CN111613788A - Hollow spherical lithium nickel manganese oxide positive electrode material and preparation method thereof - Google Patents
Hollow spherical lithium nickel manganese oxide positive electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of battery material preparation. The invention provides a preparation method of a hollow spherical lithium nickel manganese oxide positive electrode material. Reacting the mixed nickel source, manganese source and solvent with a carbonate solution to generate a precursor; and mixing the precursor suspension with oxalic acid, and sequentially drying, grinding and sintering to obtain the hollow spherical lithium nickel manganese oxide cathode material. The preparation method provided by the invention simplifies the synthesis process, improves the production efficiency, and has the advantages of simplicity, environmental protection, easiness in large-scale production and the like. The invention also provides the hollow spherical lithium nickel manganese oxide cathode material obtained by the preparation method. The lithium nickel manganese oxide material prepared by the invention is in a hollow spherical shape, contains nanometer spinel particles and micron-sized secondary particles consisting of the spinel particles, and has higher specific discharge capacity and good cycling stability.
Description
Technical Field
The invention relates to the technical field of battery material preparation, in particular to a hollow spherical lithium nickel manganese oxide positive electrode material and a preparation method thereof.
Background
With the increasingly exhaustion of traditional energy sources and the increasingly serious energy crisis and environmental problems, the development of a new energy source to replace the traditional fossil energy source has become an important challenge in social development. Ideal new energy sources such as wind energy, solar energy, tidal energy and the like seriously obstruct the application of the energy sources in real life due to severe requirements on climate and environment. Lithium ion secondary batteries are favored by researchers at home and abroad due to the advantages of no pollution, high energy density, no memory effect, long cycle life and the like, and are now an ideal power source for portable electronic products. But the defects of the anode material of the traditional lithium ion battery are too large, such as LiCoO2High price, toxicity, LiMn2O4Jahn-Teller effect and Mn of material in charging and discharging processes3+The problems of disproportionation reaction, poor cycle performance and the like seriously limit the wide application of the catalyst.
LiNi prepared by replacing part of Mn with Ni0.5Mn1.5O4(LNMO) material, which not only has the advantages of traditional cathode material, but also has high voltage (4.7V), high energy density (650Wh/kg), stable material structure, and can provide three-dimensional Li+The transmission channel and the better rate performance are considered to be one of the positive electrode materials with great future and attraction in the development of the lithium ion battery in the future. However, the LNMO materials still have some disadvantages, such as Mn formed during charging and discharging3+The collapse of material structure leads to poor chemical stability, and poor Li+And serious polarization phenomenon in the circulation process of the material caused by the electronic conductivity, short service life of the battery and the like limit the application of the LNMO material.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a hollow spherical lithium nickel manganese oxide positive electrode material and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a hollow spherical lithium nickel manganese oxide positive electrode material, which comprises the following steps:
(1) mixing a nickel source, a manganese source and a solvent to obtain a solution A;
(2) mixing the carbonate solution and the solution A to carry out double decomposition reaction to generate a precursor;
(3) mixing a precursor, a lithium source and a solvent to obtain a precursor suspension;
(4) and mixing the precursor suspension with an oxalic acid solution, and sequentially drying, grinding and sintering to obtain the hollow spherical lithium nickel manganese oxide cathode material.
Preferably, in the step (1), the molar ratio of the nickel element in the nickel source to the manganese element in the manganese source is 1: 2-4, wherein the dosage ratio of nickel element in the nickel source to the solvent is 1 mmol: (4-8) mL, wherein the solvent is an ethanol water solution.
Preferably, in the step (1), the nickel source is nickel sulfate, and the manganese source is manganese sulfate.
Preferably, in the step (2), the molar ratio of the carbonate to the sum of the moles of the nickel element in the nickel source and the moles of the manganese element in the manganese source is 4-6: 1; the concentration of the carbonate solution is 3.5-6.5 mmol/mL.
