CN113937286A - Coating modified sodium ion battery positive electrode material, preparation method thereof and battery - Google Patents
Coating modified sodium ion battery positive electrode material, preparation method thereof and battery Download PDFInfo
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Abstract
The invention discloses a coating modified sodium ion battery anode material, a preparation method thereof and a battery; the positive electrode material includes: the composite oxide comprises a layered transition metal oxide and a manganese-rich shell structure oxide coated outside the layered transition metal oxide; the layered transition metal oxide has the general formula: na (Na)xCuyFezMnaM1‑y‑z‑ aO2(ii) a Wherein M is to a transition metal siteDoping substituted elements, including one or more of Li, Ni, Mg, Zn, Co, Al, Zr and Ti; x is more than 0.5 and less than or equal to 1, y is more than 0 and less than or equal to 0.5, z is more than 0 and less than or equal to 0.5, and a is more than 0 and less than or equal to 0.5; the values of x, y, z and a satisfy the charge balance of the chemical formula; the general structural formula of the manganese-rich shell structure oxide is as follows: na (Na)jMnO2；0＜j≤0.6。
Description
Technical Field
The invention relates to the technical field of sodium ion battery materials, in particular to a coating modified sodium ion battery positive electrode material, a preparation method thereof and a battery.
Background
Environmental pollution and energy shortage are common important problems faced by human beings, and the development of large-scale efficient clean energy storage technology can greatly reduce energy and environmental problems. The sodium ion battery becomes an ideal candidate in the field of large-scale energy storage by virtue of the advantages of abundant resources, low cost, high safety and the like, and although the working principle of the sodium ion battery is similar, the mature anode material of the lithium ion battery is not suitable for a sodium ion battery system due to the larger radius of the sodium ion. Therefore, it is important to develop a high-performance electrode material capable of storing sodium rapidly and stably. Among the currently known positive electrode materials for sodium ion batteries, the sodium layered metal oxide is one of the most promising positive electrode materials for sodium ion batteries at present due to its high theoretical specific capacity and easy synthesis. However, the instability of the layered structure during charge and discharge limits its practical applications. The surface coating of the material is one of effective means for improving the cycling stability of the electrode material, and the prior coating material for the positive electrode material of the sodium-ion battery is roughly of the following four types: respectively metal oxide, non-metal element coating, sodium/lithium fast ion conductor, organic matter/conductive polymer and the like.
Although the different types of sodium-ion battery positive electrode material coating materials have advantages respectively, the same has respective disadvantages:
the oxide used in the oxide coating is electrochemical inert, does not contribute to capacity in the charging and discharging process, and reduces the energy density of the battery;
the nonmetal element coating, mainly comprising C, N elements, cannot solve the problem of high residual alkali content on the surface of the sodium-electric layered anode material and influences the processing performance of the material;
the sodium/lithium fast ion conductor is coated, the method is complex, the process flow is more, the method is not suitable for large-scale production, and the used anions have larger molecular weight, so that the energy density of the battery can be reduced;
the organic matter/conductive polymer coating has high requirements on experimental conditions, the material is easy to rapidly agglomerate due to poor control of the polymerization speed of the organic polymer, and the compatibility of the organic polymer and the electrolyte can also influence the performance of the battery.
Disclosure of Invention
The invention aims to provide a coating modified sodium-ion battery positive electrode material, a preparation method thereof and a battery aiming at the defects of the prior art. The material has a compact manganese-rich shell structure protective layer on the surface, and can reduce the contact area of the internal layered transition metal oxide exposed in the electrolyte, thereby reducing the occurrence of interface side reaction and improving the material circulation stability.
In view of the above, in a first aspect, embodiments of the present invention provide a coating-modified sodium-ion battery positive electrode material, including: the composite oxide comprises a layered transition metal oxide and a manganese-rich shell structure oxide coated outside the layered transition metal oxide;
the layered transition metal oxide has the general formula: na (Na)xCuyFezMnaM1-y-z-aO2(ii) a Wherein M is an element for doping and substituting the transition metal site, and comprises one or more of Li, Ni, Mg, Zn, Co, Al, Zr and Ti; x is more than 0.5 and less than or equal to 1, y is more than 0 and less than or equal to 0.5, z is more than 0 and less than or equal to 0.5, and a is more than 0 and less than or equal to 0.5; the values of x, y, z, a satisfy the charge of the formulaBalancing;
the general structural formula of the manganese-rich shell structure oxide is as follows: na (Na)jMnO2；0＜j≤0.6。
Preferably, the manganese-rich shell structure oxide accounts for 1-10% of the layered transition metal oxide in mass ratio.
