CN109037669B - Modified nickel-cobalt lithium aluminate anode material and preparation method and application thereof - Google Patents
Modified nickel-cobalt lithium aluminate anode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a modified nickel cobalt lithium aluminate anode material and a preparation method and application thereof. The preparation method comprises the following steps: s1: preparing a nickel source and a cobalt source into a mixed solution 1; dissolving sodium metaaluminate in an ammonia solution to obtain a mixed solution 2; s2: mixing the mixed solution 1 and the mixed solution 2, then carrying out coprecipitation reaction, washing and drying to obtain a nickel cobalt aluminum hydroxide precursor; s3: adding the nickel cobalt aluminum hydroxide precursor obtained in the step S2 into a solution containing low-valence metal ions, grinding, drying and calcining to obtain a precursor oxide containing the low-valence metal ions; s4: and grinding the precursor oxide and a lithium source, and sintering at high temperature in an oxygen atmosphere to obtain the modified nickel cobalt lithium aluminate cathode material. The preparation method provided by the invention has simple process and easy post-treatment; the prepared modified nickel cobalt lithium aluminate cathode material has excellent electrochemical performance and cycling stability.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a modified nickel-cobalt lithium aluminate anode material and a preparation method and application thereof.
Background
The dual pressures of energy crisis and environmental pollution have led to a worldwide concern about advanced technologies such as smart grids and electric vehicles. These advanced technologies aim to efficiently store and sustainably utilize clean renewable energy sources such as solar, wind, and geothermal energy, etc. Therefore, the development of an energy storage device with excellent comprehensive performance becomes the key for solving the problems. Lithium ion batteries are widely used in the fields of electric vehicles, power grids, mobile electronic devices and the like due to good electrochemical performance, high working voltage and good safety performance, but with the technological progress and the popularization of electronic products, people have made higher requirements on lithium ion batteries.
Ternary positive electrode material (LiNi)1-x-yCoxMnyO2/LiNi1-x-yCoxAlyO2) In particular, high nickel material (x + y ≦ 0.4) is one of the most promising positive electrode materials at present. In the ternary cathode material, the specific discharge capacity is increased along with the increase of the content of nickel, but the cycling stability is also correspondingly reduced. With nickel-cobalt-aluminum (LiNi)1-x-yCoxAlyO2) The nickel content of the ternary positive electrode material is generally more than 80%, and the capacity of the ternary positive electrode material is also more than 180 mAh/g. However, because the solubility product constants of aluminum, nickel and cobalt in a hydroxide system are greatly different in the synthesis process of precursors of the aluminum-cobalt-nickel composite oxide, aluminum element cannot be co-precipitated with nickel and cobalt at the same time, and is preferentially precipitated to form irregular Al (OH)3Fine particles deteriorate the electrical properties of the material. On the other hand, due to Ni2+Is difficult to be completely oxidized into Ni in the high-temperature sintering process3+Resulting in a non-stoichiometric material, which has defects in the crystalline structure of the material. This is due to Ni2+Ions with Li+Similar ionic radii, Ni2+The lithium ion is easy to migrate to a lithium layer in the high-temperature sintering and electrochemical reaction processes, so that cation mixed arrangement is caused, the order degree of the crystal structure of the material is reduced, and the electrochemical performance of the material is finally deteriorated. In order to improve the electrochemical performance of the nickel-cobalt lithium aluminate anode material, modification means such as coating, doping, shell-core structure design and the like are adopted in a large quantity, but ideal effects are not obtained.
Disclosure of Invention
The invention aims to overcome the defect and defect of non-ideal modification effect of the nickel cobalt lithium aluminate anode material in the prior art, and provides a preparation method of the modified nickel cobalt lithium aluminate anode material. The preparation method provided by the invention has simple process and easy post-treatment; the prepared modified nickel cobalt lithium aluminate cathode material has excellent electrochemical performance and cycling stability.
The invention also aims to provide a modified nickel cobalt lithium aluminate cathode material.
