAl1-x-y(OH)2Precursor, wherein the precursor is filtered and washed by deionized water; drying the filter cake in a vacuum drying oven at 110 ℃ for 12 h;
step (4) NixCoyAl1-x-y(OH)2Putting the precursor into a tube furnace, pre-burning in an oxygen atmosphere, and keeping the temperature at 500-600 ℃ for 6-10 h;
pre-burning the sample obtained in the step (5) and LiOH & H2O (molar ratio of transition metal element to lithium element in precursor =1: 1.1-1.2) and fluxing agents KCl, NaCl and Li2SO4Ball milling one of the fluxing agents for 4 hours to uniformly mix the materials; after mixing, keeping the temperature of the mixture for 8 to 18 hours in a tube furnace at the temperature of 700-900 ℃ under the oxygen atmosphere; the mass ratio of the fluxing agent to the sample obtained by pre-burning is = 0.10-0.40;
calcining the sample obtained in the step (6) and LiF or NH4·HF2(the molar ratio of the transition metal element to the F element is 1: 0.05-0.15), performing secondary calcination in a tube furnace in an oxygen atmosphere, and performing heat preservation at 850-950 ℃ for 10-20h to perform doping modification on the single crystal material;
after the materials are cooled to room temperature in the step (7), the materials are ball-milled and washed by water to remove the fluxing agent and excessive LiOH & H2O; then, the temperature is kept for 3 to 6 hours in a tube furnace at the temperature of 400-600 ℃ in the oxygen atmosphere, and the water in the material is removed; and finally, carrying out ball milling and sieving to obtain the doped modified single crystal NCA ternary cathode material.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts the method of matching the fluxing agent with the two-stage calcination, can effectively reduce the calcination temperature, is beneficial to improving the single crystallization degree of the material, and successfully avoids the defects of serious side reaction and overhigh energy consumption caused by overhigh calcination temperature. In addition, anion doping is introduced in the calcining process, so that the structural stability of the material can be further improved, and the material has better safety performance and electrochemical performance.
Drawings
Fig. 1 is a process flow diagram of preparation and doping modification of a single crystal lithium nickel cobalt aluminate material of the present invention, and fig. 2 is an SEM image of a lithium nickel cobalt aluminate ternary precursor in example 1 of the present invention.
Detailed Description
The invention relates to a preparation and doping modification of a monocrystal nickel cobalt lithium aluminate materialMethod of (1), single crystal form LiNixCoyAl1-x-yFzO2-zPositive electrode material, formula (II) 0.7<x<0.9，0.1<y<0.2，0.05<z<0.15, comprising the following steps:
preparing sulfate solution from nickel and cobalt sulfate according to the stoichiometric ratio of Ni to Co = x: y, preparing sodium metaaluminate solution containing ammonia water according to the stoichiometric ratio of Co to Al = y:1-x-y, and taking 0.5 mol/L ammonia water solution as reaction kettle bottom liquid;
step (2) starting stirring to adjust the rotation speed of 300-2Under the atmosphere, injecting a sulfate solution and a sodium metaaluminate solution into a reaction kettle containing ammonia water as a base solution through a metering pump; meanwhile, adding 10mol/L NaOH solution into the reaction kettle, and controlling the pH =10-11.5 in the kettle; after the feed is finished, keeping N2Aging for 10-20h under the condition of atmosphere and stirring;
standing and layering the kettle liquid after the reaction in the step (3) to obtain NixCoyAl1-x-y(OH)2Precursor, wherein the precursor is filtered and washed by deionized water; drying the filter cake in a vacuum drying oven at 110 ℃ for 12 h;
step (4) NixCoyAl1-x-y(OH)2Putting the precursor into a tube furnace, pre-burning in an oxygen atmosphere, and keeping the temperature at 500-600 ℃ for 6-10 h;
pre-burning the sample obtained in the step (5) and LiOH & H2Ball milling the O and the fluxing agent for 4 hours to uniformly mix the materials; after mixing, carrying out primary calcination in a tubular furnace under an oxygen atmosphere;
mixing and ball-milling the sample obtained by calcining in the step (6) and a fluorine source, and then performing secondary calcining in a tube furnace in an oxygen atmosphere to perform doping modification on the single crystal material;
after the materials are cooled to room temperature in the step (7), the materials are ball-milled and washed by water to remove the fluxing agent and excessive LiOH & H2O; then, the temperature is kept for 3 to 6 hours in a tube furnace at the temperature of 400-600 ℃ in the oxygen atmosphere, and the water in the material is removed; finally, the doped and modified single crystal NCA ternary positive electrode is obtained by ball milling and sievingA material.
