CN113517433A - Positive electrode material of anion-cation doped P2 type sodium ion battery - Google Patents
Positive electrode material of anion-cation doped P2 type sodium ion battery Download PDFInfo
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Abstract
The invention relates to a positive electrode material of a positive and negative ion doped P2 type sodium ion battery, a preparation method thereof and the positive electrode material, the chemical formula of which is Na-free0.67CuxMn1‑xO2‑yFyWherein 0 is<x≤0.35,0<y is less than or equal to 0.3, manganese salt, copper salt and sodium fluoride are weighed according to the molar ratio of Mn, Cu and F elements and dissolved in deionized water, sodium salt is added, stirring and dissolving are carried out, a mixed metal salt solution is prepared, and a citric acid solution is used as a complexing agent; adding the mixed metal salt solution into a complexing agent, adding ammonia water to adjust the pH value of the solution to 8-11, heating the solution to 60-90 ℃, and evaporating the solution to dryness under the stirring condition to obtain gel; drying the obtained gel, crushing, pre-burning in air atmosphere,and sintering, and cooling to room temperature to obtain the cathode material. The Cu ion and the F ion have synergistic effect, so that the material shows excellent electrochemical performance, such as improvement of specific capacity, rate capability and good cycling stability.
Description
Technical Field
The invention belongs to the field of preparation of electrode materials of sodium ion batteries, and particularly relates to an anion-cation co-doped modified P2 type layered positive electrode material of a sodium ion battery and a preparation method thereof.
Background
With the continuous development of new energy technology, lithium ion batteries have been successful in the past two decades due to the advantages of high energy density, high stability, long service life and the like, but the storage capacity of lithium resources in the earth crust is low, and the lithium ion batteries cannot become the key of large-scale energy storage. Therefore, sodium ion batteries have received much attention from researchers. The sodium ion battery has the advantages of low production cost, high safety and abundant raw materials, so the sodium ion battery is considered to be an ideal large-scale energy storage device.
The layered transition metal oxide sodium ion battery positive electrode material can be divided into a P2 type and an O3 type according to the stacking sequence of the arrangement of oxygen atoms, wherein Na+Occupying sodium layer (NaO)2) The triangular prism position and the octahedral position distinguish between P-type and O-type. The electrochemical performance of the P2 type layered cathode material is better than that of the O3 type because the P2 phase structure has a lower diffusion barrier and higher ion conductivity. In addition, the P2 phase structure can not generate the oxide layer slip phenomenon in the process of Na ion de-intercalation, and the structure is more stable, so the method has better commercial application prospect. But for P2-Na0.67MnO2In other words, when the material is exposed to air, water molecules will occupy Na+Resulting in increased layer spacing and reduced overall cell performance. In 2015, Cu was discovered by the Huyong victory subject group2+The doped P2 type layered sodium-ion battery cathode material can effectively improve the air stability of the material, but the material has a low reversible specific capacity of about 90mAh/g, and the material has a cycle performanceThe ring stability is poor.
The research on the co-doping of cations and anions is rarely reported about the single doping or the doping of various cations mainly focused on the transition metal site and the oxygen site.
Disclosure of Invention
The invention aims to provide a positive electrode material of a negative and positive ion doped P2 type sodium ion battery and a preparation method thereof, and at least achieves the aim of improving the electrochemical performance of the material.
In order to solve the technical problems, according to one aspect of the invention, a positive electrode material of a positive and negative ion doped P2 type sodium ion battery is provided, and the chemical formula of the positive electrode material is Na0.67CuxMn1-xO2-yFyWherein 0 is<x≤0.35,0<y≤0.3。
According to another aspect of the present invention, there is provided a method for preparing the above-mentioned positive electrode material of a zwitterion-doped P2-type sodium ion battery, which comprises:
step one, according to a chemical formula of Na0.67CuxMn1-xO2-yFyWeighing manganese salt, copper salt and sodium fluoride according to the molar ratio of Mn, Cu and F elements, dissolving the manganese salt, the copper salt and the sodium fluoride in deionized water, adding sodium salt, stirring and dissolving to prepare a mixed metal salt solution, and taking a citric acid solution as a complexing agent;
adding the mixed metal salt solution into a complexing agent, adding ammonia water to adjust the pH value of the solution to 8-11, heating to 60-90 ℃, and evaporating to dryness under the condition of stirring to obtain gel;
and step three, drying and crushing the obtained gel, pre-burning the gel in an air atmosphere, then sintering the gel, and cooling the gel to room temperature to obtain the cathode material.
