CN110885100B - Preparation method of nickel lithium manganate cathode material with hierarchical structure - Google Patents
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Abstract
The invention relates to a lithium nickel manganese oxide cathode material with a hierarchical structure and a preparation method thereof, and relates to the field of lithium ion batteries. The lithium nickel manganese oxide with the hierarchical structure can be selectively synthesized by combining a hydrothermal method with program temperature-controlled calcination. The method comprises the following steps: firstly, dissolving a certain amount of nickel source and manganese source in a mixed solvent of deionized water and ethylene glycol, dissolving a certain amount of amine fluoride and a precipitator in the mixed solution, magnetically stirring until the amine fluoride and the precipitator are fully dissolved, and then transferring the mixed solution to a reaction kettle for hydrothermal reaction to obtain a precursor. And fully mixing the obtained precursor with a certain amount of lithium carbonate, and then calcining at high temperature to obtain the lithium nickel manganese oxide product. Experimental results show that the lithium nickel manganese oxide obtained by the method is a microsphere formed by secondary assembly of rice-shaped nano particles, the particle size is 5 mu m, and the discharge capacity of an obtained sample is 140mAh g after 200 cycles under the 2C multiplying power ‑1 The capacity retention ratio was 95.2%. The lithium nickel manganese oxide positive electrode material with the hierarchical structure prepared by the invention has high specific capacity and good cycling stability. The preparation method has the advantages of simple process, low cost and good reproducibility, and is suitable for large-scale production.
Description
Technical Field
The invention relates to the field of preparation of micro-nano assembled graded materials, in particular to a preparation method of a novel graded-structure lithium nickel manganese oxide positive electrode material.
Background
With the development of mobile electronic devices, electric vehicles and other high power devices, the need for high energy density, high voltage and high cycle stability Lithium Ion Batteries (LIBs) is urgent. Lithium nickel manganese oxide with high operating voltage
High theoretical capacity->
And environmental friendliness, have attracted attention and are considered to be the most promising cathode materials in the field of high voltage lithium ion batteries.
There are many methods for synthesizing lithium nickel manganese oxide positive electrode materials, such as a solid phase reaction method, a coprecipitation method, a sol-gel method, a molten salt method, a microwave-assisted method, and the like. Studies have shown that different synthetic methods have a large impact on the morphology and purity of the product, which may further affect the electrochemical performance of the cell. Compared with other traditional methods, it is worth emphasizing that the hydrothermal method is easy to selectively control morphology and particle size. Materials with micro-nano assembled hierarchical structures have gained more attention in various morphologies because they possess the advantages of nano and micro materials. On one hand, the nano material can shorten the diffusion path of lithium ions and further the specific capacity of the battery, and on the other hand, the micron-sized material can effectively reduce the edge effect and lead to higher tap density so as to improve the cycling stability of the battery, and has certain significance for increasing the energy density of the battery.
On the basis, a novel lithium nickel manganese oxide positive electrode material with a hierarchical structure is synthesized by a hydrothermal method by using a mixed solvent, and the structure and the electrochemical performance of the lithium nickel manganese oxide are researched. The result shows that the synthesized lithium nickel manganese oxide product has a stable structure, good cycling stability and high specific capacity.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for synthesizing a novel lithium nickel manganese oxide positive electrode material with a hierarchical structure. The reagent used in the method is relatively common, non-toxic and harmless, and the preparation method is simple and easy to realize; the lithium nickel manganese oxide prepared by the method has uniform size, can improve the cycling stability of the battery when being used as a battery material, and has better capacity.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of novel hierarchical structure lithium nickel manganese oxide comprises the following steps:
(1) Dissolving a nickel source and a manganese source in deionized water, uniformly stirring by magnetic force, and adding amine fluoride into the solution under the action of magnetic stirring. Adding glycol into the solution A, and adding a certain amount of precipitator into the solution after uniformly mixing the glycol and the solution by magnetic stirring. And transferring the solution B into a hydrothermal reaction kettle for hydrothermal reaction, naturally cooling the reaction kettle, collecting a product, washing the product with secondary water and ethanol, and drying to obtain a precursor.