In a second aspect, an embodiment of the present invention provides a preparation method of the coating-modified sodium ion battery positive electrode material described in the first aspect, where the preparation method is a solvothermal method, and specifically includes:
dissolving a manganese source in an alcohol solvent, and magnetically stirring;
adding a certain amount of layered transition metal oxide, continuously heating and stirring at a certain temperature to evaporate ethanol due to heating, and taking out the obtained material powder after the ethanol is completely evaporated;
and sintering the taken material powder in a muffle furnace to obtain the coating modified sodium-ion battery anode material.
Preferably, the manganese source specifically comprises one or more of manganese element-containing compounds such as manganese acetate, manganese oxalate, manganese chloride and the like;
the alcohol solvent specifically includes: one or more of alcohol solvents such as ethanol, methanol, isopropanol and the like;
the layered transition metal oxide has the general formula: na (Na)xCuyFezMnaM1-y-z-aO2(ii) a Wherein M is an element for doping and substituting the transition metal site, and comprises one or more of Li, Ni, Mg, Zn, Co, Al, Zr and Ti; x is more than 0.5 and less than or equal to 1, y is more than 0 and less than or equal to 0.5, z is more than 0 and less than or equal to 0.5, and a is more than 0 and less than or equal to 0.5; the values of x, y, z and a satisfy the charge balance of the chemical formula.
Preferably, the stirring time of the magnetic stirring is 10min-60 min;
the stirring time of the heating and stirring is 6-10 hours, and the heating temperature is 80-100 ℃.
Preferably, the sintering temperature of the sintering is 800-1000 ℃; the sintering time is 2-4 hours.
In a third aspect, an embodiment of the present invention provides a sodium-ion battery positive electrode, including the coating modified sodium-ion battery positive electrode material described in the first aspect.
In a fourth aspect, an embodiment of the present invention provides a sodium ion battery, including the positive electrode of the sodium ion battery in the third aspect.
The coating modified sodium ion battery anode material provided by the invention adopts a solvothermal method to dissolve a manganese source in ethanol, and utilizes a sodium source provided by residual alkali on the surface of a layered transition metal oxide to generate Na on the surface of the material in situjMnO2The material forms a compact manganese-rich shell structure protective layer on the surface of the material, and reduces the contact area exposed in the electrolyte, thereby reducing the occurrence of interface side reaction, improving the material circulation stability, simultaneously playing a role in reducing residual alkali on the surface of the material, improving the processability of the material, and reducing the requirements of the material on storage and use environments. And, NajMnO2Has electrochemical activity, and can play a role in stable circulation without reducing the energy density of the material as an electrode material.
Drawings
The technical solutions of the embodiments of the present invention are further described in detail with reference to the accompanying drawings and embodiments.
Fig. 1 is a Scanning Electron Microscope (SEM) image of a coating-modified sodium ion battery positive electrode material provided in example 2 of the present invention;
FIG. 2 is a Transmission Electron Microscope (TEM) image of the coating modified positive electrode material of the sodium-ion battery provided in example 2 of the present invention;
FIG. 3 is an SEM image of a positive electrode material of a sodium-ion battery provided in comparative example 1 of the present invention;
fig. 4 is a graph comparing X-ray diffraction tests of the positive electrode materials of sodium ion batteries prepared in examples 1, 2 and 3 of the present invention and comparative example 1.