In the preparation and doping modification method of the single crystal nickel cobalt lithium aluminate anode material, sodium metaaluminate and ammonia water are selected as an aluminum source to prepare a mixed solution in the step (1); the nickel sulfate and the cobalt sulfate are configured into a sulfate solution.
The preparation and doping modification method of the single crystal nickel cobalt lithium aluminate anode material comprises the step (5) of pre-sintering transition metal elements and LiOH & H in the material2O mol ratio =1:1.1-1.2, fluxing agent is KCl, NaCl and Li2SO4Wherein the mass ratio of the fluxing agent to the pre-sintered material is =0.10-0.40, the first-stage calcining temperature is 700-900 ℃, and the heat preservation time is 8-18 h.
In the preparation and doping modification method of the single crystal nickel cobalt lithium aluminate anode material, in the step (6), the fluorine source is LiF and NH4·HF2The molar ratio of the transition metal element to the F element in the sample obtained by the first-stage calcination is =1:0.05-0.15, the second-stage calcination temperature is 850-.
For better preparation, in step (3), when the filtrate has pH =7 and BaCl is used2No SO in the filtrate is detected4 2-Stopping washing; in the steps (4) to (6), the selection of sintering conditions is also an important factor. The sintering temperature is too low, the time is too short, the solid phase mass transfer rate is slow, and a single crystal structure cannot be formed; the sintering temperature is too high, the time is too long, and the single crystal structure is easily damaged. It is necessary to preferably select proper sintering temperature and sintering time.
Example 1:
preparing 1L of sulfate solution with the total concentration of 1.9 mol/L by nickel sulfate and cobalt sulfate according to the stoichiometric ratio of Ni to Co =0.8:0.15, and preparing 1L of sodium metaaluminate according to the stoichiometric ratio of Co to Al =0.15:0.05 and containing 2mol NH3·H2O, 0.1 mol/L sodium metaaluminate solution and 0.5 mol/L ammonia water solution are taken as reaction kettle bottom liquid.
Setting the stirring speed at 500 rpm, and when the temperature of the reaction kettle reaches 50 ℃, carrying out reaction under N2Under the atmosphere, the sulfate solution and the sodium metaaluminate solution are metered according to the speed of 1 mL/minThe mixture was pumped into a 5L reactor. At the same time, 10mol/l naoh solution was added to the reaction kettle, and the pH in the kettle was controlled =11. After the feed is finished, keeping N2Aging for 14h under the condition of atmosphere and stirring.
Standing and layering the reaction kettle liquid to obtain a spherical nickel cobalt lithium aluminate ternary precursor, filtering and washing the precursor by using deionized water, and when the pH of the filtrate is =7 and BaCl is used for2No SO in the filtrate is detected4 2-The washing was stopped. The filter cake is placed in a vacuum drying oven and dried for 12 h at 110 ℃. The precursor having a particle size of about 5 μm was obtained as shown in FIG. 2.
And putting the precursor into a tube furnace, pre-sintering in an oxygen atmosphere, and keeping the temperature at 550 ℃ for 7 h.
Sample obtained by pre-sintering and LiOH & H2And mixing O (molar ratio of transition metal to lithium =1: 1.15) and a fluxing agent KCl (mass ratio of KCl to the sample obtained by pre-burning = 0.25), and then ball-milling for 4 hours to uniformly mix the materials. And preserving the temperature for 10 hours at 800 ℃ in a tube furnace under the oxygen atmosphere.
And mixing and ball-milling the calcined sample and LiF (the molar ratio of the transition metal element to the F element =1: 0.10), then performing secondary calcination in an oxygen atmosphere in a tube furnace, keeping the temperature at 900 ℃ for 12 h, and performing doping modification on the material.