Further, in the step one, the manganese salt is one or more of manganese sulfate, manganese nitrate, manganese acetate or manganese chloride; the copper salt is one or more of copper sulfate, copper nitrate or copper chloride; the sodium salt is one or more of sodium sulfate, sodium nitrate or sodium chloride.
Further, in the first step, the total molar concentration of the metal ions is 1-3 mol/L.
Further, in the first step, a citric acid solution with the mass concentration of 2% -20% is prepared to serve as a complexing agent.
And further, in the second step, placing a complexing agent on a heatable magnetic stirrer, slowly adding the mixed metal salt solution into the complexing agent, controlling the rotating speed and the temperature of the magnetic stirrer, stirring and drying by distillation to obtain the gel.
Further, in the third step, the pre-sintering is carried out at a temperature rise rate of 1-10 ℃/min to 150-400 ℃, the temperature is kept for 2-8 h, and then the temperature is continuously raised to 400-700 ℃ and kept for 2-8 h.
Further, in the third step, the sintering is carried out at the temperature rising rate of 1-10 ℃/min to 700-1500 ℃, and the temperature is kept for 8-14 h.
According to another aspect of the invention, a sodium ion battery is provided, and the positive electrode of the sodium ion battery adopts the positive electrode material of the P2 type sodium ion battery doped with anions and cations.
Furthermore, the lithium ion battery is prepared by respectively mixing the positive electrode material of the anion-cation doped P2 type sodium ion battery with a conductive agent and a binder PVDF, grinding uniformly, adding NMP to prepare slurry, uniformly coating the slurry on a pretreated aluminum foil, drying and cutting into a positive plate; and (2) assembling a sodium metal sheet as a negative electrode, a 0.1mol/L sodium perchlorate/ethylene carbonate/dimethyl carbonate solution as an electrolyte and a polypropylene film as a diaphragm to obtain the sodium-ion battery.
Compared with the prior art, the Cu and F ion co-doped P2 type sodium ion battery positive electrode material Na provided by the invention0.67CuxMn1-xO2-yFyAnd the Cu ions and the F ions have synergistic effect, so that excellent electrochemical properties are shown, such as improvement of specific capacity, rate capability and good cycling stability of the material.
The preparation method adopts a method of combining a liquid-phase synthesis precursor with high-temperature calcination, has the characteristics of simplicity, reliability and low cost, has smooth material surface, uniform particles and compact structure, shows excellent electrochemical performance, and has better industrial application prospect.
Drawings
In FIG. 1, a and b are layered Na positive electrode materials for P2 type sodium ion prepared in comparative example 3 and example 2 of the present invention0.67MnO2And Na0.67Cu0.1Mn0.9O1.85F0.15XRD pattern of (a).
In FIG. 2, a and b are Na0 in comparative example 1 and example 2, respectively.67MnO2And Na0.67Cu0.1Mn0.9O1.85F0.15SEM image of (d).
A, b and c in fig. 3 are layered sodium ion cathode materials Na0 of the P2 type prepared in comparative example 1, comparative example 3 and example 2 of the present invention, respectively.67MnO2 、Na0.67Cu0.1Mn0.9O2And Na0.67Cu0.1Mn0.9O1.85F0.15A cycle life curve chart when the voltage interval is 2-4.2V and the current density is 100 mA/g.
In FIG. 4, a and b are layered Na positive electrode materials for P2 type sodium ion prepared in comparative example 3 and example 2, respectively, according to the present invention0.67Cu0.1Mn0.9O2And Na0.67Cu0.1Mn0.9O1.85F0.15A first charge-discharge curve chart under the current density of 100mA/g and the voltage of 2-4.2V.
In FIG. 5, a and b are layered Na positive electrode materials for P2 type sodium ion prepared in comparative example 3 and example 2, respectively, according to the present invention0.67Cu0.1Mn0.9O2And Na0.67Cu0.1Mn0.9O1.85F0.15Magnification cycle plot at different currents.
