CN114203949A - Layered manganese-based sodium-ion battery positive electrode material, and preparation method and application thereof - Google Patents
Layered manganese-based sodium-ion battery positive electrode material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of sodium ion battery materials, and particularly relates to a P2 type layered manganese-based sodium ion battery positive electrode material, and a preparation method and application thereof. The invention provides a preparation method of a P2-type layered oxide anode material by improving the original solid-phase sintering method and performing two-time segmented sintering, and the anode material has the characteristics of higher energy density, good stability, low cost and environmental friendliness, and is a promising anode material for a sodium-ion battery. The anode material prepared by the invention inhibits the structural distortion generated by Jahn-Teller effect by doping Li/Zn element, and successfully reduces the Na content of P2 type layered oxide0.72Li0.12Zn0.18Mn0.7O2Irreversible phase changes present in the electrochemical cycle.
Description
Technical Field
The invention belongs to the technical field of sodium ion battery materials, and particularly relates to a P2 type layered manganese-based sodium ion battery positive electrode material, and a preparation method and application thereof.
Background
In recent years, with the rapid development of global economy, the demand for energy has also sharply increased, and with the rapid consumption of fossil fuels and environmental pollution, there is a series of problems, and it is urgently needed to find a new efficient, clean and renewable energy source to reduce the dependence on fossil fuels. Solar energy, wind energy, tidal energy and geothermal energy are focused by people, have the characteristics of large total amount, low energy density, randomness, intermittency and the like, are easily limited by natural conditions, and are difficult to efficiently utilize. In order to solve the above problems, the stability of the output power of the power grid needs to be improved to improve the utilization rate of clean energy, wherein the energy storage technology is very critical. Therefore, there is a need for the development of energy storage and conversion devices with low cost, environmental friendliness, and high energy density.
Among various energy storage devices, secondary batteries have been receiving wide attention due to their flexibility and good energy conversion efficiency, and since sony was first commercialized in the early 1990 s, lithium ion batteries have become a mainstream energy storage battery system in the world and are widely used in various portable devices and electric vehicles. However, since the content of lithium resources is very limited and the distribution is not uniform on a global scale, the application in a large-scale storage grid is limited. Based on the above considerations, people turn their goals to abundant, inexpensive metallic sodium. Sodium, which is the same main group element of lithium, has very similar chemical properties to lithium, and is expected to reduce the cost of electrochemical energy storage, and is the best choice for replacing lithium ion batteries to a certain extent.
For the sodium ion battery, the structure and performance of the electrode material are still one of the decisive factors influencing the electrochemical performance of the sodium ion battery, and the development of efficient electrode materials is crucial to promote the commercialization of the sodium ion battery. The positive electrode material of sodium ion battery is in many kinds, and there is a layered transition metal oxide NaxTMO2(TM is a transition metal element), polyanion compounds, Prussian blue compounds, tunnel oxides, and the like. Wherein the layered manganese-based cathode material has higher theoretical specific capacity (>200mAh/g), reversible sodium ion deintercalation, a simple synthetic method (solid phase sintering), environmental friendliness and the like, and is favored by researchers in the field of materials and batteries.
However, the P2 type layered manganese-based positive electrode material is due to Mn3+The Jahn-Teller effectResulting in an extension of the Mn — O bond length in one particular direction, exhibiting poor long-term cyclability. The asymmetry in the crystal structure can lead to structural disintegration, so that the capacity in the circulation process is rapidly reduced, and finally the electrochemical performance of the material is poor.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a layered positive electrode material Na of a P2 type sodium-ion battery0.72Li0.12Zn0.18Mn0.7O2The problems of low energy density and poor cycle stability of the anode material are solved by a Li/Zn co-doping mode.
One of the objects of the present invention is to provide a full d-layer metallic Zn2+The transition metal layer doped into the manganese-based anode material activates the oxidation reduction of anions in the layered material, and improves the specific capacity of the anode material to a certain extent. Provides a new idea for further improving the energy density of the sodium-ion battery.
By Li+The doping of the material stabilizes the structural change of the material in the electrochemical cycle process, inhibits the irreversible phase change of a P2 type layered oxide positive electrode material in the charge and discharge process, and reduces O particularly when the material has an anionic redox phenomenon2The release of (2) improves the cycling stability of the battery.