Cooling to room temperature, ball milling, washing with water to remove flux and excessive LiOH & H2And O. Then, the temperature is kept for 4 hours at 500 ℃ in the oxygen atmosphere of the tube furnace, and the water in the material is removed. And finally, carrying out ball milling and sieving to obtain the doped modified single crystal NCA ternary cathode material.
Example 2:
preparing 1L of nickel sulfate and cobalt sulfate into 1.9 mol/L sulfate solution according to the stoichiometric ratio of Ni to Co =0.8:0.15, and preparing 1L of sodium metaaluminate into 2mol NH according to the stoichiometric ratio of Co to Al =0.15:0.053·H2O, 0.1 mol/L sodium metaaluminate solution and 0.5 mol/L ammonia water solution are taken as reaction kettle bottom liquid.
Setting the stirring speed at 400 rpm, and when the temperature of the reaction kettle reaches 50 ℃, carrying out reaction under N2Under the atmosphere, the sulfate solution and the sodium metaaluminate solution are mixedThe mixture was fed into a 5-liter reactor through a metering pump at a rate of 1 mL/min. At the same time, 10mol/l naoh solution was added to the reaction kettle, and the pH in the kettle was controlled = 11.5. After the feed is finished, keeping N2Aging for 16 h under the condition of atmosphere and stirring.
Standing and layering the reaction kettle liquid to obtain a spherical nickel cobalt lithium aluminate ternary precursor, filtering and washing the precursor by using deionized water, and when the pH of the filtrate is =7 and BaCl is used for2No SO in the filtrate is detected4 2-The washing was stopped. The filter cake is placed in a vacuum drying oven and dried for 12 h at 110 ℃.
And putting the precursor into a tube furnace, pre-sintering in an oxygen atmosphere, and keeping the temperature at 500 ℃ for 7 h.
Sample obtained by pre-sintering and LiOH & H2And mixing O (molar ratio of transition metal to lithium =1: 1.17) and a flux NaCl (mass ratio of NaCl to the sample obtained by pre-sintering = 0.30), and then ball-milling for 4 hours to uniformly mix the materials. The temperature is kept for 10 h at 850 ℃ in a tube furnace under the oxygen atmosphere.
And mixing and ball-milling the calcined sample and LiF (the molar ratio of the transition metal element to the F element =1: 0.15), then performing secondary calcination in an oxygen atmosphere in a tube furnace, keeping the temperature at 950 ℃ for 12 hours, and performing doping modification on the material.
Cooling to room temperature, ball milling, washing with water to remove flux and excessive LiOH & H2And O. Then, the temperature is kept for 4 hours at 450 ℃ in the oxygen atmosphere of the tube furnace, and the water in the material is removed. And finally, carrying out ball milling and sieving to obtain the doped modified single crystal NCA ternary cathode material.
Example 3:
preparing 1L of nickel sulfate and cobalt sulfate into 1.9 mol/L sulfate solution according to the stoichiometric ratio of Ni to Co =0.8:0.15, and preparing 1L of sodium metaaluminate into 2mol NH according to the stoichiometric ratio of Co to Al =0.15:0.053·H2O, 0.1 mol/L sodium metaaluminate solution and 0.5 mol/L ammonia water solution are taken as reaction kettle bottom liquid.
Setting the stirring speed at 500 rpm, and when the temperature of the reaction kettle reaches 55 ℃, carrying out reaction under N2Under the atmosphere, the sulfate solution and the sodium metaaluminate solution are added according to the speed of 1 mL/minThe metering pump is injected into a 5L reaction kettle. At the same time, 10mol/l naoh solution was added to the reaction kettle, and the pH in the kettle was controlled =11. After the feed is finished, keeping N2Aging for 18h under the condition of atmosphere and stirring.
Standing and layering the reaction kettle liquid to obtain a spherical nickel cobalt lithium aluminate ternary precursor, filtering and washing the precursor by using deionized water, and when the pH of the filtrate is =7 and BaCl is used for2No SO in the filtrate is detected4 2-The washing was stopped. The filter cake is placed in a vacuum drying oven and dried for 12 h at 110 ℃.
And putting the precursor into a tube furnace, pre-sintering in an oxygen atmosphere, and keeping the temperature at 600 ℃ for 7 h.