The invention also aims to provide the application of the modified nickel cobalt lithium aluminate cathode material in a lithium ion battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a modified nickel cobalt lithium aluminate anode material comprises the following steps:
s1: preparing a nickel source and a cobalt source into a mixed solution 1; dissolving sodium metaaluminate in an ammonia solution to obtain a mixed solution 2;
s2: mixing the mixed solution 1 and the mixed solution 2, adjusting the pH value to 10.9-11.7 by using inorganic strong base, carrying out coprecipitation reaction, washing and drying to obtain a nickel cobalt aluminum hydroxide precursor; the molar ratio of nickel, cobalt and aluminum in the precursor is 80-90: 15-7: 5-3;
s3: adding the nickel cobalt aluminum hydroxide precursor obtained in the step S2 into a solution containing low-valence metal ions, grinding, drying, and calcining at 500-600 ℃ for 5-10 h to obtain a precursor oxide containing the low-valence metal ions; the molar ratio of the low-valence metal ions to the total metal content of nickel, cobalt and aluminum in the nickel-cobalt-aluminum hydroxide precursor is 1-5: 100;
s4: grinding the precursor oxide and a lithium source, and sintering at the high temperature of 720-800 ℃ for 12-20 h in an oxygen atmosphere to obtain a modified nickel-cobalt lithium aluminate cathode material; the molar ratio of lithium in the lithium source to the total metal content of nickel, cobalt and aluminum in the nickel-cobalt-aluminum hydroxide precursor is 1.02-1.10: 1.
Because aluminum ions are precipitated in preference to nickel and cobalt ions in the traditional process, a plurality of fine aluminum hydroxide particles appear in the precipitated product, and the rapid precipitation of the aluminum ions can also influence the growth of the crystal of the hydroxide precursor, so that the precursor product has small particle size and wide particle size distribution. Therefore, the method adopts sodium metaaluminate as an aluminum source, can simultaneously precipitate three elements of nickel, cobalt and aluminum under the condition that ammonia water is used as a complexing agent to obtain a precursor material with uniform particles, and the uniform spherical precursor material is beneficial to improving the stability of a final finished product material and is also convenient for subsequent processing treatment. In addition, due to the introduction of low-valence metal ions, part of divalent nickel ions in the material are converted into trivalent nickel ions, the ion mixing degree of the material is reduced, and the electrochemical performance of the material is improved. And the more stable low valence metal oxygen bond can stabilize the crystal structure of the material, thereby improving the cycling stability of the material.
The low-valence metal ions in the present invention refer to metals with valence states of one or two, such as divalent copper, divalent magnesium, etc.
The addition of low-valence metals and the addition sequence thereof are key factors influencing the performance of the modified nickel-cobalt lithium aluminate anode material.
When low-valence metal ions are added for doping during coprecipitation, because the solubility product constants of the related low-valence metal ions and nickel and cobalt in a hydroxide system are greatly different, the doped low-valence metal ions, nickel and cobalt ions cannot be simultaneously precipitated, but fine hydroxide precipitate particles are separately formed, and the electrochemical performance of a subsequent material is greatly influenced.
When low-valence metal ions are introduced into a finished product material, the secondary calcination influences the rearrangement of nickel, cobalt and aluminum elements in the main body material, so that an uncontrollable structural change is caused. Therefore, the secondary calcination temperature is generally lower (lower than the material synthesis temperature), and the calcination time is short, so that the low-valence metal ions cannot be completely diffused into the main body material, and the improvement effect is poor.
The doping strategy provided by the invention can ensure that the doped ions are uniformly diffused into the crystal lattice of the material to play a role of stabilizing the material, and the operation process is simple, saves energy consumption and is relatively economical.
The nickel-cobalt lithium aluminate anode material prepared by the preparation method has uniform particle size distribution, and a button cell assembled by the modified nickel-cobalt lithium aluminate anode material is subjected to charge and discharge tests at 0.1C (1C is 180mAh/g), and the first discharge specific capacity is more than 190 mAh/g; after the charge and discharge test is carried out at 1C and 175 times of cycles, the discharge specific capacity retention rate is about 86%, so that the nickel-cobalt lithium aluminate cathode material has excellent electrochemical performance and cycle stability.
Conventional nickel and cobalt sources may be used in the present invention.
Preferably, the nickel source in S1 is one or more of nickel sulfate, nickel nitrate and nickel acetate; the cobalt source is one or more of cobalt sulfate, cobalt nitrate or cobalt acetate.
Preferably, the sum of the metal concentrations of the nickel source and the cobalt source in the mixed solution 1 is 1-4 mol/L; the concentration of the ammonia water solution is 2-4 mol/L.