Further, Mn is diluted by Li/Zn co-doping3+Thereby reducing the influence of Jahn-Teller, Mn in the first charging cycle4+The electrochemical battery does not participate in charge compensation, only O is subjected to oxidation reduction to participate in charge compensation, the structure is well stabilized, and the electrochemical cycling stability of the battery is improved.
According to the invention, through simple element doping, irreversible phase change from P2 phase to O2 phase in a high voltage region is inhibited, the stability of a layered structure is improved, and the electrochemical performance of the anode material is further improved.
Furthermore, the P2 type layered oxide anode material is in a hexagonal block structure, and the diameter is 2-3 μm.
The second purpose of the invention is to provideProviding a P2 type manganese-based layered oxide anode material Na0.72Li0.12Zn0.18Mn0.7O2The preparation method specifically comprises the following steps:
(1) by high temperature solid phase synthesis according to Na0.72Li0.12Zn0.18Mn0.7O2The raw materials are weighed according to the stoichiometric ratio of the chemical elements, wherein Na and Li are decomposed to a certain extent at a high temperature, so that the amount of Na and Li is increased by 5% more than the theoretical amount.
The raw material is Na2CO3、Li2CO3ZnO and MnO2。
(2) Weighing raw materials, uniformly mixing, putting into a planetary ball mill for ball milling, and in order to ensure that the raw materials are uniformly mixed during ball milling, adopting a wet milling method, namely adding an absolute ethyl alcohol solution into a ball milling tank to increase the adhesiveness among the materials and be beneficial to full milling.
The ratio of the raw materials to the absolute ethyl alcohol is 3 g: 10ml, the rotating speed of the ball mill is 600rpm/min, the ball milling time is 6h, and the ball-material ratio is 6: 1.
(3) and putting the mixture after the ball milling into a tabletting grinding tool for tabletting, wherein the pressure is 8-15MPa, and the pressure maintaining time is 1-2 minutes, so as to ensure that the material particles are fully contacted and facilitate the mutual reaction at high temperature.
(4) And (3) calcining the pressed sample at high temperature in the air, sintering the sample in a box type furnace, heating to 900 ℃ at the heating rate of 3-8 ℃/min, preferably 5 ℃/min, and keeping the temperature for 12h, and after sintering, cooling the sample to room temperature along with the furnace.
(5) And (4) taking out the sintered sample, putting the sintered sample into a mortar, grinding for 10-15min to obtain powder, and pressing the powder into tablets according to the step (3).
(6) And (3) calcining the pressed sample in air again, wherein the heating rate is 5 ℃/min, the temperature is increased to 700 ℃, the heat preservation is carried out, the heat preservation time is 12 hours, after the sintering is finished, the sample is cooled to the room temperature along with the furnace to obtain the layered oxide cathode material, and the prepared sample is immediately transferred to a glove box filled with Ar gas to avoid the sample from absorbing water.
Another object of the present invention is to provide a P2-type layered oxide positive electrode material Na0.72Li0.12Zn0.18Mn0.7O2With the P2 type layered oxide anode material Na0.72Li0.12Zn0.18Mn0.7O2The positive electrode material as a battery can be applied to a sodium ion battery, and comprises the following steps;
taking the prepared P2 type manganese-based layered oxide as a positive electrode active material, taking conductive carbon black Super P as a conductive agent, taking polyvinylidene fluoride (PVDF) as a binder, uniformly mixing the active material, the Super P and the PVDF according to the mass ratio of 8:1: 1-6: 3:1, preferably 7:2:1, grinding for 30min, taking an aluminum foil as a current collector, coating the current collector into a sheet, drying the sheet in a vacuum drying box completely, and then preparing the sheet into a positive electrode sheet by a slicing machine; the metal sodium is used as a negative electrode; using glass fiber filter paper of a GF/D battery diaphragm as a diaphragm; matching sodium perchlorate electrolyte, assembling the sodium ion battery in a glove box filled with argon, standing for 10 hours, and then carrying out corresponding electrochemical performance test under a certain voltage window and current density.
The voltage windows are 2-4.5V and 1.5-4.6V, the current density is adjusted according to the theoretical specific capacity, and the current densities of 0.1C, 0.2C, 0.5C, 1C, 2C and the like are respectively selected for testing.
