CN113937286B - Coated modified sodium ion battery positive electrode material, preparation method thereof and battery - Google Patents
Coated modified sodium ion battery positive electrode material, preparation method thereof and battery Download PDFInfo
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Abstract
The invention discloses a coated modified sodium ion battery anode material, a preparation method thereof and a battery; the positive electrode material includes: a layered transition metal oxide and a manganese-rich shell structure oxide coated outside the layered transition metal oxide; the general formula of the layered transition metal oxide is: na (Na) x Cu y Fe z Mn a M 1‑y‑z‑ a O 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein M is an element for doping and substituting transition metal positions, 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 meet the charge balance of a chemical formula; the structural general formula of the manganese-rich shell structure oxide is as follows: na (Na) j MnO 2 ；0＜j≤0.6。
Description
Technical Field
The invention relates to the technical field of sodium ion battery materials, in particular to a coated modified sodium ion battery positive electrode material, a preparation method thereof and a battery.
Background
Environmental pollution and energy shortage are common major problems faced by human beings, and the development of a large-scale efficient clean energy storage technology can greatly reduce energy and environmental problems. Sodium ion batteries are ideal candidates for large-scale energy storage by virtue of the advantages of abundant resources, low cost, high safety and the like, although the larger radius of sodium ions makes the mature positive electrode material of the lithium ion batteries unsuitable for a sodium ion battery system, similar to the working principle of the lithium ion batteries. Therefore, it is particularly important to develop a high-performance electrode material capable of rapidly and stably storing sodium. Among the currently known positive electrode materials for sodium ion batteries, sodium layered metal oxide is one of the most promising positive electrode materials for sodium ion batteries to realize commercialization at present by virtue of the characteristics of high theoretical specific capacity and easy synthesis. However, instability of the layered structure during charge and discharge has limited its practical application. The surface coating of the material is one of effective means for improving the cycling stability of the electrode material, and the current coating material of the positive electrode material of the sodium ion battery is approximately of the following four types: respectively metal oxide, nonmetallic element coating, sodium/lithium fast ion conductor, organic matter/conductive polymer, etc.
Although there are advantages to different types of sodium ion battery positive electrode material coating materials, there are also respective disadvantages:
the oxide used in the oxide coating is electrochemical inert, does not contribute to capacity in the charge and discharge process, and reduces the energy density of the battery;
the nonmetallic element coating is mainly C, N two elements coating, so that the problem of high residual alkali content on the surface of the sodium-electricity layered anode material cannot be solved, and the processing performance of the material is affected;
the method for coating the sodium/lithium fast ion conductor is complex, the process flow is more, the method is not suitable for large-scale production, the used anions have larger molecular weight, and the energy density of the battery can be reduced;
the organic matter/conductive polymer coating has high requirements on experimental conditions, the poor control of the polymerization speed of the organic polymer can easily cause the rapid aggregation of materials, and the compatibility of the organic polymer and electrolyte can also influence the performance of the battery.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art and provides a coated modified sodium ion battery anode material, a preparation method thereof and a battery. The material has a compact protective layer with a manganese-rich shell structure on the surface, and can reduce the contact area of the internal layered transition metal oxide exposed to electrolyte, thereby reducing the occurrence of interface side reaction and improving the cycling stability of the material.
In view of this, in a first aspect, embodiments of the present invention provide a coating-modified sodium ion battery cathode material, comprising: a layered transition metal oxide and a manganese-rich shell structure oxide coated outside the layered transition metal oxide;
the general formula of the layered transition metal oxide is: na (Na) x Cu y Fe z Mn a M 1-y-z-a O 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein M is an element for doping and substituting transition metal positions, 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 meet the charge balance of a chemical formula;
the structural general formula of the manganese-rich shell structure oxide is as follows: na (Na) j MnO 2 ；0＜j≤0.6。
Preferably, the manganese-rich shell structure oxide accounts for 1-10% of the layered transition metal oxide according to the mass ratio.