Preferably, the temperature of the double decomposition reaction in the step (2) is 25-40 ℃, and the time of the double decomposition reaction is 2-8 h.
Preferably, in the step (3), the molar ratio of the lithium element in the lithium source to the manganese element in the manganese source is 7: 8-12, the lithium source is lithium acetate, lithium carbonate or lithium hydroxide monohydrate, and the concentration of the lithium source in the precursor suspension is 0.3-0.33 mmol/mL.
Preferably, the molar ratio of oxalic acid to the molar sum of the nickel source, the manganese source and the lithium source in the oxalic acid solution in the step (4) is 1: 60-70, and the concentration of oxalic acid in the oxalic acid solution is 0.05-0.62 mmol/mL.
Preferably, the drying temperature in the step (4) is 70-90 ℃, and the drying time is 10-14 h.
Preferably, the sintering in the step (4) is a first-step sintering and a second-step sintering which are sequentially carried out, wherein the temperature of the first-step sintering is 300-600 ℃, and the time of the first-step sintering is 2-5 hours; the temperature of the second sintering step is 600-1000 ℃, and the time of the second sintering step is 8-15 h.
The invention also provides the hollow spherical lithium nickel manganese oxide cathode material obtained by the preparation method.
The invention provides a preparation method of a hollow spherical lithium nickel manganese oxide positive electrode material. Reacting the mixed nickel source, manganese source and solvent with a carbonate solution to generate a precursor; mixing a precursor, a lithium source and a solvent to obtain a precursor suspension; and mixing the precursor suspension with oxalic acid, and sequentially drying, grinding and sintering to obtain the hollow spherical lithium nickel manganese oxide cathode material. The preparation method provided by the invention omits a hydrothermal step of preparing the hollow spherical lithium nickel manganese oxide material by a traditional method in the synthesis process, simplifies the synthesis process, improves the production efficiency, and has the advantages of simplicity, environmental protection, easiness in large-scale production and the like.
The invention also provides the hollow spherical lithium nickel manganese oxide cathode material obtained by the preparation method. The lithium nickel manganese oxide material prepared by the invention is in a hollow spherical shape, contains nanometer spinel particles and micron-sized secondary particles consisting of the spinel particles, and has higher specific discharge capacity and good cycling stability.
Drawings
FIG. 1 is an XRD spectrum of a hollow spherical lithium nickel manganese oxide cathode material prepared in example 1;
FIG. 2 is a scanning electron micrograph of a hollow spherical lithium nickel manganese oxide cathode material prepared in example 1;
FIG. 3 is a graph showing the cycle performance at 5C of the battery assembled by using the hollow spherical lithium nickel manganese oxide prepared in example 1 as a positive electrode material.
Detailed Description
The invention provides a preparation method of a hollow spherical lithium nickel manganese oxide positive electrode material, which comprises the following steps:
(1) mixing a nickel source, a manganese source and a solvent to obtain a solution A;
(2) mixing the carbonate solution and the solution A to carry out double decomposition reaction to generate a precursor;
(3) mixing a precursor, a lithium source and a solvent to obtain a precursor suspension;
(4) and mixing the precursor suspension with an oxalic acid solution, and sequentially drying, grinding and sintering to obtain the hollow spherical lithium nickel manganese oxide cathode material.
In the present invention, in the step (1), the molar ratio of the nickel element in the nickel source to the manganese element in the manganese source is preferably 1: 2-4, and more preferably 1: 2.2 to 3.8, more preferably 1: 2.6 to 3.4. The dosage ratio of the nickel element in the nickel source to the solvent is preferably 1 mmol: (4-8) mL, more preferably 1 mmol: (5-7) mL, more preferably 1 mmol: (5.5-6.5) mL. The solvent is preferably an aqueous ethanol solution, and the volume fraction of ethanol in the aqueous ethanol solution is preferably not less than 40%, more preferably not less than 50%, and still more preferably not less than 60%.