The P2-type layered positive electrode material Na0.72Li0.12Zn0.18Mn0.7O2The anion redox phenomenon can be generated, a higher charging voltage platform is provided, and the test with the optimal performance can not be obtained within 2-4.5V, so the voltage is expanded to 1.5-4.6V to realize high specific capacity and high energy density.
The P2-type layered manganese-based positive electrode material Na is successfully synthesized through the metal element doping and twice sintering method0.72Li0.12Zn0.18Mn0.7O2. Successfully reduces the Na of P2-type layered oxide by the co-doping of inactive elements Li/Zn0.72Li0.12Zn0.18Mn0.7O2The phase change in the anode material improves the cycling stability. Meanwhile, Li/Zn element codoping activates oxygen oxidation reduction of the layered oxide, so that larger specific capacity (about 192mAh/g) is successfully obtained in a voltage range of 1.5-4.6V, and higher energy density is realized. The elements of the anode material are rich and widely distributed in the current earth crust, have low cost and belong to environment-friendly elements.
Compared with the prior art, the invention has the beneficial effects that:
(1) the anode material prepared by the invention inhibits the structural distortion generated by Jahn-Teller effect by doping Li/Zn element, and successfully reduces the Na content of P2 type layered oxide0.72Li0.12Zn0.18Mn0.7O2Irreversible phase changes present in the electrochemical cycle.
(2) The invention fully dopes d layers of transition metal elements Zn in the Mn-based layered material, thereby achieving the purpose of activating the layered oxide Na0.72Li0.12Zn0.18Mn0.7O2The specific capacity is greatly improved and higher energy density is realized by oxidation reduction of the anion in the process.
(3) The invention stabilizes the phenomenon of anion oxidation reduction by doping of alkali metal element Li and stronger interaction between Li and O, obtains more reversible oxidation reduction of oxygen and obtains higher cycling stability.
(4) The invention provides a preparation method of a P2-type layered oxide anode material by improving the original solid-phase sintering method and performing two-time segmented sintering, and the anode material has the characteristics of higher energy density, good stability, low cost and environmental friendliness, and is a promising anode material for a sodium-ion battery.
Drawings
FIG. 1 shows a positive electrode material Na prepared in example 10.72Li0.12Zn0.18Mn0.7O2X-ray diffraction pattern (XRD).
Fig. 2 is a Scanning Electron Microscope (SEM) photograph of the cathode material prepared in example 1.
Fig. 3 is a typical charge and discharge curve for the first 3 cycles of the battery prepared in example 1.
Fig. 4 is a graph of the cycle performance of the first 50 cycles of the battery prepared in example 1.
FIG. 5 is a dQ/dV curve for the cell prepared in example 1.
Fig. 6 is a constant current charge and discharge curve of the battery prepared in example 1 at different rates.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the present invention will be further described in detail with reference to specific embodiments. The following description is intended only to illustrate the invention and not to limit the contents, and all reagents and materials are commercially available in the art.
Example 1
(I) preparation of cathode Material Na0.72Li0.12Zn0.18Mn0.7O2。
(1) According to Na0.72Li0.12Zn0.18Mn0.7O2Weighing Na according to the stoichiometric ratio of each chemical element2CO3、Li2CO3ZnO and MnO2Raw material, Na2CO3With Li2CO3Decomposition at high temperature needs to be prevented, and the actual weighed mass is 5% more than the theoretically calculated mass.
(2) Weighing a sample with the total mass of 3g, placing the sample in an agate ball milling tank, adding 10ml of absolute ethyl alcohol solution, carrying out wet ball milling in a planetary ball mill with the ball-material ratio of 6:1, the rotating speed of the ball mill of 600rpm/min and the ball milling time of 6h, drying the sample after the ball milling is finished, and then grinding the sample for 3-8min by using a mortar.
(3) The milled mixture was pressed into a circular tablet having a diameter of 20mm and a thickness of about 1mm by a tablet press and a tablet press to prepare a ready-to-burn tablet. The pressure is 8-15MPa, and the pressure maintaining time is 1-2 min.