In a second aspect, an embodiment of the present invention provides a method for preparing the coated modified positive electrode material of a sodium ion battery according to 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 lamellar 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 (5) placing the taken material powder into a muffle furnace for sintering to obtain the coated modified sodium ion battery anode material.
Preferably, 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 comprises: one or more of alcohol solvents such as ethanol, methanol, isopropanol, etc.;
the general formula of the layered transition metal oxide is: na (Na) x Cu y Fe z Mn a M 1-y-z-a O 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein M is an element for doping and substituting transition metal positions, 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-60min;
the stirring time of 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 positive electrode of a sodium ion battery, including the coating modified positive electrode material of a sodium ion battery 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 described in the third aspect.
The coated and modified sodium ion battery anode material provided by the invention adopts a solvothermal method to dissolve a manganese source in ethanol, and the sodium source provided by residual alkali on the surface of the layered transition metal oxide can be utilizedIn situ generation of Na on the surface of a material j MnO 2 The material has the advantages that a compact protective layer of a manganese-rich shell structure is formed on the surface of the material, the contact area of the interior exposed to electrolyte is reduced, so that the occurrence of interface side reactions is reduced, the cycling stability of the material is improved, the effect of reducing residual alkali on the surface of the material is simultaneously achieved, the processability of the material is improved, and the requirements of the material on storage and use environments are reduced. Also, na j MnO 2 Has electrochemical activity, plays a role in stabilizing circulation and does not reduce the energy density of the material used as an electrode material.
Drawings
The technical scheme of the embodiment of the invention is further described in detail through the drawings and the embodiments.
FIG. 1 is a Scanning Electron Microscope (SEM) image of a coated modified sodium ion battery anode material provided in example 2 of the present invention;
FIG. 2 is a Transmission Electron Microscope (TEM) image of the coated modified sodium-ion battery cathode material provided in example 2 of the present invention;
FIG. 3 is an SEM image of the positive electrode material of a sodium ion battery provided in comparative example 1;
fig. 4 is a graph showing comparison of X-ray diffraction tests of positive electrode materials for sodium ion batteries prepared in examples 1, 2, and 3 according to the present invention and comparative example 1.
Detailed Description
The embodiment of the invention provides a coated modified sodium ion battery anode material, which comprises the following components: layered transition metal oxide and manganese-rich shell structure oxide coated outside the layered transition metal oxide. The general formula of the layered transition metal oxide is: na (Na) x Cu y Fe z Mn a M 1-y-z-a O 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein M is an element for doping and substituting transition metal positions, 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 meet the charge balance of a chemical formula; the structural general formula of the manganese-rich shell structure oxide is as follows: na (Na) j MnO 2 The method comprises the steps of carrying out a first treatment on the surface of the J is more than 0 and less than or equal to 0.6. In the positive electrode material, the manganese-rich shell structure oxide is layered according to the mass ratio1% -10% of transition metal oxide.
The positive electrode 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 lamellar transition metal oxide, continuing 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, placing the taken material powder into a muffle furnace for sintering to obtain the coated 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 comprises: one or more of alcohol solvents such as ethanol, methanol, isopropanol, etc.; the stirring time of the magnetic stirring is 10min-60min; the stirring time of heating and stirring is 6-10 hours, and the heating temperature is 80-100 ℃. The sintering temperature of sintering is 800-1000 ℃; the sintering time is 2-4 hours.
Na can be generated on the surface of the material in situ by dissolving a manganese source in ethanol by adopting a solvothermal method and utilizing a sodium source provided by residual alkali on the surface of the layered transition metal oxide j MnO 2 The material has the advantages that a compact protective layer of a manganese-rich shell structure is formed on the surface of the material, the contact area of the interior exposed to electrolyte is reduced, so that the occurrence of interface side reactions is reduced, the cycling stability of the material is improved, the effect of reducing residual alkali on the surface of the material is simultaneously achieved, the processability of the material is improved, and the requirements of the material on storage and use environments are reduced. The coated and modified sodium ion battery anode material prepared by the invention is used for the sodium ion battery anode. Na (Na) j MnO 2 Has electrochemical activity, plays a role in stabilizing circulation and does not reduce the energy density of the material used as an electrode material.