(2) And fully mixing the precursor with a certain amount of lithium carbonate, and then calcining at high temperature to obtain the lithium nickel manganese oxide product.
On the basis of the technical scheme, the molar ratio of the nickel source to the manganese source in the step (1) is 1: 3, and the molar weight is 5 millimole and 15 millimole respectively. The molar amount of amine fluoride was 5 mmol, the volume of deionized water was 35 ml, and the magnetic stirring time was 20 minutes.
On the basis of the technical scheme, the adding amount of the ethylene glycol in the step (1) is 35 ml, and the adding amount of the precipitator is 25 mmol.
On the basis of the technical scheme, the temperature of the hydrothermal reaction in the step (1) is 140 ℃, the reaction time is 20 hours, and the heating rate is 5 ℃/min.
On the basis of the technical scheme, the amount of the lithium carbonate in the step (2) is 10.5 millimoles, the high-temperature calcination condition is that the lithium carbonate is calcined at 350 ℃ for 2 hours and then at 750 ℃ for 4 hours, and the heating rate is 5 ℃/min.
On the basis of the technical scheme, the selected nickel source is nickel nitrate hexahydrate.
On the basis of the technical scheme, the selected manganese source is manganese acetate tetrahydrate.
On the basis of the technical scheme, the selected precipitator is urea.
The lithium manganate prepared by the technical scheme is a microsphere formed by secondary assembly of rice-shaped nano particles, has the particle size of 5 mu m, and can keep better capacity after being charged and discharged for 200 times under the condition of the capacitance of 2C.
Compared with the prior art, the invention has the following advantages and positive effects:
1. the invention adopts a hydrothermal method to synthesize the novel nickel lithium manganate anode material with the hierarchical structure, and the product has better circulation stability and higher specific capacity.
2. The addition of the amine fluoride can slow down the precipitation speed of manganese ions and nickel ions, and is beneficial to the formation of a hierarchical structure in the hydrothermal process.
3. The urea is used as a precipitator, and can slowly release carbonate compared with other carbonate precipitants, so that the growth of a hierarchical structure in a hydrothermal process is facilitated.
4. According to the invention, the glycol and the water are used as solvents, the viscosity of the glycol is much higher than that of the ethanol and the water, and the proper addition of the glycol can increase the viscosity of the whole reaction system, reduce the precipitation speed of ions and be beneficial to the growth of a hierarchical structure in a hydrothermal process.
Drawings
FIG. 1 shows a simple flow chart of preparation of a hierarchical structure lithium nickel manganese oxide positive electrode material.
FIG. 2 shows an X-ray diffraction spectrum of the lithium nickel manganese oxide cathode material with the hierarchical structure.
FIGS. 3a and b show SEM images of the precursor of the lithium nickel manganese oxide cathode material with the hierarchical structure at different magnifications, FIGS. 3c and d show SEM images of the lithium nickel manganese oxide cathode material with the hierarchical structure at different magnifications, and FIGS. 3f, g and h show element distribution diagrams of Ni, mn and O of the lithium nickel manganese oxide cathode material in FIG. 3 e.
FIGS. 4a and b respectively show a charge-discharge test chart and a rate performance chart of the hierarchical structure lithium nickel manganese oxide cathode material.
Fig. 5 shows the specific discharge capacity and coulombic efficiency of the lithium nickel manganese oxide cathode material with the graded structure.
FIGS. 6a and b show cyclic voltammetry curves and alternating current impedance maps of the hierarchical lithium nickel manganese oxide cathode material, respectively.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. It is to be understood that the specific embodiments described herein are merely illustrative of and not restrictive on the broad application.