Preferably, the strong inorganic base in S2 is sodium hydroxide or potassium hydroxide.
Preferably, the concentration of the inorganic strong base in S2 is 2-8 mol/L.
Preferably, the pH is adjusted to 11.1 in S2.
Preferably, the molar ratio of nickel, cobalt and aluminium in the precursor in S2 is 80:15: 5.
Preferably, the mixed solution containing the low-valence metal ions in the S3 is one or more of magnesium acetate, copper acetate or zinc acetate solution.
During the subsequent sintering process of the acetate, the acetate ions are decomposed into gas to escape, and impurities cannot be introduced into the material.
Preferably, the solvent in the mixed solution containing the low-valence metal ions in S3 is ethanol or water.
Preferably, the molar ratio of the low-valent metal ion to the total metal content of nickel, cobalt and aluminum in the nickel, cobalt and aluminum hydroxide precursor in S3 is 2: 100.
Preferably, the calcination is carried out in S3 at 500 ℃ for 5 h.
Conventional lithium sources may be used in the present invention.
Preferably, the lithium source in S4 is one or more of lithium hydroxide monohydrate, lithium carbonate or lithium acetate.
Preferably, the sintering is carried out for 15h at 780 ℃ in S4.
Preferably, the molar ratio of lithium in the lithium source to the total amount of metals of nickel, cobalt and aluminum in the nickel, cobalt and aluminum hydroxide precursor in S4 is 1.06: 1.
The modified nickel-cobalt lithium aluminate cathode material is prepared by the preparation method.
The application of the modified nickel cobalt lithium aluminate cathode material in the lithium ion battery is also within the protection scope of the invention.
The button cell assembled by the modified nickel cobalt lithium aluminate anode material provided by the invention has the advantages that the capacity is basically kept unchanged at 0.2 ℃ after 20 times of circulation; after the charge and discharge test is carried out at 1C and 175 times of circulation, the discharge specific capacity retention rate is about 86%, so that the nickel-cobalt lithium aluminate anode material has excellent electrochemical performance.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method provided by the invention has simple process and easy post-treatment, and the three metal elements of nickel, cobalt and aluminum are simultaneously precipitated by adopting sodium metaaluminate as an aluminum source to obtain a precursor material with uniform particles; in addition, the performance of the prepared modified nickel cobalt lithium aluminate anode material is greatly improved by introducing low-valence metal ions; the modified nickel cobalt lithium aluminate cathode material provided by the invention has excellent electrochemical performance and cycling stability.
Drawings
FIG. 1 is a scanning electron micrograph of a nickel cobalt aluminum hydroxide precursor provided in example 1;
FIG. 2 is a transmission image of a scanning electron microscope of the Mg-doped Ni-Co lithium aluminate cathode material provided in example 1;
FIG. 3 is an XRD pattern of a magnesium doped lithium nickel cobalt aluminate cathode material provided in example 1;
FIG. 4 is a graph of rate capability of the Mg-doped Ni-Co lithium aluminate cathode material provided in example 1;
fig. 5 is a 0.2C cycle performance graph of the magnesium-doped lithium nickel cobalt aluminate cathode material provided in example 1.
Detailed Description
The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
Example 1
The embodiment provides a modified nickel cobalt lithium aluminate cathode material. Prepared by the following preparation method.
(1) Preparation of nickel hydroxide cobalt aluminum precursor
Firstly, nickel sulfate and cobalt sulfate are prepared into a 4mol/L solution (raw material 1) according to a molar ratio, and then sodium metaaluminate with a corresponding molar weight is dissolved in an ammonia water solution (raw material 2) so that the concentration of ammonia water is 4 mol/L. 8mol/L sodium hydroxide solution (feed 3) was used as a precipitant and to adjust the pH of the system. And finally, simultaneously adding the three raw materials into a reactor for coprecipitation reaction, wherein the rotating speed of a stirring paddle is 1000r/min, and adjusting the feeding speed of sodium hydroxide to enable the pH value of the system to be 11.1. And after the precipitation reaction is carried out for 12 hours, filtering, washing and drying the obtained precipitate to obtain the nickel-cobalt-aluminum hydroxide precursor. Nickel in the prepared precursor: cobalt: the molar ratio of aluminum was 80:15: 5.