Sample obtained by pre-sintering and LiOH & H2O (transition metal to lithium element molar ratio =1: 1.19) and a flux Li2SO4（Li2SO4And mixing with the sample obtained by pre-sintering = 0.15), and then ball-milling for 4h to uniformly mix the materials. And keeping the temperature of the mixture in a tube furnace for 10 hours at 750 ℃ under an oxygen atmosphere.
Calcining the resulting sample with NH4·HF2(the molar ratio of the transition metal element to the F element is =1: 0.10), and then the mixture is subjected to secondary calcination in an oxygen atmosphere in a tube furnace, and the mixture is subjected to heat preservation at 850 ℃ for 12 hours to perform doping modification on the material.
Cooling to room temperature, ball milling, washing with water to remove flux and excessive LiOH & H2And O. Then, the temperature is preserved for 4 hours at 550 ℃ in the oxygen atmosphere of the tube furnace, and the water in the material is removed. And finally, carrying out ball milling and sieving to obtain the doped modified single crystal NCA ternary cathode material.
Example 4:
preparing 1L of nickel sulfate and cobalt sulfate into 1.9 mol/L sulfate solution according to the stoichiometric ratio of Ni to Co =0.8:0.15, and preparing 1L of sodium metaaluminate into 2mol NH according to the stoichiometric ratio of Co to Al =0.15:0.053·H2O, 0.1 mol/L sodium metaaluminate solution and 0.5 mol/L ammonia water solution are taken as reaction kettle bottom liquid.
Setting the stirring speed at 400 rpm, and when the temperature of the reaction kettle reaches 55 ℃, carrying out reaction under the condition of N2Sulfate salt under atmosphereThe solution and the sodium metaaluminate solution are injected into a 5L reaction kettle through a metering pump at the speed of 1 mL/min. At the same time, 10mol/l naoh solution was added to the reaction kettle, and the pH in the kettle was controlled = 11.5. After the feed is finished, keeping N2Aging for 20h under the condition of atmosphere and stirring.
Standing and layering the reaction kettle liquid to obtain a spherical nickel cobalt lithium aluminate ternary precursor, filtering and washing the precursor by using deionized water, and when the pH of the filtrate is =7 and BaCl is used for2No SO in the filtrate is detected4 2-The washing was stopped. The filter cake is placed in a vacuum drying oven and dried for 12 h at 110 ℃.
And putting the precursor into a tube furnace, pre-sintering in an oxygen atmosphere, and keeping the temperature at 550 ℃ for 9 hours.
Sample obtained by pre-sintering and LiOH & H2And mixing O (molar ratio of transition metal to lithium =1: 1.13) and a fluxing agent KCl (mass ratio of KCl to the sample obtained by pre-burning = 0.35), and then ball-milling for 4 hours to uniformly mix the materials. And keeping the temperature of the tube furnace at 800 ℃ for 15 h under the oxygen atmosphere.
Calcining the resulting sample with NH4·HF2(the molar ratio of the transition metal element to the F element is =1: 0.05), and then the mixture is subjected to secondary calcination in an oxygen atmosphere in a tube furnace, and the temperature is maintained at 900 ℃ for 17 hours to perform doping modification on the material.
Cooling to room temperature, ball milling, washing with water to remove flux and excessive LiOH & H2And O. Then, the temperature is kept for 6 hours at 500 ℃ in the oxygen atmosphere of the tube furnace, and the water in the material is removed. And finally, carrying out ball milling and sieving to obtain the doped modified single crystal NCA ternary cathode material.
In summary, the disclosure of the present invention is not limited to the above-mentioned embodiments, and any modifications and improvements based on the disclosure are within the scope of the present invention.