The implementation schematic diagram of the invention is shown in fig. 1, and the embodiment of the invention provides a novel hierarchical structure lithium nickel manganese oxide and a preparation method thereof, wherein the preparation method comprises the following steps:
s1, dissolving 4-6 mmol of nickel source and 12-18 mmol of manganese source in 30-40 ml of deionized water, uniformly stirring by magnetic force, and adding 4-6 mmol of amine fluoride into the solution under the action of magnetic stirring to obtain a solution A. Adding 30-40 ml of ethylene glycol into the solution A, and adding 20-30 mmol of precipitant into the solution after magnetic stirring and uniform mixing to obtain a solution B. And transferring the solution B into a hydrothermal reaction kettle for hydrothermal reaction at the temperature of 130-150 ℃ for 18-24 hours. And after the reaction kettle is naturally cooled, collecting a product, washing the product with secondary water and ethanol, and drying to obtain a precursor.
S2, mixing the obtained precursor with 8-12 mmol of lithium carbonate, pre-calcining for 2 hours at the temperature of 300-400 ℃ and calcining for 3-5 hours at the temperature of 700-800 ℃ to obtain the final product of the lithium nickel manganese oxide.
In the present example, the molar ratio of the nickel source to the manganese source was 1: 3, and the molar amounts were 5 and 15 millimoles, respectively. The molar amount of amine fluoride was 5 mmol, the volume of deionized water was 35 ml, and the magnetic stirring time was 20 minutes.
In the present example, the amount of precipitant added was 25 mmol.
In the embodiment of the invention, the temperature of the hydrothermal reaction is 140 ℃, the reaction time is 20 hours, and the heating rate is 2-6 ℃/min.
In the embodiment of the invention, the amount of lithium carbonate is 10.5 millimoles, the high-temperature calcination condition is that the lithium carbonate is calcined at 350 ℃ for 2 hours and then at 750 ℃ for 4 hours, and the temperature rise rate is 5 ℃/min.
In the embodiment of the invention, the nickel source is selected from nickel chloride, nickel nitrate, a hydrate of nickel chloride or a hydrate of nickel nitrate.
In the present example, the nickel source selected is nickel nitrate hexahydrate.
In the embodiment of the invention, the manganese source is selected from manganese chloride, manganese acetate, a hydrate of manganese chloride or a hydrate of manganese acetate.
In the present example, the manganese source selected was manganese acetate tetrahydrate.
In the embodiment of the invention, the precipitant is carbonate or organic matter containing carbonyl.
In the present example, the precipitating agent selected is urea.
The lithium nickel manganese oxide prepared by the method is characterized in that: the lithium nickel manganese oxide is a microsphere formed by secondary assembly of rice-shaped nano particles, the particle size of the microsphere is 5 mu m, and the lithium nickel manganese oxide can keep a good capacity after being charged and discharged for 200 times under the condition that the capacitance is 2C.
The novel hierarchical structure lithium nickel manganese oxide provided by the present invention, its preparation method and application 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:
(1) 5 mmol of nickel nitrate hexahydrate and 15 mmol of manganese acetate tetrahydrate are dissolved in 35 ml of deionized water and are stirred uniformly by magnetic force, and 5 mmol of amine fluoride is added into the solution under the action of magnetic stirring to obtain a solution A. Adding 35 ml of ethylene glycol into the solution A, and adding 25 mmol of precipitator urea into the solution after magnetic stirring and uniform mixing to obtain a solution B. And transferring the solution B into a hydrothermal reaction kettle for hydrothermal reaction at the temperature of 140 ℃ for 20 hours. And after the reaction kettle is naturally cooled, collecting a product, washing the product with secondary water and ethanol, and drying to obtain a precursor.
(2) And mixing the obtained precursor with 10.5 millimole of lithium carbonate, pre-calcining at 350 ℃ for 2 hours, and calcining at 750 ℃ for 4 hours to obtain a lithium nickel manganese oxide final product.
FIG. 1 is a simple flow chart for synthesizing hierarchical lithium nickel manganese oxide according to example 1 of the present invention.