The positive electrode material of the present invention, and the preparation method and properties thereof are described in further detail by means of some specific examples.
Example 1
0.178g of manganese acetate is weighed and dissolved in 10ml of ethanol, and the mixture is magnetically stirred for 30 minutes; then 10g was addedLayered transition metal oxide positive electrode material Na 0.9 Cu 0.22 Fe 0.3 Mn 0.48 Continuously placing the mixture on a magnetic stirrer, stirring at a constant speed of 600rpm, keeping the temperature at 80 ℃ to evaporate ethanol, heating and stirring for 8 hours, and taking out the material powder after the ethanol is completely evaporated; and (3) placing the taken material powder into a muffle furnace, and sintering for 3 hours at 900 ℃ to obtain the coated modified sodium ion battery anode material. Wherein the manganese-rich shell structure oxide Na 0.44 MnO 2 The mass percentage of the lamellar transition metal oxide is 1%.
Example 2
Weighing 0.534g of manganese acetate, dissolving in 10ml of ethanol, and magnetically stirring for 30 minutes; next, 10g of a layered transition metal oxide positive electrode material Na was added 0.9 Cu 0.22 Fe 0.3 Mn 0.48 Continuously placing the mixture on a magnetic stirrer, stirring at a constant speed of 600rpm, keeping the temperature at 80 ℃ to evaporate ethanol, heating and stirring for 8 hours, and taking out the material powder after the ethanol is completely evaporated; and (3) placing the taken material powder into a muffle furnace, and sintering for 3 hours at 900 ℃ to obtain the coated modified sodium ion battery anode material. Wherein the manganese-rich shell structure oxide Na 0.44 MnO 2 The mass percentage of the lamellar transition metal oxide is 3%. The positive electrode material obtained in example 2 was subjected to a Scanning Electron Microscope (SEM) test, and the result is shown in fig. 1. The resulting material was uniformly coated as can be seen by SEM images. Fig. 2 is a transmission electron microscope image of the coating modified positive electrode material of the sodium ion battery in this embodiment, and it can be seen that, as shown by the dotted line in the image, an oxide coating layer with a manganese-rich shell structure is provided on the surface of the layered transition metal oxide positive electrode material.
Example 3
1.781g of manganese acetate was weighed and dissolved in 10ml of ethanol, and magnetically stirred for 30 minutes; next, 10g of a layered transition metal oxide positive electrode material Na was added 0.9 Cu 0.22 Fe 0.3 Mn 0.48 Continuously placing the mixture on a magnetic stirrer, stirring at a constant speed of 600rpm, keeping the temperature at 80 ℃ to evaporate ethanol, heating and stirring for 8 hours, and taking out the material powder after the ethanol is completely evaporated; placing the taken-out material powder into a muffle furnaceAnd sintering at 900 ℃ for 3 hours to obtain the coated modified sodium ion battery anode material. Wherein the manganese-rich shell structure oxide Na 0.44 MnO 2 The mass percentage of the layered transition metal oxide is 10%.
Example 4
Weighing 0.147g of manganese oxalate, dissolving in 10ml of ethanol, and magnetically stirring for 30 minutes; next, 10g of a layered transition metal oxide positive electrode material Na was added 0.9 Cu 0.22 Fe 0.3 Mn 0.48 Continuously placing the mixture on a magnetic stirrer, stirring at a constant speed of 600rpm, keeping the temperature at 80 ℃ to evaporate ethanol, heating and stirring for 8 hours, and taking out the material powder after the ethanol is completely evaporated; and (3) placing the taken material powder into a muffle furnace, and sintering for 3 hours at 900 ℃ to obtain the coated modified sodium ion battery anode material. Wherein the manganese-rich shell structure oxide Na 0.44 MnO 2 The mass percentage of the lamellar transition metal oxide is 1%.