Detailed Description
The embodiment of the invention provides a coating modified sodium ion battery positive electrode material, which comprises the following components: layered transition metal oxide and manganese-rich shell structure oxide coated outside the layered transition metal oxide. Laminated ceramic tileThe transition metal oxide has the general formula: na (Na)xCuyFezMnaM1-y-z-aO2(ii) a Wherein M is an element for doping and substituting the transition metal site, and comprises one or more of Li, Ni, Mg, Zn, Co, Al, Zr and Ti; x is more than 0.5 and less than or equal to 1, y is more than 0 and less than or equal to 0.5, z is more than 0 and less than or equal to 0.5, and a is more than 0 and less than or equal to 0.5; the values of x, y, z and a satisfy the charge balance of the chemical formula; the general structural formula of the manganese-rich shell structure oxide is as follows: na (Na)jMnO2(ii) a J is more than 0 and less than or equal to 0.6. In the anode material, the manganese-rich shell structure oxide accounts for 1-10% of the layered transition metal oxide in mass ratio.
The cathode material can be prepared by a solvothermal method. Firstly, dissolving a manganese source in an alcohol solvent, and magnetically stirring; then, adding a certain amount of layered transition metal oxide, continuously heating and stirring at a certain temperature to evaporate ethanol due to heating, and taking out the obtained material powder after the ethanol is completely evaporated; and finally, putting the taken material powder into a muffle furnace for sintering to obtain the coated and modified sodium-ion battery anode material.
In the method, the manganese source specifically comprises one or more of manganese-containing compounds such as manganese acetate, manganese oxalate, manganese chloride and the like; the alcohol solvent specifically includes: one or more of alcohol solvents such as ethanol, methanol, isopropanol and the like; the stirring time of magnetic stirring is 10min-60 min; the stirring time of heating and stirring is 6-10 hours, and the heating temperature is 80-100 ℃. The sintering temperature of the sintering is 800-1000 ℃; the sintering time is 2-4 hours.
The manganese source is dissolved in the ethanol by adopting a solvothermal method, and Na source provided by the residual alkali on the surface of the layered transition metal oxide can be used for generating Na on the surface of the material in situjMnO2The material forms a compact manganese-rich shell structure protective layer on the surface of the material, and reduces the contact area exposed in the electrolyte, thereby reducing the occurrence of interface side reaction, improving the material circulation stability, simultaneously playing a role in reducing residual alkali on the surface of the material, improving the processability of the material, and reducing the requirements of the material on storage and use environments. The coating modified sodium ion battery anode prepared by the inventionThe material is used for the positive electrode of the sodium-ion battery. Na (Na)jMnO2Has electrochemical activity, and can play a role in stable circulation without reducing the energy density of the material as an electrode material.
The positive electrode material of the present invention, and the preparation method and properties thereof are further described in detail by some specific examples below.
Example 1
Weighing 0.178g of manganese acetate, dissolving in 10ml of ethanol, and magnetically stirring for 30 minutes; then 10g of layered transition metal oxide positive electrode material Na was added0.9Cu0.22Fe0.3Mn0.48Continuously placing the mixture on a magnetic stirrer, stirring at a constant speed of 600rpm, keeping the stirring at 80 ℃ to evaporate the ethanol, heating and stirring for 8 hours, and taking out the material powder after the ethanol is completely evaporated; and sintering the taken material powder in a muffle furnace at 900 ℃ for 3 hours to obtain the coating modified sodium ion battery anode material. Wherein the manganese-rich shell structure oxide Na0.44MnO2The content of the layered transition metal oxide is 1% by mass.
Example 2
Weighing 0.534g of manganese acetate, dissolving in 10ml of ethanol, and magnetically stirring for 30 minutes; then 10g of layered transition metal oxide positive electrode material Na was added0.9Cu0.22Fe0.3Mn0.48Continuously placing the mixture on a magnetic stirrer, stirring at a constant speed of 600rpm, keeping the stirring at 80 ℃ to evaporate the ethanol, heating and stirring for 8 hours, and taking out the material powder after the ethanol is completely evaporated; and sintering the taken material powder in a muffle furnace at 900 ℃ for 3 hours to obtain the coating modified sodium ion battery anode material. Wherein the manganese-rich shell structure oxide Na0.44MnO2The content of the layered transition metal oxide is 3% by mass. The positive electrode material obtained in example 2 was subjected to a Scanning Electron Microscope (SEM) test, and the results are shown in fig. 1. The resulting material was uniformly coated as seen by SEM. FIG. 2 is a transmission electron microscope image of the coated and modified positive electrode material of the Na-ion battery of this embodiment, and it can be seen that the surface of the layered transition metal oxide positive electrode material has a manganese-rich shell junction as shown by the dotted line in the imageAnd forming an oxide coating layer.