FIG. 2 is an XRD spectrum of the hierarchical structure lithium nickel manganese oxide prepared in example 1 of the present invention. By comparing the X-ray spectrogram of the product with a standard card No.80-2162, the obtained product can be determined to be lithium nickel manganese oxide, and has less impurities and good crystallinity.
FIG. 3 is a scanning electron microscope image and an element distribution diagram of the hierarchical structure lithium nickel manganese oxide prepared in example 1 of the present invention. By SEM (3 a and b) of the precursor under different magnifications, the whole body can be observed to present a spherical shape with the diameter of about 5 microns, and the surface of the spherical shape is assembled by a plurality of nano sheets under magnification. FIGS. 3c and 3d show that the whole lithium nickel manganese oxide still maintains the spherical shape, and the spherical lithium nickel manganese oxide can be observed to be secondarily assembled by nano-meter-shaped particles through a large multiplying power. In FIG. 3f, g and h, the uniform distribution of the three elements of Ni, mn and O in the lithium nickel manganese oxide can be observed.
FIG. 4 is a charging and discharging performance diagram and a rate performance diagram of the hierarchical structure lithium nickel manganese oxide prepared in example 1 of the present invention. FIG. 4a shows the charge-discharge curve of lithium nickel manganese oxide, which shows that the discharge capacity of lithium nickel manganese oxide in the first circle is 147 mAh g at 2C rate -1 And after two hundred cycles, the discharge capacity is 141mAh g -1 From this, it can be seen that the product has better cycle stability and higher discharge capacity. FIG. 4b shows that the specific discharge capacity of the lithium nickel manganese oxide can reach 147, 141, 137, 128, 120, 114mAh g at the multiplying power of 0.1, 2, 5, 10, 15 and 20C -1 Therefore, the product has better rate capability and cycle stability.
Fig. 5 is a graph of specific discharge capacity and coulombic efficiency of the lithium nickel manganese oxide with the hierarchical structure prepared in example 1 of the present invention. It can be seen from the graph that there is a slight decay in discharge capacity with the cycling of the battery. The initial discharge capacity and the discharge capacity of the nickel lithium manganate for two hundred circles of circulation are 147 mAh g and 141mAh g respectively -1 From this, it was found that the capacity retention rate of lithium nickel manganese oxide was 95.2%. The initial coulombic efficiency of the lithium nickel manganese oxide is 81.8%, and the coulombic efficiency after the lithium nickel manganese oxide is cycled for 200 circles under the 2C multiplying power is 98.6%, so that the lithium nickel manganese oxide has higher discharge capacity and better cycling stability.
FIG. 6 is a graph showing cyclic voltammetry curves and impedance of lithium nickel manganese oxide having a hierarchical structure obtained in example 1 of the present invention. 6a is the cyclic voltammogram of the product at a sweep rate of 0.1mV/s, with the redox peaks corresponding one-to-one to the voltage plateaus in FIG. 4 a. FIG. 6b shows the initial impedance of the product, and it can be seen that the lithium nickel manganese oxide product synthesized by the method has smaller impedance and better lithium ion transmission efficiency.
Example 2
The procedure of example 1 was followed except that nickel nitrate hexahydrate in step one was replaced with nickel acetate tetrahydrate to likewise produce the graded micron-sphere morphology assembled from nano-meter shaped particles as shown in figure 3.
Example 3
The procedure of example 1 was followed except that manganese acetate tetrahydrate in step 1 was replaced with manganese chloride tetrahydrate to similarly obtain a graded micron-sphere morphology assembled from nano-meter shaped particles as shown in fig. 3.
Example 4
Following the procedure of example 1 except adjusting the amount of nickel nitrate hexahydrate and manganese acetate tetrahydrate to 6 millimoles and 18 millimoles respectively, the hierarchical microspherical morphology assembled from the nano-meter particles shown in fig. 3 was also obtained.
Example 5
The preparation procedure and experimental procedure of example 1 were followed except that the hydrothermal reaction time in step 1 was adjusted to 22 hours, and the graded micron-spherical morphology assembled from nano-meter-shaped particles as shown in fig. 3 was also obtained.