Example 5
Weighing 0.442g of manganese oxalate, dissolving in 10ml of ethanol, and magnetically stirring for 30 minutes; next, 10g of a layered transition metal oxide positive electrode material Na was added 0.9 Cu 0.22 Fe 0.3 Mn 0.48 Continuously placing the mixture on a magnetic stirrer, stirring at a constant speed of 600rpm, keeping the temperature at 80 ℃ to evaporate ethanol, heating and stirring for 8 hours, and taking out the material powder after the ethanol is completely evaporated; and (3) placing the taken material powder into a muffle furnace, and sintering for 3 hours at 900 ℃ to obtain the coated modified sodium ion battery anode material. Wherein the manganese-rich shell structure oxide Na 0.44 MnO 2 The mass percentage of the lamellar transition metal oxide is 3%.
Example 6
1.472g of manganese oxalate is weighed and dissolved in 10ml of ethanol, and magnetically stirred for 30 minutes; next, 10g of a layered transition metal oxide positive electrode material Na was added 0.9 Cu 0.22 Fe 0.3 Mn 0.48 Continuously placing the mixture on a magnetic stirrer, stirring at a constant speed of 600rpm, keeping the temperature at 80 ℃ to evaporate ethanol, heating and stirring for 8 hours, and taking out the material powder after the ethanol is completely evaporated; placing the taken-out material powder into a muffle furnaceAnd sintering at 900 ℃ for 3 hours to obtain the coated modified sodium ion battery anode material. Wherein the manganese-rich shell structure oxide Na 0.44 MnO 2 The mass percentage of the layered transition metal oxide is 10%.
Example 7
Weighing 0.130g of manganese chloride, dissolving in 10ml of ethanol, and magnetically stirring for 30 minutes; next, 10g of a layered transition metal oxide positive electrode material Na was added 0.9 Cu 0.22 Fe 0.3 Mn 0.48 Continuously placing the mixture on a magnetic stirrer, stirring at a constant speed of 600rpm, keeping the temperature at 80 ℃ to evaporate ethanol, heating and stirring for 8 hours, and taking out the material powder after the ethanol is completely evaporated; and (3) placing the taken material powder into a muffle furnace, and sintering for 3 hours at 900 ℃ to obtain the coated modified sodium ion battery anode material. Wherein the manganese-rich shell structure oxide Na 0.44 MnO 2 The mass percentage of the lamellar transition metal oxide is 1%.
Example 8
0.389g of manganese chloride is weighed and dissolved in 10ml of ethanol, and the mixture is magnetically stirred for 30 minutes; next, 10g of a layered transition metal oxide positive electrode material Na was added 0.9 Cu 0.22 Fe 0.3 Mn 0.48 Continuously placing the mixture on a magnetic stirrer, stirring at a constant speed of 600rpm, keeping the temperature at 80 ℃ to evaporate ethanol, heating and stirring for 8 hours, and taking out the material powder after the ethanol is completely evaporated; and (3) placing the taken material powder into a muffle furnace, and sintering for 3 hours at 900 ℃ to obtain the coated modified sodium ion battery anode material. Wherein the manganese-rich shell structure oxide Na 0.44 MnO 2 The mass percentage of the lamellar transition metal oxide is 3%.
Example 9
1.296g of manganese chloride is weighed and dissolved in 10ml of ethanol, and the mixture is magnetically stirred for 30 minutes; next, 10g of a layered transition metal oxide positive electrode material Na was added 0.9 Cu 0.22 Fe 0.3 Mn 0.48 Continuously placing the mixture on a magnetic stirrer, stirring at a constant speed of 600rpm, keeping the temperature at 80 ℃ to evaporate ethanol, heating and stirring for 8 hours, and taking out the material powder after the ethanol is completely evaporated; placing the taken-out material powder into a muffle furnaceAnd sintering at 900 ℃ for 3 hours to obtain the coated modified sodium ion battery anode material. Wherein the manganese-rich shell structure oxide Na 0.44 MnO 2 The mass percentage of the layered transition metal oxide is 10%.