Detailed Description
The invention provides a cathode material of a negative and positive ion doped P2 type sodium ion battery, which has a chemical formula of Na0.67CuxMn1-xO2-yFyWherein 0 is<x≤0.35,0<y≤0.3。
The overall concept of the invention is that Cu ions are used for replacing part of trivalent manganese ions to inhibit Jahn-Taller effect, so that the material circulation stability is improved, meanwhile, F ions are doped to reduce the average valence state of Mn ions in the material, so that the initial capacity of the material is high, and the material structure is further stable due to the strong favorable attraction effect of the F ions, so that the material circulation stability is further improved, and the electrochemical performance of the material is improved.
Experiments prove that the cathode material used for the sodium ion battery shows excellent electrochemical properties, such as high specific capacity, good rate capability and good cycling stability.
The invention also provides a preparation method of the cathode material of the zwitterion-doped P2 type sodium ion battery, which comprises the following steps.
Step one, according to a chemical formula of Na0.67CuxMn1-xO2-yFyWeighing manganese salt, copper salt and sodium fluoride according to the molar ratio of Mn, Cu and F elements, dissolving the manganese salt, the copper salt and the sodium fluoride in deionized water, adding sodium salt, stirring and dissolving to prepare a mixed metal salt solution, and taking a citric acid solution as a complexing agent.
Preferably, the total molar concentration of metal ions is 1-3 mol/L, and a citric acid solution with the mass concentration of 2-20% is prepared as a complexing agent.
Preferably, the manganese salt in the first step is one or more of manganese sulfate, manganese nitrate, manganese acetate or manganese chloride; the copper salt is one or more of copper sulfate, copper nitrate or copper chloride, and the sodium salt is one or more of sodium sulfate, sodium nitrate or sodium chloride.
Adding the mixed metal salt solution into a complexing agent, adding ammonia water to adjust the pH value of the solution to 8-11, heating to 60-90 ℃, and evaporating to dryness under the condition of stirring to obtain gel;
preferably, in the second step, the complexing agent is placed on a heatable magnetic stirrer, the mixed metal salt solution is slowly added into the complexing agent, the rotating speed and the temperature of the magnetic stirrer are controlled, and the gel is obtained by stirring and drying. The rotating speed of the magnetic stirrer is 200-600 rpm.
And step three, drying and crushing the obtained gel, pre-burning the gel in an air atmosphere, then sintering the gel, and cooling the gel to room temperature to obtain the cathode material.
Preferably, in the third step, the pre-burning is carried out at a temperature rise rate of 1-10 ℃/min to 150-400 ℃, and the temperature is kept for 2-8 hours, so that the citric acid is automatically combusted. And then continuously heating to 400-700 ℃, and preserving the heat for 2-8 hours to decompose the organic compounds.
In the third step, the sintering is carried out at the temperature rising rate of 1-10 ℃/min to 700-1500 ℃, and the temperature is kept for 8-14 h.
The method has the advantages of good repeatability, simple operation and low cost, is different from the traditional solid phase sintering method, and can uniformly and quantitatively dope some trace elements by adopting a simplified sol-gel method to realize intermolecular doping. The sodium ion battery anode material prepared by the method has the advantages of smooth surface, uniform particles, compact structure and excellent electrochemical performance. Because the primary particles are nano particles, the larger specific surface area is beneficial to the desorption of sodium ions in the circulation process, the full contact between the electrolyte and the material is increased, and the capacity and the circulation performance of the material are improved.
The claimed solution is further illustrated by the following examples. However, the examples and comparative examples are intended to illustrate the embodiments of the present invention without departing from the scope of the subject matter of the present invention, and the scope of the present invention is not limited by the examples. Unless otherwise specifically indicated, the materials and reagents used in the present invention are available from commercial products in the art.
Comparative example 1
(1) According to the synthesis of 2g of Na0.67MnO2Weighing sodium acetate (excessive 5%) and manganese acetate according to the molar ratio of the Na and Mn elements, dissolving the sodium acetate and the manganese acetate in deionized water to ensure that the total concentration of metal ions is 2mol/L, and continuously stirring until a metal salt solution is dissolved. Preparing a citric acid solution with the mass concentration of 10%, slowly adding a metal salt solution into the citric acid solution, adjusting the pH value of the mixed solution to 8 by using ammonia water, and stirring and evaporating at 80 ℃ to dryness to obtain a gel substance.