Example 3
Weighing 1.781g of manganese acetate, dissolving in 10ml of ethanol, and magnetically stirring for 30 minutes; then 10g of layered transition metal oxide positive electrode material Na was added0.9Cu0.22Fe0.3Mn0.48Continuously placing the mixture on a magnetic stirrer, stirring at a constant speed of 600rpm, keeping the stirring at 80 ℃ to evaporate the ethanol, heating and stirring for 8 hours, and taking out the material powder after the ethanol is completely evaporated; and sintering the taken material powder in a muffle furnace at 900 ℃ for 3 hours to obtain the coating modified sodium ion battery anode material. Wherein the manganese-rich shell structure oxide Na0.44MnO2The content of the layered transition metal oxide is 10% by mass.
Example 4
Weighing 0.147g of manganese oxalate, dissolving in 10ml of ethanol, and magnetically stirring for 30 minutes; then 10g of layered transition metal oxide positive electrode material Na was added0.9Cu0.22Fe0.3Mn0.48Continuously placing the mixture on a magnetic stirrer, stirring at a constant speed of 600rpm, keeping the stirring at 80 ℃ to evaporate the ethanol, heating and stirring for 8 hours, and taking out the material powder after the ethanol is completely evaporated; and sintering the taken material powder in a muffle furnace at 900 ℃ for 3 hours to obtain the coating modified sodium ion battery anode material. Wherein the manganese-rich shell structure oxide Na0.44MnO2The content of the layered transition metal oxide is 1% by mass.
Example 5
Weighing 0.442g of manganese oxalate, dissolving in 10ml of ethanol, and magnetically stirring for 30 minutes; then 10g of layered transition metal oxide positive electrode material Na was added0.9Cu0.22Fe0.3Mn0.48Continuously placing the mixture on a magnetic stirrer, stirring at a constant speed of 600rpm, keeping the stirring at 80 ℃ to evaporate the ethanol, heating and stirring for 8 hours, and taking out the material powder after the ethanol is completely evaporated; and sintering the taken material powder in a muffle furnace at 900 ℃ for 3 hours to obtain the coating modified sodium ion battery anode material. Wherein the manganese-rich shell structure oxide Na0.44MnO2Of layered transition metal oxidesThe mass percentage is 3%.
Example 6
Weighing 1.472g of manganese oxalate, dissolving in 10ml of ethanol, and magnetically stirring for 30 minutes; then 10g of layered transition metal oxide positive electrode material Na was added0.9Cu0.22Fe0.3Mn0.48Continuously placing the mixture on a magnetic stirrer, stirring at a constant speed of 600rpm, keeping the stirring at 80 ℃ to evaporate the ethanol, heating and stirring for 8 hours, and taking out the material powder after the ethanol is completely evaporated; and sintering the taken material powder in a muffle furnace at 900 ℃ for 3 hours to obtain the coating modified sodium ion battery anode material. Wherein the manganese-rich shell structure oxide Na0.44MnO2The content of the layered transition metal oxide is 10% by mass.
Example 7
Weighing 0.130g of manganese chloride, dissolving in 10ml of ethanol, and magnetically stirring for 30 minutes; then 10g of layered transition metal oxide positive electrode material Na was added0.9Cu0.22Fe0.3Mn0.48Continuously placing the mixture on a magnetic stirrer, stirring at a constant speed of 600rpm, keeping the stirring at 80 ℃ to evaporate the ethanol, heating and stirring for 8 hours, and taking out the material powder after the ethanol is completely evaporated; and sintering the taken material powder in a muffle furnace at 900 ℃ for 3 hours to obtain the coating modified sodium ion battery anode material. Wherein the manganese-rich shell structure oxide Na0.44MnO2The content of the layered transition metal oxide is 1% by mass.