Comparative example 1
Directly using layered transition metal oxide as positive electrode material Na 0.9 Cu 0.22 Fe 0.3 Mn 0.48 As a positive electrode material of a 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 for sodium ion batteries prepared in examples 1, 2 and 3 and comparative example 1 were subjected to an X-ray diffraction test, and the results are shown in fig. 3.
The positive electrode materials for sodium ion batteries prepared in each example and comparative example 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 positive electrode material, the residual alkali content on the surface of the coated material is obviously reduced, the measured PH value is also obviously reduced, the processing performance of the material is improved, and meanwhile, the requirements of the material on storage and use environments are also reduced.
The positive electrode materials of the sodium ion batteries prepared in each example and comparative example are mixed with conductive carbon black and polyvinylidene fluoride binder according to the following ratio of 7:2:1, and adding an N-methyl pyrrolidone solution until grinding in a normal-temperature dry environment to form slurry; uniformly coating the prepared slurry on an aluminum foil of a current collector, and cutting into round pole pieces with the diameter of 12mm after primary drying; the round pole piece is dried for 12 hours at 120 ℃ under vacuum condition and then is transferred into a glove box for standby.
The invention is characterized in that the assembly of the simulated battery is carried out in a glove box with Ar atmosphere, metal sodium is used as a counter electrode, glass fiber is used as a diaphragm, and 1mol/L NaPF is used 6 The solution of Ethylene Carbonate (EC)/dimethyl carbonate (DMC) (volume ratio 1:1) is used as electrolyte to assemble the CR2032 button cell. Using constant current charge-discharge mode, at 1C currentAnd (5) performing charge and discharge test under the density. The test conditions were: the discharge cut-off voltage was 2.5V and the charge cut-off voltage was 4.0V. The test results are shown in Table 2 below.
| Positive electrode material | First effect% | 1C charge-discharge 100 cycles retention% |
| 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 positive electrode material, the first-week coulomb efficiency of the coated material is obviously improved, and the long-cycle capacity retention rate is high.
The coated and modified sodium ion battery anode material provided by the embodiment of the invention has the advantages of simple preparation method, low cost and easiness in large-scale production. The coating effect is uniform, the manganese source is dissolved in 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 oxide j MnO 2 The material has the advantages that a compact protective layer of a manganese-rich shell structure is formed on the surface of the material, the contact area of the interior exposed to electrolyte is reduced, so that the occurrence of interface side reactions is reduced, the cycling stability of the material is improved, the effect of reducing residual alkali on the surface of the material is simultaneously achieved, the processability of the material is improved, and the requirements of the material on storage and use environments are reduced. Also, na j MnO 2 Has electrochemical activity, plays a role in stabilizing circulation and does not reduce the energy density of the material used as an electrode material.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (6)
1. The preparation method of the coated and modified sodium ion battery positive electrode material is characterized by comprising the following steps of: a layered transition metal oxide and a manganese-rich shell structure oxide coated outside the layered transition metal oxide;
the general formula of the layered transition metal oxide is: na (Na) 0.9 Cu 0.22 Fe 0.3 Mn 0.48 O 2 The structural general formula of the manganese-rich shell structure oxide is as follows: na (Na) 0.44 MnO 2 ；
The manganese-rich shell layer and the layered transition metal oxide have an obvious interface;
the preparation method is a solvothermal method and specifically comprises the following steps:
dissolving a manganese source in an alcohol solvent, and magnetically stirring, wherein the stirring time of the magnetic stirring is 10-60 min; the manganese source comprises one or more of manganese acetate, manganese oxalate and manganese chloride;
adding a certain amount of lamellar transition metal oxide, continuing heating and stirring at a certain temperature, wherein the stirring time of heating and stirring is 6-10 hours, the heating temperature is 80-100 ℃, the alcohol solvent is evaporated due to heating, and the obtained material powder is taken out after the alcohol solvent is completely evaporated;
placing the taken material powder into a muffle furnace for sintering to obtain the coated modified sodium ion battery anode material, wherein the sintering temperature of the sintering is 800-1000 ℃; the sintering time is 2-4 hours;
na source provided by residual alkali on surface of layered transition metal oxide is utilized to generate Na on surface of layered transition metal oxide in situ 0.44 MnO 2 And a material forms a compact protective layer with a manganese-rich shell structure on the surface of the layered transition metal oxide, so that residual alkali on the surface of the material is reduced.