In the present invention, the nickel source in the step (1) is preferably nickel sulfate, and the manganese source is preferably manganese sulfate.
In the invention, the mixing in the step (1) is preferably carried out under stirring conditions, and the stirring rotation speed is preferably 500-700 rpm, more preferably 540-660 rpm, and more preferably 580-620 rpm; the stirring time is preferably 30-90 min, more preferably 40-80 min, and even more preferably 50-70 rpm.
In the present invention, the ethanol aqueous solution used in step (1) can induce the transition metal ions to grow along a specific crystal plane, forming a three-dimensional channel.
In the invention, the mole ratio of the carbonate in the step (2) to the sum of the moles of the nickel element in the nickel source and the manganese element in the manganese source is preferably 4-6: 1, more preferably 4.2 to 5.8: 1, more preferably 4.6 to 5.4: 1; the concentration of the carbonate solution is preferably 3.5 to 6.5mmol/mL, more preferably 4.5 to 5.5mmol/mL, and still more preferably 4.8 to 5.2 mmol/mL.
In the invention, ammonium carbonate is preferably used as a solute in the carbonate solution in the step (2), carbonate is preferably dispersed in water in the carbonate solution, the dispersion mode is preferably stirring, and the rotation speed of the stirring is preferably 500-700 rpm, more preferably 540-660 rpm, and more preferably 580-620 rpm; the stirring time is preferably 10-30 min, more preferably 12-28 min, and even more preferably 18-22 min.
In the present invention, the mixing in the step (2) is preferably performed by dropping a carbonate solution into the solution a, the dropping rate is preferably 1 to 2 drops/sec, and the double decomposition reaction is performed at the beginning of the dropping.
In the invention, the temperature of the double decomposition reaction in the step (2) is preferably 25-40 ℃, more preferably 30-35 ℃, and more preferably 32-33 ℃; the time of the double decomposition reaction is preferably 2-8 h, more preferably 3-7 h, and even more preferably 4-6 h; the double decomposition reaction is carried out in a stirring state, and the stirring rotating speed is 200-800 rpm, more preferably 300-700 rpm, and even more preferably 400-600 rpm.
In the present invention, after the metathesis reaction in the step (2) is completed, the product system is preferably sequentially filtered, washed and dried; the filtration has no special requirements, and all precipitates can be obtained; the washing detergent is preferably an ethanol water solution, and the volume ratio of ethanol to water in the ethanol water solution is preferably 1: 1-2, more preferably 1: 1.2 to 1.8, more preferably 1: 1.4 to 1.6; the ratio of the amount of the precipitate to the amount of the detergent is preferably 1 g: (60-80) mL, more preferably 1 g: (62-78) mL, more preferably 1 g: (68-72) mL, wherein the washing frequency is preferably 2-6 times, and more preferably 3-5 times; the drying temperature is preferably 60-100 ℃, more preferably 70-90 ℃, and more preferably 75-85 ℃; the drying time is preferably 4-10 h, more preferably 5-9 h, and even more preferably 6-8 h. And filtering, washing and drying in sequence to obtain the precursor.
In the invention, the precursor in the step (2) is Ni0.25Mn0.75CO3The precursor is grass green.
In the present invention, in the step (3), the molar ratio of the lithium element in the lithium source to the manganese element in the manganese source is preferably 7: 8-12, more preferably 7: 9-11; the lithium source is preferably lithium acetate, lithium carbonate or lithium hydroxide monohydrate, and is more preferably lithium acetate; the concentration of the lithium source in the precursor suspension is preferably 0.3-0.33 mmol/mL, and more preferably 0.31-0.32 mmol/mL.
In the present invention, the solvent in the step (3) is preferably an ethanol aqueous solution, and the volume fraction of ethanol in the ethanol aqueous solution is preferably 50% or more, more preferably 60% or more, and more preferably 65% or more.