(2) Modified doping of nickel cobalt aluminum hydroxide precursor
Adding the prepared nickel-cobalt-aluminum hydroxide precursor into a mixed solution containing magnesium acetate, fully grinding, evaporating ethanol in the mixture, and drying in an oven at 100 ℃ for 12 h. Then calcining the precursor oxide at 500 ℃ for 5 hours to obtain the precursor oxide containing magnesium ions. The molar ratio of the magnesium ions to the total amount of the precursor nickel-cobalt-aluminum metal is 2%. The amount of the ethanol is 10 times of the mass of the precursor.
(3) Preparation of modified nickel cobalt lithium aluminate anode material
And grinding the obtained precursor oxide containing the magnesium ions and lithium hydroxide monohydrate for 45min, and sintering at high temperature of 780 ℃ for 15h in an oxygen atmosphere to obtain the magnesium ion-doped nickel-cobalt lithium aluminate anode material. The ratio of the amount of lithium in the lithium hydroxide monohydrate to the total amount of nickel, cobalt and aluminum in the nickel cobalt aluminum hydroxide precursor was 1.06: 1.
Example 2
The embodiment provides a modified nickel cobalt lithium aluminate cathode material. Prepared by the following preparation method.
(1) Preparation of nickel hydroxide cobalt aluminum precursor
Firstly, nickel nitrate and cobalt nitrate are prepared into a 4mol/L solution (raw material 1) according to a molar ratio, and then sodium metaaluminate with a corresponding molar weight is dissolved in an ammonia water solution (raw material 2) so that the concentration of ammonia water is 4 mol/L. 8mol/L potassium hydroxide solution (feed 3) was used as a precipitant and to adjust the pH of the system. And finally, simultaneously adding the three raw materials into a reactor for coprecipitation reaction, wherein the rotating speed of a stirring paddle is 1000r/min, and adjusting the feeding speed of sodium hydroxide to enable the pH value of the system to be 11.1. And after the precipitation reaction is carried out for 12 hours, filtering, washing and drying the obtained precipitate to obtain the nickel-cobalt-aluminum hydroxide precursor. Nickel in the prepared precursor: cobalt: the molar ratio of aluminum was 80:15: 5.
(2) Modified doping of nickel cobalt aluminum hydroxide precursor
Adding the prepared nickel-cobalt-aluminum hydroxide precursor into a mixed solution containing copper acetate, fully grinding, evaporating ethanol in the mixture, and drying in an oven at 100 ℃ for 12 h. Then calcining the copper-containing precursor oxide at 500 ℃ for 5 hours to obtain the precursor oxide containing copper ions. The molar ratio of the copper ions to the total amount of the precursor nickel-cobalt-aluminum metal is 2%, and the amount of the ethanol is 10 times of the mass of the precursor.
(3) Preparation of modified nickel cobalt lithium aluminate anode material
And fully grinding the obtained precursor oxide containing the copper ions and lithium nitrate for 45min, and sintering at high temperature for 15h under the conditions of an oxygen atmosphere and 780 ℃ to obtain the nickel-cobalt lithium aluminate anode material doped with the copper ions. The ratio of the amount of lithium in the lithium nitrate to the total amount of nickel, cobalt and aluminum in the nickel-cobalt-aluminum hydroxide precursor was 1.06: 1.
Example 3
The embodiment provides a modified nickel cobalt lithium aluminate cathode material. Prepared by the following preparation method.
(1) Preparation of nickel hydroxide cobalt aluminum precursor
Firstly, nickel acetate and cobalt acetate are prepared into a 4mol/L solution (raw material 1) according to a molar ratio, and then sodium metaaluminate with a corresponding molar weight is dissolved in an ammonia water solution (raw material 2) so that the concentration of the ammonia water is 4 mol/L. 8mol/L sodium hydroxide solution (feed 3) was used as a precipitant and to adjust the pH of the system. And finally, simultaneously adding the three raw materials into a reactor for coprecipitation reaction, wherein the rotating speed of a stirring paddle is 1000r/min, and adjusting the feeding speed of sodium hydroxide to enable the pH value of the system to be 11.1. And after the precipitation reaction is carried out for 12 hours, filtering, washing and drying the obtained precipitate to obtain the nickel-cobalt-aluminum hydroxide precursor. Nickel in the prepared precursor: cobalt: the molar ratio of aluminum was 80:15: 5.