2. The method according to claim 1, wherein,
the alcohol solvent specifically comprises: ethanol, methanol, isopropanol.
3. A coated modified sodium ion battery positive electrode material, characterized in that the positive electrode material comprises: a layered transition metal oxide and a manganese-rich shell structure oxide coated outside the layered transition metal oxide;
the general formula of the layered transition metal oxide is: na (Na) 0.9 Cu 0.22 Fe 0.3 Mn 0.48 O 2 The structural general formula of the manganese-rich shell structure oxide is as follows: na (Na) 0.44 MnO 2 ；
The manganese-rich shell layer and the layered transition metal oxide have an obvious interface;
the sodium ion battery anode material is prepared by a solvothermal method, and specifically comprises the following steps:
dissolving a manganese source in an alcohol solvent, and magnetically stirring, wherein the stirring time of the magnetic stirring is 10-60 min; the manganese source comprises one or more of manganese acetate, manganese oxalate and manganese chloride;
adding a certain amount of lamellar transition metal oxide, continuing heating and stirring at a certain temperature, wherein the stirring time of heating and stirring is 6-10 hours, the heating temperature is 80-100 ℃, the alcohol solvent is evaporated due to heating, and the obtained material powder is taken out after the alcohol solvent is completely evaporated;
placing the taken material powder into a muffle furnace for sintering to obtain the coated modified sodium ion battery anode material, wherein the sintering temperature of the sintering is 800-1000 ℃; the sintering time is 2-4 hours;
sodium source provided by residual alkali on surface of layered transition metal oxide in layered transition metal oxidationIn situ formation of Na on the surface of the object 0.44 MnO 2 And a material forms a compact protective layer with a manganese-rich shell structure on the surface of the layered transition metal oxide, so that residual alkali on the surface of the material is reduced.
4. The coated modified positive electrode material for sodium ion battery according to claim 3, wherein the manganese-rich shell structure oxide is 1% -10% of the layered transition metal oxide in terms of mass ratio.
5. A positive electrode of a sodium ion battery, characterized in that the positive electrode of the sodium ion battery comprises a coated modified positive electrode material of a sodium ion battery prepared by the preparation method of claim 1 or 2 or a coated modified positive electrode material of a sodium ion battery of claim 3 or 4.