(2) Drying the gel obtained in the step (1) at 120 ℃, crushing, heating to 200 ℃ at a heating rate of 5 ℃/min in the air atmosphere, preserving heat for 2h, and then continuing toContinuously heating to 500 ℃ and preserving the heat for 3 h. And then heating to 800 ℃ at the heating rate of 1 ℃/min, preserving the heat for 10 hours, and cooling to room temperature to obtain the P2 type layered sodium ion anode material Na0.67MnO2。
Comparative example 2
(1) According to the synthesis of 2g of Na0.67Cu0.05Mn0.95O2Weighing sodium acetate (excessive 5 percent), copper acetate and manganese acetate according to the molar ratio of Na, Cu and Mn elements, dissolving the sodium acetate, the copper acetate and the manganese acetate in deionized water to ensure that the total concentration of metal ions is 2mol/L, and continuously stirring until a metal salt solution is dissolved. Preparing a citric acid solution with the mass concentration of 10%, slowly adding a metal salt solution into the citric acid solution, adjusting the pH value of the mixed solution to 9 by using ammonia water, stirring and evaporating at 85 ℃ to dryness to obtain a gel substance.
(2) And (2) drying the gel obtained in the step (1) at 115 ℃, crushing, heating to 250 ℃ at a heating rate of 2 ℃/min in an air atmosphere, keeping the temperature for 3h, and then continuously heating to 550 ℃ and keeping the temperature for 5 h. And then heating to 850 ℃ at the heating rate of 2 ℃/min, preserving the heat for 11h, and cooling to room temperature to obtain the Cu-doped P2 type layered sodium ion cathode material Na0.67Cu0.05Mn0.95O2。
Comparative example 3
(1) According to the synthesis of 2g of Na0.67Cu0.1Mn0.9O2Sodium nitrate (5 percent in excess), copper nitrate and manganese nitrate are weighed according to the molar ratio of Na, Cu and Mn elements and dissolved in deionized water to ensure that the total concentration of metal ions is 2mol/L, and the solution is continuously stirred until the metal salt solution is dissolved. Preparing a citric acid solution with the mass concentration of 15%, slowly adding a metal salt solution into the citric acid solution, adjusting the pH value of the mixed solution to 10 by using ammonia water, and stirring and evaporating at 90 ℃ to dryness to obtain a gel substance.
(2) And (2) drying the gel obtained in the step (1) at 100 ℃, crushing, heating to 300 ℃ at a heating rate of 3 ℃/min in an air atmosphere, preserving heat for 3.5h, and then continuously heating to 600 ℃ and preserving heat for 5.5 h. Then heating to 900 ℃ at the heating rate of 3 ℃/min, preserving the heat for 12h, and cooling to room temperature to obtain the Cu-doped P2 type layered sodium ion cathode material Na0.67Cu0.1Mn0.9O2。
Comparative example 4
(1) According to the synthesis of 2g of Na0.67Cu0.2Mn0.8O2Weighing sodium sulfate (excessive 5 percent), copper sulfate and manganese sulfate according to the molar ratio of Na, Cu and Mn elements, dissolving the sodium sulfate, the copper sulfate and the manganese sulfate in deionized water to ensure that the total concentration of metal ions is 3mol/L, and continuously stirring until a metal salt solution is dissolved. Preparing a citric acid solution with the mass concentration of 20%, slowly adding a metal salt solution into the citric acid solution, adjusting the pH value of the mixed solution to 9 by using ammonia water, stirring and evaporating at 90 ℃ to dryness to obtain a gel substance.
(2) And (2) drying the gel obtained in the step (1) at 110 ℃, crushing, heating to 350 ℃ at a heating rate of 4 ℃/min in an air atmosphere, keeping the temperature for 4h, and then continuously heating to 650 ℃ and keeping the temperature for 6 h. And then heating to 950 ℃ at the heating rate of 4 ℃/min, preserving the heat for 13h, and cooling to room temperature to obtain the Cu-doped P2 type layered sodium ion cathode material Na0.67Cu0.2Mn0.8O2。
Example 1
(1) According to the synthesis of 2g of Na0.67Cu0.1Mn0.9O1.9F0.1Weighing sodium acetate (excessive 5 percent), copper acetate, manganese acetate and sodium fluoride according to the molar ratio of Na, Cu, Mn and F elements, dissolving the sodium acetate, the copper acetate, the manganese acetate and the sodium fluoride in deionized water to ensure that the total concentration of metal ions is 2mol/L, and continuously stirring until a metal salt solution is dissolved. Preparing a citric acid solution with the mass concentration of 10%, slowly adding a metal salt solution into the citric acid solution, adjusting the pH value of the mixed solution to 9 by using ammonia water, stirring and evaporating at 85 ℃ to dryness to obtain a gel substance.