In the present invention, the molar ratio of oxalic acid to the sum of moles of the nickel source, the manganese source and the lithium source in the solution of oxalic acid in step (4) is preferably 1: 60-70, more preferably 1: 62-68, more preferably 1: 64 to 66; the concentration of oxalic acid in the oxalic acid solution is preferably 0.05-0.62 mmol/mL, more preferably 0.1-0.5 mmol/mL, and even more preferably 0.2-0.4 mmol/mL.
In the present invention, the mixing in the step (4) is preferably performed under stirring, the stirring is a first-step stirring and a second-step stirring performed sequentially, and the rotation speed of the first-step stirring is preferably 400 to 800rpm, more preferably 500 to 700rpm, and even more preferably 550 to 650 rpm; the first-step stirring time is preferably 20-40 min, and more preferably 25-35 min; the rotation speed of the second-step stirring is preferably 400-800 rpm, more preferably 500-700 rpm, and even more preferably 550-650 rpm; the second-step stirring time is preferably 60-120 min, more preferably 70-110 min, and even more preferably 80-100 min; the temperature of the second-step stirring is preferably 70-90 ℃, more preferably 72-88 ℃, and most preferably 76-84 ℃.
In the invention, the drying temperature in the step (4) is preferably 70-90 ℃, more preferably 72-88 ℃, and more preferably 78-82 ℃; the drying time is preferably 10-14 h, and more preferably 11-13 h.
In the invention, the grinding in the step (4) has no special requirement, and the grinding can be carried out to form uniform powder, and no obvious aggregation phenomenon is observed by naked eyes.
In the invention, the sintering in the step (4) is preferably a first-step sintering and a second-step sintering which are sequentially performed, wherein the temperature of the first-step sintering is preferably 300-600 ℃, more preferably 400-500 ℃, and more preferably 430-470 ℃; the first-step sintering time is preferably 2-5 h, more preferably 3-4 h, and even more preferably 3.4-3.6 h; the temperature of the second sintering step is preferably 600-1000 ℃, more preferably 700-900 ℃, and more preferably 730-770 ℃; the time of the second-step sintering is preferably 8-15 hours, more preferably 9-14 hours, and even more preferably 11-12 hours.
In the invention, the heating rate of the first-step sintering and the second-step sintering which are sequentially carried out is preferably 1-5 ℃/min, and more preferably 2-4 ℃/min. And after the second-step sintering is finished, preferably naturally cooling to room temperature.
In the invention, in the two-step sintering process, the carbonate reacts with oxalic acid to generate carbon dioxide gas to promote the generated lithium nickel manganese oxide material to be in a porous structure, and the hollow spherical lithium nickel manganese oxide positive electrode material is generated due to the Cokendall effect.
The invention also provides the hollow spherical lithium nickel manganese oxide cathode material obtained by the preparation method.
In the invention, the hollow spherical lithium nickel manganese oxide cathode material preferably consists of secondary particles, the secondary particles preferably consist of spinel particles, the spinel particles are preferably octahedral, and the size of the spinel particles is preferably 200-250 nm, more preferably 210-240 nm, and even more preferably 220-230 nm.
In the present invention, the size of the secondary particles is preferably 1 to 3 μm, more preferably 1.2 to 2.0 μm; the secondary particles are hollow spheres, and the inner diameter of each hollow sphere is preferably 400-1800 nm, more preferably 600-1600 nm, and even more preferably 1000-1200 nm; the wall thickness of the hollow sphere is preferably 250-350 nm, more preferably 270-330 nm, and even more preferably 290-310 nm.