(2) Modified doping of nickel cobalt aluminum hydroxide precursor
Adding the prepared nickel-cobalt-aluminum hydroxide precursor into a mixed solution containing zinc acetate, fully grinding, evaporating ethanol in the mixture, and drying in an oven at 100 ℃ for 12 h. Then calcining the precursor oxide at 500 ℃ for 5 hours to obtain the precursor oxide containing zinc ions. The molar ratio of the zinc ions to the total amount of the nickel-cobalt-aluminum precursor metal is 2%. The amount of the ethanol is 10 times of the mass of the precursor.
(3) Preparation of modified nickel cobalt lithium aluminate anode material
And fully grinding the obtained precursor oxide containing the zinc ions and lithium acetate for 45min, and sintering at high temperature of 780 ℃ for 15h in an oxygen atmosphere to obtain the zinc ion doped nickel cobalt lithium aluminate anode material. The ratio of the amount of lithium in the lithium acetate to the total amount of nickel, cobalt and aluminum in the nickel-cobalt-aluminum hydroxide precursor was 1.06: 1.
Example 4
The embodiment provides a modified nickel cobalt lithium aluminate cathode material. Prepared by the following preparation method.
(1) Preparation of nickel hydroxide cobalt aluminum precursor
Firstly, nickel sulfate and cobalt sulfate are prepared into a 1mol/L solution (raw material 1) according to a molar ratio, and then sodium metaaluminate with a corresponding molar weight is dissolved in an ammonia water solution (raw material 2) so that the concentration of the ammonia water is 2 mol/L. 2mol/L sodium hydroxide solution (feed 3) was used as precipitant and to adjust the pH of the system. And finally, simultaneously adding the three raw materials into a reactor for coprecipitation reaction, wherein the rotating speed of a stirring paddle is 700r/min, and adjusting the feeding speed of sodium hydroxide to enable the pH value of the system to be 11.7. And after the precipitation reaction is carried out for 12 hours, filtering, washing and drying the obtained precipitate to obtain the nickel-cobalt-aluminum hydroxide precursor. Nickel in the prepared precursor: cobalt: the molar ratio of aluminum was 90:7: 3.
(2) Modified doping of nickel cobalt aluminum hydroxide precursor
Adding the prepared nickel-cobalt-aluminum hydroxide precursor into a mixed solution containing magnesium acetate, fully grinding, evaporating deionized water in the mixture, and drying for 12h at the temperature of 110 ℃ in an oven. Then calcining the precursor oxide at the temperature of 600 ℃ for 10 hours to obtain the precursor oxide containing magnesium ions. The molar ratio of the magnesium ions to the total amount of the precursor nickel-cobalt-aluminum metal is 1%. The content of the deionized water is 5 times of the mass of the precursor.
(3) Preparation of modified nickel cobalt lithium aluminate anode material
And fully grinding the obtained precursor oxide containing the magnesium ions and lithium hydroxide monohydrate for 60min, and sintering at high temperature of 720 ℃ for 12h in an oxygen atmosphere to obtain the magnesium ion-doped nickel-cobalt lithium aluminate cathode material. The ratio of the amount of lithium in the lithium hydroxide monohydrate to the total amount of nickel, cobalt and aluminum in the nickel cobalt aluminum hydroxide precursor is 1.02: 1.
Example 5
(1) Preparation of nickel hydroxide cobalt aluminum precursor
Firstly, nickel sulfate and cobalt sulfate are prepared into a 4mol/L solution (raw material 1) according to a molar ratio, and then sodium metaaluminate with a corresponding molar weight is dissolved in an ammonia water solution (raw material 2) so that the concentration of ammonia water is 4 mol/L. 8mol/L sodium hydroxide solution (feed 3) was used as a precipitant and to adjust the pH of the system. And finally, simultaneously adding the three raw materials into a reactor for coprecipitation reaction, wherein the rotating speed of a stirring paddle is 1200r/min, and adjusting the feeding speed of sodium hydroxide to enable the pH value of the system to be 10.9. And after the precipitation reaction is carried out for 12 hours, filtering, washing and drying the obtained precipitate to obtain the nickel-cobalt-aluminum hydroxide precursor. Nickel in the prepared precursor: cobalt: the molar ratio of aluminum was 80:15: 5.