(2) And (2) drying the gel obtained in the step (1) at 115 ℃, crushing, heating to 250 ℃ at a heating rate of 2 ℃/min in an air atmosphere, keeping the temperature for 3h, and then continuously heating to 550 ℃ and keeping the temperature for 5 h. Then heating to 850 ℃ at the heating rate of 2 ℃/min, preserving the heat for 11h, and cooling to room temperature to obtain the Cu and F co-doped P2 type layered sodium ion anode material Na0.67Cu0.1Mn0.9O1.9F0.1。
Example 2
(1) According to the synthesis of 2g of Na0.67Cu0.1Mn0.9O1.85F0.15Weighing sodium nitrate (excessive 5 percent), copper nitrate, manganese nitrate and sodium fluoride according to the molar ratio of Na, Cu, Mn and F elements, dissolving the sodium nitrate, the copper nitrate, the manganese nitrate and the sodium fluoride in deionized water to ensure that the total concentration of metal ions is 2mol/L, and continuously stirring until a metal salt solution is dissolved. Preparing a citric acid solution with the mass concentration of 15%, slowly adding a metal salt solution into the citric acid solution, adjusting the pH value of the mixed solution to 10 by using ammonia water, and stirring and evaporating at 90 ℃ to dryness to obtain a gel substance.
(2) And (2) drying the gel obtained in the step (1) at 100 ℃, crushing, heating to 300 ℃ at a heating rate of 3 ℃/min in an air atmosphere, preserving heat for 3.5h, and then continuously heating to 600 ℃ and preserving heat for 5.5 h. Then heating to 900 ℃ at the heating rate of 3 ℃/min, preserving the heat for 12h, and cooling to room temperature to obtain the Cu and F co-doped P2 type layered sodium ion anode material Na0.67Cu0.1Mn0.9O1.85F0.15。
Example 3
(1) According to the synthesis of 2g of Na0.67Cu0.1Mn0.9O1.8F0.2Sodium sulfate (5 percent of excessive amount), copper sulfate, manganese sulfate and sodium fluoride are weighed according to the molar ratio of Na, Cu, Mn and F elements and dissolved in deionized water, so that the total concentration of metal ions is 3mol/L, and the mixture is continuously stirred until a metal salt solution is dissolved. Preparing a citric acid solution with the mass concentration of 20%, slowly adding a metal salt solution into the citric acid solution, adjusting the pH value of the mixed solution to 9 by using ammonia water, stirring and evaporating at 90 ℃ to dryness to obtain a gel substance.
(2) And (2) drying the gel obtained in the step (1) at 110 ℃, crushing, heating to 350 ℃ at a heating rate of 4 ℃/min in an air atmosphere, keeping the temperature for 4h, and then continuously heating to 650 ℃ and keeping the temperature for 6 h. Then heating to 950 ℃ at the heating rate of 4 ℃/min, preserving the heat for 13h, and cooling to room temperature to obtain the Cu-doped P2 type layered sodium ion cathode material Na0.67Cu0.1Mn0.9O1.8F0.2。
Example 4
(1) According to the synthesis of 2g of Na0.67Cu0.1Mn0.9O1.8F0.2Weighing sodium chloride (excessive 5 percent) according to the molar ratio of Na, Cu, Mn and F elements, dissolving the sodium chloride, the copper chloride, the manganese chloride and the sodium fluoride in deionized water to enable the total concentration of metal ions to be 3mol/L, and continuously stirring until the metal salt solution is dissolved. Preparing a citric acid solution with the mass concentration of 20%, slowly adding a metal salt solution into the citric acid solution, adjusting the pH value of the mixed solution to 11 by using ammonia water, and stirring and evaporating at 60 ℃ to dryness to obtain a gel substance.