In the invention, the hollow spherical lithium nickel manganese oxide positive electrode material is a spinel type with a disordered spatial structure, and the crystal cell parameter of the hollow spherical lithium nickel manganese oxide positive electrode material is
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Uniformly dispersing 90mmol of manganese sulfate and 30mmol of nickel sulfate in a mixed solution of 60mL of absolute ethyl alcohol and 120mL of deionized water, and stirring for 60min to obtain a solution A containing manganese sulfate and nickel;
uniformly dispersing 600mmol of ammonium carbonate in 200mL of deionized water, and stirring for 30min to obtain an ammonium carbonate solution; dropwise adding the ammonium carbonate solution into the solution A at a rate of 1 drop/second, and stirring at a rotating speed of 500rpm for 180min to obtain a product system;
filtering the product system, washing with ethanol water solution for 3 times, and drying at 60 deg.C for 5 hr to obtain grass green precursor Ni0.25Mn0.75CO3；
Dissolving 63mmol of lithium acetate and a precursor in a mixed solution of 100mL of deionized water and 100mL of ethanol to obtain a precursor suspension;
dissolving 2.8mmol of oxalic acid in 50mL of deionized water to obtain an oxalic acid solution;
adding an oxalic acid solution into the precursor suspension, stirring at the rotating speed of 600rpm for 30min, heating to 80 ℃, and continuously stirring at the same rotating speed for 90 min;
after being stirred uniformly, the mixture is placed in a forced air drying oven and dried for 12 hours at the temperature of 80 ℃; grinding the dried mixture uniformly;
heating the ground mixture to 400 ℃ at the speed of 3 ℃/min, and sintering for 4 h; and after the first-step sintering time is up, heating to 800 ℃ at a speed of 3 ℃/min, sintering for 10h, and naturally cooling to room temperature to obtain the hollow spherical lithium nickel manganese oxide material.
The X-ray diffraction analysis of the hollow spherical lithium nickel manganese oxide material prepared in the present example is performed, and the result is shown in fig. 1, the product prepared in the present example is spinel type crystal structure lithium nickel manganese oxide (JCPDS #80-2162), and weak impurity peaks appear at 37.5 °, 43.6 °, and 63.4 °, which indicates that the prepared lithium nickel manganese oxide material is of a disordered spatial structure.
The hollow spherical lithium nickel manganese oxide material prepared in the example is subjected to electron microscope scanning, and as a result, as shown in fig. 2, the material is in a hollow spherical structure and is 2 μm in size.
The hollow spherical lithium nickel manganese oxide material prepared in the embodiment is tested, the hollow spherical lithium nickel manganese oxide material is used as a positive electrode material to be assembled into a battery, and the cycle is performed at a rate of 5C, and the result is shown in fig. 3: the figure shows that the specific discharge capacity is 110.7mAh/g after 100 cycles, the capacity retention rate is close to 100 percent, and the synthesized hollow spherical lithium nickel manganese oxide has better electrochemical performance.
Example 2
Uniformly dispersing 90mmol of manganese sulfate and 30mmol of nickel sulfate in a mixed solution of 60mL of absolute ethyl alcohol and 120mL of deionized water, and stirring for 60min to obtain a solution A containing manganese sulfate and nickel;
uniformly dispersing 600mmol of ammonium carbonate in 200mL of deionized water, and stirring for 30min to obtain an ammonium carbonate solution; dropwise adding the ammonium carbonate solution into the solution A at a rate of 1 drop/second, and stirring at a rotating speed of 600rpm for 5 hours to obtain a product system;
filtering the product system, washing with ethanol water solution for 3 times, and drying at 60 deg.C for 4h to obtain grass green precursor Ni0.25Mn0.75CO3；
Dissolving 63mmol of lithium acetate and a precursor in a mixed solution of 100mL of deionized water and 100mL of ethanol to obtain a precursor suspension;
dissolving 2.8mmol of oxalic acid in 50mL of deionized water to obtain an oxalic acid solution;
adding an oxalic acid solution into the precursor suspension, stirring at the rotating speed of 600rpm for 30min, heating to 80 ℃, and continuously stirring at the same rotating speed for 80 min;
after being stirred uniformly, the mixture is placed in a blast drying oven and dried for 11 hours at the temperature of 75 ℃; grinding the dried mixture uniformly;
heating the ground mixture to 500 ℃ at the speed of 3 ℃/min, and sintering for 4 h; and after the first-step sintering time is up, heating to 900 ℃ at a speed of 3 ℃/min, sintering for 10h, and naturally cooling to room temperature to obtain the hollow spherical lithium nickel manganese oxide material.