(2) Modified doping of nickel cobalt aluminum hydroxide precursor
Adding the prepared nickel-cobalt-aluminum hydroxide precursor into a mixed solution containing magnesium acetate, fully grinding, evaporating deionized water in the mixture, and drying for 12h at the temperature of 110 ℃ in an oven. Then calcining the precursor oxide at 500 ℃ for 5 hours to obtain the precursor oxide containing magnesium ions. The molar ratio of the magnesium ions to the total amount of the precursor nickel-cobalt-aluminum metal is 5%. The content of the deionized water is 10 times of the mass of the precursor.
(3) Preparation of modified nickel cobalt lithium aluminate anode material
And fully grinding the obtained precursor oxide containing the magnesium ions and lithium hydroxide monohydrate for 30min, and sintering at the high temperature of 800 ℃ for 20h in an oxygen atmosphere to obtain the magnesium ion-doped nickel-cobalt lithium aluminate cathode material. The ratio of the amount of lithium in the lithium hydroxide monohydrate to the total amount of nickel, cobalt and aluminum in the nickel cobalt aluminum hydroxide precursor was 1.10: 1.
Physical characterization analysis
The morphology of the nickel cobalt aluminum hydroxide precursor prepared in example 1 was analyzed by a scanning electron microscope, and the test results are shown in fig. 1, from which it can be seen that the prepared nickel cobalt aluminum hydroxide precursor has a uniform particle size of about 10 μm. The shape analysis of the magnesium-doped lithium nickel cobalt aluminate cathode material prepared in example 1 is performed by using a scanning electron microscope, and the test result is shown in fig. 2, which shows that the prepared lithium nickel cobalt aluminate cathode material has primary particles of about 500nm and secondary particles of about 10 μm. XRD analysis of the lithium nickel cobalt aluminate cathode material prepared in example 1 is carried out by an X-ray instrument, and the test result is shown in figure 3, and as can be seen in the figure, diffraction peaks in the graph are sharp, so that the crystallinity of the material is good, and the clear peak splitting of (006)/(012) and (018)/(110) l indicates that the material has a well-ordered layered structure. The ratio of the (003) peak to the (104) peak can be used to characterize the degree of miscibility of the lithium nickel cation of the material, and a larger value indicates a smaller degree of miscibility, and it is generally considered that a value greater than 1.2 indicates an acceptable range of ion miscibility of the material. As can be seen from the figure, the ratio of the (003) peak to the (104) peak is about 1.7 and is far greater than 1.2, which proves that the obtained lithium nickel cobalt aluminate cathode material has smaller cation mixing degree and is supposed to have better electrochemical performance.
(II) analysis of electrochemical Properties
1. Battery preparation
(1) Preparing a battery positive plate: grinding and uniformly mixing the modified nickel-cobalt lithium aluminate positive electrode material, acetylene black and a polyvinylidene fluoride binder according to a mass ratio of 80:13:7, adding a proper amount of NMP (N-methyl pyrrolidone) as a solvent, fully stirring to obtain viscous slurry, uniformly coating the viscous slurry on the surface of an aluminum foil, drying the viscous slurry in a vacuum drying oven at 120 ℃ for 12 hours, and cooling to room temperature to obtain the nickel-cobalt lithium aluminate positive electrode sheet.
(2) Assembling the battery: and cutting the obtained battery positive plate into a wafer with the diameter of 14mm by using a slicer, accurately weighing the mass of the wafer, calculating the mass of an active substance in the positive plate according to the actual formula composition, and assembling the positive plate into a 2025 type testable button battery in a glove box (the oxygen content is less than 1.0ppm, and the water content is less than 0.1ppm) by using a diaphragm with the diameter of 19mm and a metal lithium plate with the diameter of 15 mm.
2. The electrochemical performance test method comprises the following steps:
and (3) carrying out charge and discharge tests on the assembled battery at various multiplying powers by using the Shenzhen Xinwei high-performance battery test system.