(2) And (2) drying the gel obtained in the step (1) at 100 ℃, crushing, heating to 150 ℃ at a heating rate of 1 ℃/min in an air atmosphere, keeping the temperature for 8h, and then continuously heating to 400 ℃ and keeping the temperature for 8 h. Then heating to 700 ℃ at the heating rate of 1 ℃/min, preserving the heat for 14h, and cooling to room temperature to obtain the Cu-doped P2 type layered sodium ion cathode material Na0.67Cu0.1Mn0.9O1.8F0.2。
Example 5
(1) According to the synthesis of 2g of Na0.67Cu0.1Mn0.9O1.8F0.2Weighing sodium nitrate (excessive 5 percent), copper nitrate, manganese nitrate and sodium fluoride according to the molar ratio of Na, Cu, Mn and F elements, dissolving the sodium nitrate, the copper nitrate, the manganese nitrate and the sodium fluoride in deionized water to enable the total concentration of metal ions to be 1mol/L, and continuously stirring until a metal salt solution is dissolved. Preparing a citric acid solution with the mass concentration of 2%, slowly adding a metal salt solution into the citric acid solution, adjusting the pH value of the mixed solution to 8 by using ammonia water, and stirring and evaporating at 90 ℃ to dryness to obtain a gel substance.
(2) And (2) drying the gel obtained in the step (1) at 110 ℃, crushing, heating to 400 ℃ at a heating rate of 10 ℃/min in an air atmosphere, keeping the temperature for 2h, and then continuously heating to 700 ℃ and keeping the temperature for 2 h. Then heating to 1500 ℃ at the heating rate of 10 ℃/min, preserving the heat for 8h, and cooling to room temperature to obtain the Cu-doped P2 type layered sodium ion cathode material Na0.67Cu0.1Mn0.9O1.8F0.2。
Application examples
Respectively grinding the P2 type layered sodium ion positive electrode material obtained in comparative examples 1-4 and examples 1-3 with a conductive agent and a binder PVDF uniformly according to the mass ratio of 8:1:1, adding a proper amount of NMP to prepare slurry, uniformly coating the slurry on a pretreated aluminum foil, drying the pretreated aluminum foil for 1h at 80 ℃ in a forced air drying oven, and drying the pretreated aluminum foil for 12h at 120 ℃ in a vacuum drying oven; then, the anode plate was cut into a 12mm circular anode plate by a cutter. A sodium metal sheet with the diameter of 12mm and the thickness of 0.2mm is taken as a negative electrode, 0.1mol/L sodium perchlorate/ethylene carbonate/dimethyl carbonate solution is taken as electrolyte, a polypropylene film with the diameter of 19mm is taken as a diaphragm, and the CR2016 button cell is assembled in a glove box filled with high-purity argon. And testing the electrochemical performance of the material within a voltage range of 2.2V-4.2V.
The XRD pattern shown in figure 1 can be seen to have a layered structure, and the diffraction peak is sharp, the splitting is obvious, and no other obvious impurity peak exists; as can be seen from the graph (b), the peak pattern of the XRD pattern of the positive electrode material co-doped with anions and cations is consistent with that of PDF #27-0751, but the positions of diffraction peaks are slightly shifted, which indicates that Cu ions and F ions have been doped into the material.
The SEM image shown in FIG. 2 shows that the primary particles of the two materials both have a nano-sheet structure, smooth secondary surfaces and compact structures; as can be seen from the graph (b), the primary particles become significantly larger after co-doping with anions and cations.
FIG. 3 shows three materials Na when the voltage range is 2-4.2V and the current density is 100mA/g0.67MnO2(curve a), Na0.67Cu0.1Mn0.9O2(curves b) and Na0.67Cu0.1Mn0.9O1.85F0.15(curve c) cycle life plot. It can be seen from the figure that after 50 cycles, the capacity retention rate of the sodium ion battery prepared from the P2 type layered metal oxide cathode material subjected to anion and cation co-doping modification is 92.8%, which is better than 85.4% of that of cation doping, and which is better than 65.3% of that of unmodified.