Example 8
Weighing 0.389g of manganese chloride, dissolving in 10ml of ethanol, and magnetically stirring for 30 minutes; then 10g of layered transition metal oxide positive electrode material Na was added0.9Cu0.22Fe0.3Mn0.48Continuously placing the mixture on a magnetic stirrer, stirring at a constant speed of 600rpm, keeping the stirring at 80 ℃ to evaporate the ethanol, heating and stirring for 8 hours, and taking out the material powder after the ethanol is completely evaporated; and sintering the taken material powder in a muffle furnace at 900 ℃ for 3 hours to obtain the coating modified sodium ion battery anode material. Wherein the manganese-rich shell structure oxide Na0.44MnO2Of layered transition metal oxidesThe mass percentage is 3%.
Example 9
Weighing 1.296g of manganese chloride, dissolving in 10ml of ethanol, and magnetically stirring for 30 minutes; then 10g of layered transition metal oxide positive electrode material Na was added0.9Cu0.22Fe0.3Mn0.48Continuously placing the mixture on a magnetic stirrer, stirring at a constant speed of 600rpm, keeping the stirring at 80 ℃ to evaporate the ethanol, heating and stirring for 8 hours, and taking out the material powder after the ethanol is completely evaporated; and sintering the taken material powder in a muffle furnace at 900 ℃ for 3 hours to obtain the coating modified sodium ion battery anode material. Wherein the manganese-rich shell structure oxide Na0.44MnO2The content of the layered transition metal oxide is 10% by mass.
Comparative example 1
Directly using layered transition metal oxide as anode material Na0.9Cu0.22Fe0.3Mn0.48As the positive electrode material of the sodium-ion battery. The positive electrode material of comparative example 1 was subjected to a Scanning Electron Microscope (SEM) test, and the result is shown in fig. 2.
The positive electrode materials of sodium ion batteries prepared in examples 1, 2 and 3 and comparative example 1 were subjected to X-ray diffraction test, and the results are shown in fig. 3.
The positive electrode materials of sodium ion batteries prepared in the respective examples and comparative examples were subjected to PH test, and the results are shown in table 1 below.
| Positive electrode material | pH value |
| Example 1 | 12.67 |
| Example 2 | 12.25 |
| Example 3 | 12.41 |
| Example 4 | 12.56 |
| Example 5 | 12.33 |
| Example 6 | 12.55 |
| Example 7 | 12.44 |
| Example 8 | 12.32 |
| Example 9 | 12.45 |
| Comparative example 1 | 13.27 |
TABLE 1
According to the test result, compared with the uncoated anode material, the coated anode material has the advantages that the residual alkali content on the surface of the coated anode material is obviously reduced, the measured PH value is also obviously reduced, the processing performance of the material is improved, and the requirements of the material on the storage and use environment are also reduced.
The positive electrode materials of the sodium-ion batteries prepared in the examples and the comparative examples are mixed with conductive carbon black and polyvinylidene fluoride binder according to the weight ratio of 7: 2: 1, and adding an N-methyl pyrrolidone solution until grinding in a normal-temperature drying environment to form slurry; uniformly coating the prepared slurry on an aluminum foil of a current collector, and cutting the aluminum foil into a circular pole piece with the diameter of 12mm after primary drying; the circular pole piece was dried under vacuum at 120 ℃ for 12 hours and then transferred to a glove box for further use.
The assembly of the simulated battery is carried out in a glove box in Ar atmosphere, metal sodium is used as a counter electrode, glass fiber is used as a diaphragm, and 1mol/L NaPF6And (2) using a solution of Ethylene Carbonate (EC)/dimethyl carbonate (DMC) (volume ratio of 1: 1) as an electrolyte to assemble the CR2032 button cell. The charge and discharge test was performed at a current density of 1C using a constant current charge and discharge mode. The test conditions were: the discharge cutoff voltage was 2.5V and the charge cutoff voltage was 4.0V. The test results are shown in table 2 below.
| Positive electrode material | First effect% | Retention rate of 1C charging and discharging 100 circles% |
| Example 1 | 93.9 | 83.0 |
| Example 2 | 94.4 | 89.2 |
| Example 3 | 95.7 | 82.5 |
| Example 4 | 93.6 | 84.9 |
| Example 5 | 95.4 | 87.8 |
| Example 6 | 95.9 | 83.3 |
| Example 7 | 92.4 | 83.8 |
| Example 8 | 95.1 | 86.9 |
| Example 9 | 94.6 | 80.6 |
| Comparative example 1 | 92.0 | 73.5 |
TABLE 2
According to the test result, compared with the uncoated anode material, the first-cycle coulombic efficiency of the coated material is obviously improved, and the long-cycle capacity retention rate is high.