Claims (4)
1. A method for preparing monocrystal Ni-Co-Li aluminate material and doping modification is characterized in that monocrystal LiNixCoyAl1-x-yFzO2-zPositive electrode material, formula (II) 0.7<x<0.9，0.1<y<0.2，0.05<z<0.15, comprising the following steps:
preparing sulfate solution from nickel and cobalt sulfate according to the stoichiometric ratio of Ni to Co = x: y, preparing sodium metaaluminate solution containing ammonia water according to the stoichiometric ratio of Co to Al = y:1-x-y, and taking 0.5 mol/L ammonia water solution as reaction kettle bottom liquid;
step (2) starting stirring to adjust the rotation speed of 300-2Under the atmosphere, injecting a sulfate solution and a sodium metaaluminate solution into a reaction kettle containing ammonia water as a base solution through a metering pump; meanwhile, adding 10mol/L NaOH solution into the reaction kettle, and controlling the pH =10-11.5 in the kettle; after the feed is finished, keeping N2Aging for 10-20h under the condition of atmosphere and stirring;
standing and layering the kettle liquid after the reaction in the step (3) to obtain NixCoyAl1-x-y(OH)2Precursor, wherein the precursor is filtered and washed by deionized water; drying the filter cake in a vacuum drying oven at 110 ℃ for 12 h;
step (4) NixCoyAl1-x-y(OH)2Putting the precursor into a tube furnace, pre-burning in an oxygen atmosphere, and keeping the temperature at 500-600 ℃ for 6-10 h;
pre-burning the sample obtained in the step (5) and LiOH & H2Ball milling the O and the fluxing agent for 4 hours to uniformly mix the materials; after mixing, carrying out primary calcination in a tubular furnace under an oxygen atmosphere;
mixing and ball-milling the sample obtained by calcining in the step (6) and a fluorine source, and then performing secondary calcining in a tube furnace in an oxygen atmosphere to perform doping modification on the single crystal material;
after the materials are cooled to room temperature in the step (7), the materials are ball-milled and washed by water to remove the fluxing agent and excessive LiOH & H2O; then, the temperature is kept for 3 to 6 hours in a tube furnace at the temperature of 400-600 ℃ in the oxygen atmosphere, and the water in the material is removed; and finally, carrying out ball milling and sieving to obtain the doped modified single crystal NCA ternary cathode material.
2. The method for preparing and doping modification of the single crystal lithium nickel cobalt aluminate anode material according to claim 1, wherein in the step (1), the aluminum source is selected from sodium metaaluminate, sodium metaaluminate and ammonia water to prepare a mixed solution; the nickel sulfate and the cobalt sulfate are configured into a sulfate solution.
3. The method for preparing and doping modification of single crystal lithium nickel cobalt aluminate anode material according to claim 1, wherein transition metal element and LiOH H in the pre-sintered material in the step (5)2O mol ratio =1:1.1-1.2, fluxing agent is KCl, NaCl and Li2SO4Wherein the mass ratio of the fluxing agent to the pre-sintered material is =0.10-0.40, the first-stage calcining temperature is 700-900 ℃, and the heat preservation time is 8-18 h.
4. The method for preparing and doping modification of single crystal lithium nickel cobalt aluminate anode material according to claim 1, wherein the fluorine source in step (6) is LiF and NH4·HF2The molar ratio of the transition metal element to the F element in the sample obtained by the first-stage calcination is =1:0.05-0.15, the second-stage calcination temperature is 850-.
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Cited By (5)
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| CN114937773A (en) * | 2022-06-02 | 2022-08-23 | 桂林理工大学 | Synthetic method and application of highly monodisperse single crystal type high-nickel ternary positive electrode material |
| CN117525333A (en) * | 2023-11-16 | 2024-02-06 | 南开大学 | Titanium molten salt-assisted cladding doped monocrystal cobalt-free lithium nickel oxide positive electrode material, and preparation method and application thereof |
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| CN112652771A (en) * | 2020-12-22 | 2021-04-13 | 北京理工大学重庆创新中心 | Polyanion-doped single-crystal high-nickel positive electrode material and preparation method thereof |
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| CN114937773A (en) * | 2022-06-02 | 2022-08-23 | 桂林理工大学 | Synthetic method and application of highly monodisperse single crystal type high-nickel ternary positive electrode material |
| CN114937773B (en) * | 2022-06-02 | 2023-04-07 | 桂林理工大学 | Synthetic method and application of highly monodisperse single crystal type high-nickel ternary positive electrode material |
| CN117525333A (en) * | 2023-11-16 | 2024-02-06 | 南开大学 | Titanium molten salt-assisted cladding doped monocrystal cobalt-free lithium nickel oxide positive electrode material, and preparation method and application thereof |
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Application publication date: 20200911 |