6. A sodium ion battery comprising the positive electrode of claim 5.
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| CN115504526B (en) * | 2022-10-31 | 2024-01-02 | 无锡零一未来新材料技术研究院有限公司 | Oxide sodium ion battery positive electrode material, and preparation method and application thereof |
| CN116143199B (en) * | 2023-04-21 | 2023-08-08 | 江苏正力新能电池技术有限公司 | Surface-coated layered oxide, preparation method thereof, positive plate, sodium ion battery and electric equipment |
| CN117497728A (en) * | 2023-12-04 | 2024-02-02 | 湖南美特新材料科技有限公司 | Sodium ion battery positive electrode material and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009135092A (en) * | 2007-11-09 | 2009-06-18 | Sumitomo Chemical Co Ltd | Compound metal oxide and sodium secondary battery |
| CN103050682A (en) * | 2012-12-24 | 2013-04-17 | 北京理工大学 | Sodium ion battery electrode material and preparation method thereof |
| KR101613435B1 (en) * | 2014-11-26 | 2016-04-20 | 한국생산기술연구원 | A manufacturing method of Na0.44MnO2 nano-rod for an electrode and a manufacturing method sodium rechargeable battery thereof |
| WO2017017944A1 (en) * | 2015-07-24 | 2017-02-02 | Sharp Kabushiki Kaisha | Sodium transition metal oxide compounds for Na-ion batteries |
| CN107732180A (en) * | 2017-09-27 | 2018-02-23 | 肇庆市华师大光电产业研究院 | A kind of preparation method for water system sodium-ion battery anode composite material |
| CN109524649A (en) * | 2018-11-12 | 2019-03-26 | 北京中科海钠科技有限责任公司 | A kind of sodium-ion battery positive material of clad structure and its preparation method and application |
| CN109638273A (en) * | 2018-12-04 | 2019-04-16 | 北京中科海钠科技有限责任公司 | A kind of method for coating and its secondary cell of sodium-ion battery positive material |
| CN110277540A (en) * | 2018-03-14 | 2019-09-24 | 中国科学院物理研究所 | A kind of core-shell structure sodium-ion battery positive material and its preparation method and application |
| CN110838576A (en) * | 2018-08-17 | 2020-02-25 | 中国科学院物理研究所 | Doped coated sodium-ion battery positive electrode material and preparation method and application thereof |
| CN111342049A (en) * | 2020-03-04 | 2020-06-26 | 溧阳中科海钠科技有限责任公司 | Modified sodium ion battery positive electrode material, preparation method and battery |
-
2020
- 2020-06-29 CN CN202010604410.2A patent/CN113937286B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009135092A (en) * | 2007-11-09 | 2009-06-18 | Sumitomo Chemical Co Ltd | Compound metal oxide and sodium secondary battery |
| CN103050682A (en) * | 2012-12-24 | 2013-04-17 | 北京理工大学 | Sodium ion battery electrode material and preparation method thereof |
| KR101613435B1 (en) * | 2014-11-26 | 2016-04-20 | 한국생산기술연구원 | A manufacturing method of Na0.44MnO2 nano-rod for an electrode and a manufacturing method sodium rechargeable battery thereof |
| WO2017017944A1 (en) * | 2015-07-24 | 2017-02-02 | Sharp Kabushiki Kaisha | Sodium transition metal oxide compounds for Na-ion batteries |
| CN107732180A (en) * | 2017-09-27 | 2018-02-23 | 肇庆市华师大光电产业研究院 | A kind of preparation method for water system sodium-ion battery anode composite material |
| CN110277540A (en) * | 2018-03-14 | 2019-09-24 | 中国科学院物理研究所 | A kind of core-shell structure sodium-ion battery positive material and its preparation method and application |
| CN110838576A (en) * | 2018-08-17 | 2020-02-25 | 中国科学院物理研究所 | Doped coated sodium-ion battery positive electrode material and preparation method and application thereof |
| CN109524649A (en) * | 2018-11-12 | 2019-03-26 | 北京中科海钠科技有限责任公司 | A kind of sodium-ion battery positive material of clad structure and its preparation method and application |
| CN109638273A (en) * | 2018-12-04 | 2019-04-16 | 北京中科海钠科技有限责任公司 | A kind of method for coating and its secondary cell of sodium-ion battery positive material |
| CN111342049A (en) * | 2020-03-04 | 2020-06-26 | 溧阳中科海钠科技有限责任公司 | Modified sodium ion battery positive electrode material, preparation method and battery |
Non-Patent Citations (1)
| Title |
|---|
| 钠离子电池正极材料Na_(0.44)MnO_2的研究进展;史文静;燕永旺;徐守冬;陈良;刘世斌;张鼎;;化工进展(09);全文 * |
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