(4) And (3) putting the pressed wafer into air for high-temperature calcination, sintering in a common box-type furnace at a heating rate of 5 ℃/min to 900 ℃, preserving heat for 12h, and then cooling to room temperature along with the furnace.
(5) Taking out the sintered sample, putting the sintered sample into a mortar, manually grinding for 10min, and then tabletting again according to the same steps as the step (3).
(6) And (3) performing secondary calcination on the pressed sample in the air again, namely, performing secondary calcination in a box-type furnace at the temperature rising rate of preferably 5 ℃/min, raising the temperature to 700 ℃, preserving the temperature for 12h, and then cooling to room temperature along with the furnace. The sample can be prepared and is quickly transferred into a glove box after being prepared, so that the sample is prevented from absorbing moisture.
And (II) assembling the sodium-ion battery.
And (2) taking the anode material prepared in the step (I) as an anode active substance, taking conductive carbon black Super P as a conductive agent, taking polyvinylidene fluoride (PVDF) as a binder, adding the active material, the Super P and the PVDF into a mortar according to the mass ratio of preferably 7:2:1, and grinding for 30 min. Coating the aluminum foil serving as a current collector into a thin sheet, and preparing the thin sheet into a positive plate through a slicing machine after the thin sheet is completely dried in a vacuum drying oven; the negative electrode is metallic sodium, and the electrolyte is NaClO4The (+ FEC) solution was assembled in an argon glove box with a water oxygen value below 0.01ppm using a porous glass fiber membrane (GF/D) as the separator.
And (III) testing the electrochemical performance of the sodium-ion battery.
The assembled cells were tested for electrochemical performance using a blue electrochemical workstation. The voltage window is set at 1.5-4.6V, and electrochemical performance tests are carried out by respectively selecting constant rates of current density of 0.1C, 0.2C, 0.5C, 1C and 2C according to the specific capacity obtained by theoretical calculation and the mass of the corresponding positive pole piece active substance. Typical charge and discharge curves are shown in fig. 3.
Example 2
The molar ratio of each substance is changed, and Na is accurately weighed according to the molar ratio of 0.67:0.07:0.23:0.72CO3，Li2CO3ZnO and MnO2According to the same method as that of the step (one) in example 1, a positive electrode material of a sodium ion battery, the molecular formula of which is Na, is prepared0.67Li0.07Zn0.23Mn0.7O2。
The remaining assembled sodium ion cells and electrochemical performance tests were performed as in example 1.
Example 3
The molar ratio of each substance is changed, and Na is accurately weighed according to the molar ratio of 0.75:0.15:0.15:0.72CO3，Li2CO3ZnO and MnO2According to the same method as that of the step (one) in example 1, a positive electrode material of a sodium ion battery, the molecular formula of which is Na, is prepared0.75Li0.15Zn0.15Mn0.7O2。
The remaining assembled sodium ion cells and electrochemical performance tests were performed as in example 1.
Example 4
The molar ratio of each substance is changed, and Na is accurately weighed according to the molar ratio of 0.77:0.17:0.13:0.72CO3，Li2CO3ZnO and MnO2According to the same method as that of the step (one) in example 1, a positive electrode material of a sodium ion battery, the molecular formula of which is Na, is prepared0.77Li0.17Zn0.13Mn0.7O2。
The remaining assembled sodium ion cells and electrochemical performance tests were performed as in example 1.
Example 5
The molar ratio of each substance is changed, and Na is accurately weighed according to the molar ratio of 0.78:0.18:0.12:0.72CO3，Li2CO3ZnO and MnO2According to the same method as that of the step (one) in example 1, a positive electrode material of a sodium ion battery, the molecular formula of which is Na, is prepared0.78Li0.18Zn0.12Mn0.7O2。
The remaining assembled sodium ion cells and electrochemical performance tests were performed as in example 1.
Example 6
Changing the molar ratio of each substance, and accurately weighing Na according to the molar ratio of 0.8:0.2:0.1:0.72CO3，Li2CO3ZnO and MnO2According toIn the same manner as in the first step of example 1, a positive electrode material for a sodium ion battery, having a molecular formula of Na, was prepared0.8Li0.2Zn0.1Mn0.7O2。
The remaining assembled sodium ion cells and electrochemical performance tests were performed as in example 1.