The magnesium-doped lithium nickel cobalt aluminate cathode material obtained in example 1 was assembled into a button 2025 battery by the above-mentioned half-cell assembly method, and then the battery was subjected to charge and discharge tests at various rates by using a shenzhen newway high performance battery test system. The average specific discharge capacities under various current density tests were 193(0.1C),188(0.2C),180(0.5C),173(1.0C),160(3.0C),153(5.0C),141mAh/g (10C), respectively, as shown in FIG. 4. At a magnification of 0.2C, the capacity remained substantially unchanged by 20 cycles, as shown in fig. 5. The capacity retention rate can reach 86% after 175 times of 1.0C circulation.
The nickel cobalt lithium aluminate cathode materials obtained in examples 1 to 5 were assembled into a button 2025 battery by the above-mentioned half-cell assembly method, and then the battery was subjected to charge and discharge tests at various rates by using the shenzhen newway high performance battery test system, with the test results shown in table 1.
Table 1 battery charge and discharge test results at 0.2C and 1.0C rates
From the analysis, the nickel cobalt lithium aluminate cathode material obtained by the preparation method has excellent electrochemical performance and cycling stability.
It will be appreciated by those of ordinary skill in the art that the examples provided herein are intended to assist the reader in understanding the principles of the invention and are to be construed as being without limitation to such specifically recited examples and embodiments. Those skilled in the art can make various other specific changes and combinations based on the teachings of the present invention without departing from the spirit of the invention, and these changes and combinations are within the scope of the invention.
Claims (9)
1. A preparation method of a modified nickel cobalt lithium aluminate anode material is characterized by comprising the following steps:
s1: preparing a nickel source and a cobalt source into a mixed solution 1; dissolving sodium metaaluminate in an ammonia solution to obtain a mixed solution 2;
s2: mixing the mixed solution 1 and the mixed solution 2, adjusting the pH value to 10.9-11.7 by using inorganic strong base, carrying out coprecipitation reaction, washing and drying to obtain a nickel cobalt aluminum hydroxide precursor; the molar ratio of nickel, cobalt and aluminum in the precursor is 80-90: 15-7: 5-3;
s3: adding the nickel cobalt aluminum hydroxide precursor obtained in the step S2 into a solution containing low-valence metal ions, grinding, drying, and calcining at 500-600 ℃ for 5-10 h to obtain a precursor oxide containing the low-valence metal ions; the molar ratio of the low-valence metal ions to the total metal content of nickel, cobalt and aluminum in the nickel-cobalt-aluminum hydroxide precursor is 1-5: 100; the mixed solution containing low-valence metal ions in the S3 is one or more of magnesium acetate, copper acetate or zinc acetate solution;
s4: grinding the precursor oxide and a lithium source, and sintering at the high temperature of 720-800 ℃ for 12-20 h in an oxygen atmosphere to obtain a modified nickel-cobalt lithium aluminate cathode material; the molar ratio of lithium in the lithium source to the total metal content of nickel, cobalt and aluminum in the nickel-cobalt-aluminum hydroxide precursor is 1.02-1.10: 1.
2. The preparation method of claim 1, wherein the nickel source in S1 is one or more of nickel sulfate, nickel nitrate or nickel acetate; the cobalt source is one or more of cobalt sulfate, cobalt nitrate or cobalt acetate.
3. The preparation method according to claim 1, wherein the sum of the metal concentrations of the nickel source and the cobalt source in the mixed solution 1 is 1 to 4 mol/L; the concentration of the ammonia water solution is 2-4 mol/L.
4. The method according to claim 1, wherein the molar ratio of nickel, cobalt and aluminum in the precursor in S2 is 80:15: 5.
5. The method of claim 1, wherein the molar ratio of the lower valent metal ion in S3 to the total amount of nickel, cobalt, and aluminum in the nickel cobalt aluminum hydroxide precursor is 2: 100.
6. The method according to claim 1, wherein the lithium source in S4 is one or more of lithium hydroxide monohydrate, lithium carbonate or lithium acetate.
7. The method of claim 1, wherein the molar ratio of lithium in the lithium source to the total amount of metals of nickel, cobalt, and aluminum in the nickel cobalt aluminum hydroxide precursor in S4 is 1.06: 1.
8. A modified nickel cobalt lithium aluminate cathode material is characterized by being prepared by the preparation method of any one of claims 1 to 7.
9. Use of the modified nickel cobalt lithium aluminate positive electrode material of claim 8 in a lithium ion battery.
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