The coated and modified sodium-ion battery positive electrode material provided by the embodiment of the invention has the advantages of simple preparation method, low cost and easiness for large-scale production. The coating effect is uniform, the manganese source is dissolved in the ethanol by adopting a solvothermal method, and Na can be generated on the surface of the material in situ by utilizing the sodium source provided by the residual alkali on the surface of the layered transition metal oxidejMnO2Of a substance forming a dense rich layer on the surface of the materialThe protective layer of the manganese shell structure reduces the contact area of the interior exposed to the electrolyte, thereby reducing the occurrence of interface side reaction, improving the material circulation stability, simultaneously playing a role in reducing the residual alkali on the surface of the material, improving the processing performance of the material and reducing the requirements of the material on the storage and use environment. And, NajMnO2Has electrochemical activity, and can play a role in stable circulation without reducing the energy density of the material as an electrode material.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (8)
1. A coating modified sodium-ion battery positive electrode material is characterized by comprising: the composite oxide comprises a layered transition metal oxide and a manganese-rich shell structure oxide coated outside the layered transition metal oxide;
the layered transition metal oxide has the general formula: na (Na)xCuyFezMnaM1-y-z-aO2(ii) a Wherein M is an element for doping and substituting the transition metal site, and comprises one or more of Li, Ni, Mg, Zn, Co, Al, Zr and Ti; x is more than 0.5 and less than or equal to 1, y is more than 0 and less than or equal to 0.5, z is more than 0 and less than or equal to 0.5, and a is more than 0 and less than or equal to 0.5; the values of x, y, z and a satisfy the charge balance of the chemical formula;
the general structural formula of the manganese-rich shell structure oxide is as follows: na (Na)jMnO2；0＜j≤0.6。
2. The coating-modified sodium-ion battery positive electrode material as claimed in claim 1, wherein the manganese-rich shell structure oxide is 1-10% of the layered transition metal oxide by mass ratio.
3. The preparation method of the coating modified sodium-ion battery positive electrode material as claimed in claim 1 or 2, which is characterized in that the preparation method is a solvothermal method, and specifically comprises the following steps:
dissolving a manganese source in an alcohol solvent, and magnetically stirring;
adding a certain amount of layered transition metal oxide, continuously heating and stirring at a certain temperature to evaporate ethanol due to heating, and taking out the obtained material powder after the ethanol is completely evaporated;
and sintering the taken material powder in a muffle furnace to obtain the coating modified sodium-ion battery anode material.
4. The preparation method according to claim 3, wherein the manganese source specifically comprises one or more of manganese-containing compounds such as manganese acetate, manganese oxalate, manganese chloride and the like;
the alcohol solvent specifically includes: one or more of alcohol solvents such as ethanol, methanol, isopropanol and the like;
the layered transition metal oxide has the general formula: na (Na)xCuyFezMnaM1-y-z-aO2(ii) a Wherein M is an element for doping and substituting the transition metal site, and comprises one or more of Li, Ni, Mg, Zn, Co, Al, Zr and Ti; x is more than 0.5 and less than or equal to 1, y is more than 0 and less than or equal to 0.5, z is more than 0 and less than or equal to 0.5, and a is more than 0 and less than or equal to 0.5; the values of x, y, z and a satisfy the charge balance of the chemical formula.
5. The preparation method according to claim 3, wherein the stirring time of the magnetic stirring is 10min to 60 min;
the stirring time of the heating and stirring is 6-10 hours, and the heating temperature is 80-100 ℃.
6. The method for preparing the ceramic material according to claim 3, wherein the sintering temperature of the sintering is 800-1000 ℃; the sintering time is 2-4 hours.
7. A positive electrode for sodium-ion battery, characterized in that it comprises the coating-modified positive electrode material for sodium-ion battery according to claim 1 or 2.
8. A sodium-ion battery comprising the positive electrode for a sodium-ion battery according to claim 7.
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