Example 7
The molar ratio of each substance is changed, and Na is accurately weighed according to the molar ratio of 0.67:0.07:0.23:0.72CO3，Li2CO3ZnO and MnO2According to the same method as that of the step (one) in example 1, a positive electrode material of a sodium ion battery, the molecular formula of which is Na, is prepared0.67Li0.07Zn0.23Mn0.7O2。
The remaining assembled sodium ion cells and electrochemical performance tests were performed as in example 1.
Example 8
The precursor MnO2 in example 1 was replaced by Fe2O3, and Na was accurately weighed in a molar ratio of 0.8:0.13:0.2:0.672CO3，Li2CO3ZnO and Fe2O3According to the same method as that of the step (one) in example 1, a positive electrode material of a sodium ion battery, the molecular formula of which is Na, is prepared0.8Li0.13Zn0.2Fe0.67O2. Whether similar iron-based positive electrode materials can achieve the same effect is studied.
The remaining assembled sodium ion cells and electrochemical performance tests were performed as in example 1.
The positive electrode material of the sodium-ion battery prepared in the above example was assembled into a battery, and then subjected to the following electrochemical performance test.
1. The test voltage was between 1.5 and 4.6V, and the current density was 0.2C (1C 188mA/g) for charge and discharge performance, and the results are shown in fig. 3 and table 1.
| Item | Specific charging capacity (mAh/g) | Specific discharge capacity (mAh/g) | Coulombic efficiency (%) |
| Example 1 | 192 | 183 | 95.31 |
| Example 2 | 168 | 159 | 94.64 |
| Example 3 | 169 | 163 | 96.44 |
| Example 4 | 172 | 164 | 95.34 |
| Example 5 | 170 | 162 | 95.29 |
| Example 6 | 167 | 156 | 93.41 |
2. The charge-discharge cycle stability of the material is tested, the test voltage is 1.5-4.6V, the current density is 0.5C, the capacity can still keep 82% after 50 cycles, and the cycle performance chart is shown in figure 3.
3. The test voltage is between 1.5 and 4.6V, and the electrochemical performance test is carried out under the conditions that the current density is respectively 10mA/g, 20mA/g, 50mA/g, 100mA/g and 200 mA/g. The test results are shown in FIG. 5.
Fig. 1 is an X-ray diffraction pattern of the cathode material prepared in example 1 of the present invention, which is seen to correspond to the characteristic peak of the P2-type layered oxide, indicating that the sample has a P63/mmc space group structure. FIG. 2 is a scanning electron micrograph of the material showing a hexagonal block structure with a diameter of about 2-3 μm.
Electrochemical performance tests were performed on the sodium ion batteries prepared as described above, and the results are shown in fig. 3 to 4. As can be seen from figure 3, the first-turn specific charge capacity of the material under the voltage conditions of 0.5C and 1.5-4.6V can reach 173mAh/g, the total capacity is contributed by oxygen participating in oxidation reduction, when the material is discharged to 1.5V, the discharge capacity can reach 192mAh/g, and the capacity is higher than that of other most Mn-based sodium-ion batteries researched in the past. From the second circle, it can be seen that Mn starts to participate in redox, the discharge capacity can reach 188mAh/g, and can be stably maintained. Fig. 4 is a graph of the cycle performance of the first 50 cycles of the battery, and it can be seen from the graph that the specific capacity can still maintain 82% of the initial capacity after 50 cycles under the conditions of 0.5C and 1.5-4.6V.
In order to research the mechanism of valence-change elements in the charging and discharging processes, a corresponding dQ/dV curve is shown in fig. 5, only O valence change participates in oxidation reduction in the first charging process, Mn valence change participates in oxidation reduction from the first discharging process, Mn and O simultaneously participate in charge compensation in the subsequent circulating process, and the reversibility degree is high.
Further researching the multiplying power performance, as shown in fig. 6, the reversible specific capacity of 88mAh/g can be achieved under the current density of 200mA/g, and the multiplying power performance is good.
Compared with the research of related anion redox sodium ion batteries, the method has great advantages in the aspects of integrating the specific capacity and the cycle performance of the battery.