FIG. 4 shows the positive ion-doped Na ion positive electrode material at a voltage range of 2-4.2V and a current density of 100mA/g0.67Cu0.1Mn0.9O2(Curve a) and anion and cation co-doped sodium ion cathode material Na0.67Cu0.1Mn0.9O1.85F0.15(curve b) first charge-discharge curve. As can be seen from the figure, the initial discharge capacity of the P2 type layered metal oxide anode material modified by anion and cation co-doping is 129.4mAh/g, which is better than 109mAh/g doped by single cation.
FIG. 5 shows a P2-type layered Na ion positive electrode material0.67Cu0.1Mn0.9O2(FIG. a) and Na0.67Cu0.1Mn0.9O1.85F0.15(graph b) power cycle plot at different currents. As can be seen from the figure: the multiplying power performance of the Cu and F co-doped P2 type layered sodium ion cathode material is obviously superior to that of a single Cu ion doped P2 type layered sodium ion cathode material.
The foregoing embodiments illustrate the principles, main features and advantages of the present invention, and the present invention is not limited to the above embodiments, which are only illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the scope of the principles of the present invention, and these changes and modifications should be construed as being included in the protection scope of the present invention.
Claims (10)
1. The positive electrode material of the anion-cation doped P2 type sodium ion battery is characterized in that: has a chemical formula of Na0.67CuxMn1- xO2-yFyWherein 0 is<x≤0.35,0<y≤0.3。
2. The method for preparing the positive electrode material of the zwitterion-doped P2 type sodium ion battery of claim 1, wherein the method comprises the following steps:
step one, according to a chemical formula of Na0.67CuxMn1-xO2-yFyWeighing manganese salt, copper salt and sodium fluoride according to the molar ratio of Mn, Cu and F elements, dissolving the manganese salt, the copper salt and the sodium fluoride in deionized water, adding sodium salt, stirring and dissolving to prepare a mixed metal salt solution, and taking a citric acid solution as a complexing agent;
adding the mixed metal salt solution into a complexing agent, adding ammonia water to adjust the pH value of the solution to 8-11, heating to 60-90 ℃, and evaporating to dryness under the condition of stirring to obtain gel;
and step three, drying and crushing the obtained gel, pre-burning the gel in an air atmosphere, then sintering the gel, and cooling the gel to room temperature to obtain the cathode material.
3. The method of claim 2, wherein: in the first step, the manganese salt is one or more of manganese sulfate, manganese nitrate, manganese acetate or manganese chloride; the copper salt is one or more of copper sulfate, copper nitrate or copper chloride; the sodium salt is one or more of sodium sulfate, sodium nitrate or sodium chloride.
4. The production method according to claim 2 or 3, characterized in that: in the first step, the total molar concentration of the metal ions is 1-3 mol/L.
5. The method of claim 4, wherein: in the first step, a citric acid solution with the mass concentration of 2% -20% is prepared to serve as a complexing agent.
6. The method of claim 4, wherein: and step two, placing the complexing agent on a heatable magnetic stirrer, slowly adding the mixed metal salt solution into the complexing agent, controlling the rotating speed and the temperature of the magnetic stirrer, stirring and drying by distillation to obtain the gel.
7. The production method according to claim 2, 3, 5 or 6, characterized in that: in the third step, the pre-sintering is carried out at a temperature rise rate of 1-10 ℃/min to 150-400 ℃, the temperature is kept for 2-8 h, and then the temperature is continuously raised to 400-700 ℃ and kept for 2-8 h.
8. The method of claim 7, wherein: in the third step, the sintering is carried out at the temperature rising rate of 1-10 ℃/min to 700-1500 ℃, and the temperature is kept for 8-14 h.
9. A sodium ion battery, characterized by: the positive electrode adopts the positive electrode material of the anion-cation doped P2 type sodium ion battery in claim 1.
10. The sodium-ion battery of claim 9, wherein: the positive electrode material of the zwitterion-doped P2 type sodium ion battery of claim 1, which is prepared by mixing a conductive agent and a binder PVDF respectively, then uniformly grinding, adding NMP to prepare a slurry, uniformly coating the slurry on a pretreated aluminum foil, drying and cutting into a positive plate; and (2) assembling a sodium metal sheet as a negative electrode, a 0.1mol/L sodium perchlorate/ethylene carbonate/dimethyl carbonate solution as an electrolyte and a polypropylene film as a diaphragm to obtain the sodium-ion battery.
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