The hollow spherical lithium nickel manganese oxide material prepared in the embodiment is tested, the hollow spherical lithium nickel manganese oxide material is used as a positive electrode material to be assembled into a battery, circulation is carried out under 5C multiplying power, the specific discharge capacity after 100 cycles is 112.4mAh/g, the capacity retention rate is 99.6%, and the battery has good circulation stability.
The embodiment shows that the hollow spherical lithium nickel manganese oxide material provided by the invention has nano-sized spinel particles and micron-sized secondary particles, under the condition of 5C, after 100 cycles, the specific discharge capacity retention rate is close to 100%, and the material has good cycle stability and excellent electrochemical performance, and is an excellent lithium ion battery cathode material.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The preparation method of the hollow spherical lithium nickel manganese oxide cathode material is characterized by comprising the following steps of:
(1) mixing a nickel source, a manganese source and a solvent to obtain a solution A;
(2) mixing the carbonate solution and the solution A to carry out double decomposition reaction to generate a precursor;
(3) mixing a precursor, a lithium source and a solvent to obtain a precursor suspension;
(4) and mixing the precursor suspension with an oxalic acid solution, and sequentially drying, grinding and sintering to obtain the hollow spherical lithium nickel manganese oxide cathode material.
2. The method according to claim 1, wherein the molar ratio of the nickel element in the nickel source to the manganese element in the manganese source in step (1) is 1: 2-4, wherein the dosage ratio of nickel element in the nickel source to the solvent is 1 mmol: (4-8) mL, wherein the solvent is an ethanol water solution.
3. The method according to claim 2, wherein the nickel source in step (1) is nickel sulfate and the manganese source is manganese sulfate.
4. The preparation method according to claim 1, wherein the molar ratio of the carbonate in the step (2) to the molar sum of the nickel element in the nickel source and the manganese element in the manganese source is 4-6: 1; the concentration of the carbonate solution is 3.5-6.5 mmol/mL.
5. The method according to any one of claims 1 to 4, wherein the temperature of the metathesis reaction in the step (2) is 25 to 40 ℃ and the time of the metathesis reaction is 2 to 8 hours.
6. The method according to claim 5, wherein the molar ratio of the lithium element in the lithium source to the manganese element in the manganese source in the step (3) is 7: 8-12, the lithium source is lithium acetate, lithium carbonate or lithium hydroxide monohydrate, and the concentration of the lithium source in the precursor suspension is 0.3-0.33 mmol/mL.
7. The method according to claim 1, wherein the molar ratio of oxalic acid to the sum of moles of the nickel source, the manganese source and the lithium source in the oxalic acid solution in step (4) is 1: 60-70, and the concentration of oxalic acid in the oxalic acid solution is 0.05-0.62 mmol/mL.
8. The method according to claim 1, 2, 3, 4, 6 or 7, wherein the drying temperature in the step (4) is 70 to 90 ℃ and the drying time is 10 to 14 hours.
9. The preparation method according to claim 8, wherein the sintering in the step (4) is a first-step sintering and a second-step sintering which are sequentially carried out, wherein the temperature of the first-step sintering is 300-600 ℃, and the time of the first-step sintering is 2-5 h; the temperature of the second sintering step is 600-1000 ℃, and the time of the second sintering step is 8-15 h.
10. The hollow spherical lithium nickel manganese oxide cathode material obtained by the preparation method of any one of claims 1 to 9.
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