Claims (8)
1. The layered manganese-based sodium-ion battery positive electrode material is characterized by being a P2 type sodium-ion battery layered positive electrode material Na0.72Li0.12Zn0.18Mn0.7O2。
2. The layered manganese-based sodium-ion battery positive electrode material as claimed in claim 1, wherein the layered manganese-based sodium-ion battery positive electrode material has a hexagonal block structure and a diameter of 2-3 μm.
3. The preparation method of the layered manganese-based sodium-ion battery positive electrode material according to claim 1, characterized by comprising the following specific steps:
(1) by high temperature solid phase synthesis according to Na0.72Li0.12Zn0.18Mn0.7O2The stoichiometric ratio of each chemical element in the raw material
(2) Weighing raw materials, uniformly mixing, and putting into a planetary ball mill for ball milling;
(3) putting the mixture after ball milling into a tabletting grinding tool for tabletting;
(4) calcining the pressed sample at high temperature in the air, sintering in a box furnace, heating to 900 ℃ at the heating rate of 3-8 ℃/min, keeping the temperature for 12h, and cooling the sample to room temperature along with the furnace after sintering is finished;
(5) taking out the sintered sample, grinding the sintered sample in a mortar to obtain powder, and pressing the powder into tablets according to the same steps in the step (3);
(6) and (3) calcining the pressed sample in the air again, wherein the heating rate is 5 ℃/min, the temperature is increased to 700 ℃, the heat preservation is carried out, the heat preservation time is 12h, and after the sintering is finished, the sample is cooled to the room temperature along with the furnace, so that the layered manganese-based sodium-ion battery anode material can be obtained.
4. The method for preparing the positive electrode material of the layered manganese-based sodium-ion battery according to claim 3, wherein in the step (1), the raw material is Na2CO3、Li2CO3ZnO and MnO2(ii) a Because Na and Li can generate certain decomposition at high temperature, the weight of Na element and Li element is required to be added by 5 percent more than that of theoretical weight when the Na element and Li element are weighed; in the step (2), in order to ensure that the raw materials are uniformly mixed during ball milling, a wet milling method is adopted, namely, an absolute ethyl alcohol solution is added into a ball milling tank, so that the adhesion among the materials is increased, and the full milling is facilitated; the ratio of the raw materials to the absolute ethyl alcohol is 3 g: 10ml, the rotating speed of the ball mill is 600rpm/min, the ball milling time is 6h, and the ball-material ratio is 6: 1.
5. the method for preparing a layered manganese-based sodium-ion battery positive electrode material according to claim 3, wherein in the step (3), the pressure for pressing into tablets is 8-15MPa, and the dwell time is 1-2 minutes; in the step (4), the heating rate is 5 ℃/min.
6. The method for preparing the anode material of the layered manganese-based sodium-ion battery according to claim 3, wherein in the step (5), the grinding time is 10-15 min; and (6) immediately transferring the obtained layered manganese-based sodium-ion battery positive electrode material into a glove box filled with Ar gas to avoid water absorption of the sample.
7. The use of the layered manganese-based sodium-ion battery positive electrode material as claimed in claim 1, wherein the layered manganese-based sodium-ion battery positive electrode material is used as a positive electrode active material, conductive carbon black Super P is used as a conductive agent, polyvinylidene fluoride is used as a binder, the positive electrode active material, the conductive carbon black Super P and the polyvinylidene fluoride are uniformly mixed according to the mass ratio of 8:1: 1-6: 3:1, the mixture is ground, coated into a thin sheet by taking an aluminum foil as a current collector, and the thin sheet is made into a positive electrode sheet by a slicing machine after being completely dried in a vacuum drying oven; then taking metal sodium as a negative electrode; using glass fiber filter paper of a GF/D battery diaphragm as a diaphragm; matching with sodium perchlorate electrolyte, and assembling the sodium ion battery in a glove box filled with argon.
8. Use according to claim 7, wherein the mass ratio of positive active material, conductive carbon black Super P and polyvinylidene fluoride is 7:2: 1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114914390A (en) * | 2022-04-08 | 2022-08-16 | 东莞市沃泰通新能源有限公司 | Preparation method of modified sodium ion battery positive electrode material, positive electrode plate and battery |
| CN115490267A (en) * | 2022-09-27 | 2022-12-20 | 东华理工大学 | High-air-stability power type layered oxide positive electrode material and preparation method thereof |
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