Example 6
The preparation steps and experimental procedures of example 1 were followed except that the temperature of the hydrothermal reaction in step 1 was adjusted to 130 ℃, and the graded micron-sphere morphology assembled from nano-meter-like particles as shown in fig. 3 was also obtained.
Example 7
The preparation procedure and experimental procedure of example 1 were followed except that the temperature rise rate during the calcination procedure in step 2 was adjusted to 6 degrees celsius per minute, and the graded micron-spherical morphology assembled from nano-meter-like particles was also obtained as shown in fig. 3.
The foregoing embodiments are merely illustrative of the principles and functions of this invention, and are not to be construed as limiting thereof. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Therefore, it is intended that all modifications and variations which may occur to those skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims be embraced thereby.
Claims (12)
1. A preparation method of a lithium nickel manganese oxide cathode material with a hierarchical structure is characterized by comprising the following steps:
(1) Preparation of solution a: dissolving 4-6 mmol of nickel source and 12-18 mmol of manganese source in 30-40 ml of deionized water, uniformly stirring by magnetic force, and adding 4-6 mmol of amine fluoride into the solution under the action of magnetic stirring;
(2) Preparation of solution B: adding 30-40 ml of glycol into the solution A, and adding 20-30 mmol of precipitator into the solution after uniformly mixing the mixture by magnetic stirring;
(3) Preparing a precursor: transferring the solution B into a hydrothermal reaction kettle for hydrothermal reaction at the temperature of 130-150 ℃ for 18-24 hours, collecting a product after the reaction kettle is naturally cooled, washing the product with secondary water and ethanol, and drying to obtain a precursor;
(4) Preparation of the final product: and (5) mixing the precursor obtained in the step (4) with 8-12 millimoles of lithium carbonate, and calcining at the high temperature of 700-800 ℃ for 3-5 hours to obtain a lithium nickel manganese oxide final product.
2. The method according to claim 1, wherein the molar ratio of the nickel source to the manganese source in step (1) is 1: 3, the molar amounts are 5 and 15 mmol, respectively, the molar amount of the amine fluoride is 5 mmol, the volume of the deionized water is 35 ml, and the magnetic stirring time is 20 minutes.
3. The method according to claim 1, wherein the ethylene glycol is added in an amount of 35 ml and the precipitant is added in an amount of 25 mmol in step (2).
4. The preparation method according to claim 1, wherein the hydrothermal reaction in the step (3) is carried out at a temperature of 140 degrees centigrade for 20 hours at a rate of 2-6 ℃/min.
5. The method according to claim 1, wherein the amount of the lithium carbonate in the step (4) is 10.5 mmol, the calcination at a high temperature is performed under the conditions of calcination at 350 ℃ for 2 hours and calcination at 750 ℃ for 4 hours, and the temperature increase rate is 5 ℃/min.
6. The method of claim 1, wherein: the nickel source is selected from nickel chloride, nickel nitrate, a hydrate of nickel chloride or a hydrate of nickel nitrate.
7. The method of claim 6, wherein: the nickel source selected was nickel nitrate hexahydrate.
8. The method of claim 1, wherein: the manganese source is selected from manganese chloride, manganese acetate, a hydrate of manganese chloride or a hydrate of manganese acetate.
9. The method of claim 8, wherein: the manganese source selected was manganese acetate tetrahydrate.
10. The method of claim 1, wherein: the precipitant is carbonate or organic matter containing carbonyl.
11. The method of claim 10, wherein: the precipitating agent selected is urea.
12. A lithium nickel manganese oxide produced by the method of any one of claims 1 to 11, wherein: the lithium nickel manganese oxide is a microsphere formed by secondary assembly of rice-shaped nano particles, the particle size of the microsphere is 5 mu m, and the lithium nickel manganese oxide can keep 95.4% of capacity after charging and discharging for 200 times under the condition that the capacitance is 2C.
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