CN115911331A - Preparation method of low-nickel copper manganese-based sodium ion battery positive electrode material - Google Patents
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Abstract
The invention comprises the following steps: and (2) carrying out improved coprecipitation reaction on a nickel source, a manganese source, a copper source and a carbonate precipitation complexing agent to obtain a carbonate precursor, uniformly mixing the carbonate precursor with the carbon nano tube, then adding a sodium source, and calcining the mixture to obtain the anode material. According to the invention, nickel with a lower proportion is used for preparing the copper-manganese-based sodium ion battery anode material, the structure is more stable, the ionic conductivity is good, and the discharge specific capacity is improved. The precursor and the carbon nano tube are mixed and sintered, thereby obviously hindering the promotion of crystal grains and crystal boundaries, maintaining the stable structure of a crystal phase and solving the problem of crystal phase transformation. The sintered carbon nano tube forms an electronic conduction structure with a network structure, reduces the contact between the anode material and the electrolyte, inhibits the occurrence of side reaction, has stable structure under the condition of high voltage, and improves the cycle performance of the material. The synthesis method is simple, easy to operate, short in synthesis period and suitable for large-scale production.
Description
Technical Field
The invention belongs to the field of positive electrode materials of sodium-ion batteries, and particularly relates to a preparation method of a low-nickel copper manganese-based positive electrode material of a sodium-ion battery.
Background
Sodium ion batteries have become a research and development hot spot of battery technology in recent years due to the characteristics of abundant raw materials, low cost, high safety and the like. Since the radius of sodium ions is larger than that of lithium ions, the current research is critical to develop an electrode material capable of stably and rapidly extracting and intercalating sodium ions. Researchers have made a great deal of effort to improve the electrochemical properties and structural stability of positive electrode materials of sodium ion batteries.
Sodium nickel manganese oxide is a classic sodium electric anode material, and is favored by vast researchers of energy storage due to the fact that the sodium nickel manganese oxide is large in specific capacity, high in working voltage and capable of stably existing in air. However, in the process of charging and discharging, due to the change of Na concentration in the material, the transition metal layer will generate relative slip, and the P2 phase will generate P2 — O2 transformation, accompanied with severe capacity fading. In order to improve the electrochemical performance of the sodium nickel manganese oxide cathode material, the main methods adopted by the current research are doping substitution, surface coating and the like, so that the performance of the material is improved from different angles.
For example, CN115064670A discloses a preparation method of a doped coated modified sodium nickel manganese oxide cathode material, which comprises the following steps: (1) Performing surface treatment on the nickel sodium manganate anode material by using a hydrogen peroxide solution to obtain a surface-treated nickel sodium manganate anode material; (2) And (2) mixing the surface-treated sodium nickel manganese oxide anode material in the step (1) with sodium salt and MgO powder, grinding, and roasting to obtain the doped coated modified sodium nickel manganese oxide anode material. The nickel-sodium manganate anode material with the surface lean in sodium is prepared by a simple surface treatment method, and is mixed with MgO and a sodium source, calcined and subjected to one-step reaction to prepare the Mg2+ surface doped Mg0.4Ni0.6O surface-coated nickel-sodium manganate anode material, so that the purposes of improving the cycling stability and rate capability of the material are achieved.
CN114388794A discloses an aluminum-doped zinc oxide coated sodium nickel manganese oxide positive electrode material for a sodium ion battery and a preparation method thereof, wherein the positive electrode material is of a core-shell structure, and the aluminum-doped zinc oxide is used as a shell to coat sodium nickel manganese oxide. The preparation method of the cathode material comprises the steps of adding sodium nickel manganese oxide into an aqueous solution containing an aluminum source, a zinc source and a complexing agent to obtain gel, drying to obtain dry gel, grinding, and calcining in the air to obtain the aluminum-doped zinc oxide coated sodium nickel manganese oxide.
Although the electrochemical performance of the positive electrode material of the sodium-ion battery is improved to a certain extent, the operation process is complex, the cost is high, and the conductivity, the specific capacity and the cycle performance of the positive electrode material of the sodium-ion battery still have room for further improvement. Therefore, the preparation method of the doping coating modified sodium nickel manganese oxide cathode material with simple doping and coating processes and good electrochemical performance has very important practical significance.
Disclosure of Invention
The invention aims to provide a preparation method of a low-nickel copper manganese-based sodium ion battery anode material, which has the advantages of simple process and low cost, and the obtained anode material has better conductivity, specific capacity and rate characteristic and longer cycle life.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a low-nickel copper manganese-based sodium ion battery positive electrode material comprises the following steps:
(1) Adding a nickel source, a manganese source and a copper source into pure water, and grinding and refining to obtain a mixed solution A; dissolving carbonate in pure water to obtain a solution B; the sand milling rotation speed is 1800-2500rpm, and the sand milling time is 0.5-2h; the proportion of the nickel source, the copper source and the manganese source is (0.01-0.03): (0.20-0.40): 0.60-0.80);
(2) Adding the solution A and the solution B in the step (1) into a reaction kettle filled with a base solution for coprecipitation reaction to obtain a carbonate precursor; during the coprecipitation reaction, the particle size is controlled to be 2-8um, the reaction temperature is controlled to be 40-70 ℃, the stirring speed is 400-800rpm, the reaction pH is 7-9, and the reaction time is 10-20h;
(3) Uniformly mixing the carbonate precursor obtained in the step (2) with CNTs, adding a sodium source, and calcining the mixture to obtain the anode material; the adding amount of the carbon source is 3-8% of the mass of the precursor.
The general formula of the cathode material is NaxNiCubMn (1-a-b) O2@ CNTs, wherein x is more than or equal to 0.5 and less than 1, a is more than or equal to 0.01 and less than 0.03, and 0.2< -b < -0.4.
The nickel source in the step (1) is one or more of nickel sulfate, nickel chloride, nickel nitrate or nickel acetate; the manganese source is one or more of manganese sulfate, manganese nitrate, manganese chloride, manganous manganic oxide or manganese acetate; the copper source is one or more of copper sulfate, copper oxide, cuprous oxide, copper chloride, copper nitrate or copper acetate; the carbonate precipitant is one or more of ammonium bicarbonate, sodium bicarbonate, ammonium carbonate and sodium carbonate.
In the step (1), the solid content of the material liquid used for sanding and refining is 20-60%; the carbonate in the solution B is supersaturated solution, and the concentration is 2.0-2.5mol/L.
The base solution in the step (2) is ammonium bicarbonate, and the concentration of the ammonium bicarbonate is 1.4-1.8mol/L.
In the step (3), the sodium source is any one or more of sodium hydroxide, sodium carbonate, sodium oxalate, sodium nitrite, disodium hydrogen phosphate, sodium bicarbonate, sodium citrate or sodium lactate.
The adding amount of the carbon source in the step (3) is 3-8% of the mass of the precursor; the addition amount of the sodium source is 50-80% of the mass of the precursor.
In the step (3), the sintering is carried out at the temperature rising rate of 2-4 ℃/min to 700-1000 ℃ and the heat preservation time is 4-6h.
And (3) making the buckle: assembling the obtained positive electrode material into a button cell, mixing the obtained positive electrode material with conductive carbon black and a binder PVDF according to the mass ratio of 8. Coating the slurry on an aluminum foil, vacuum drying and rolling to prepare a positive pole piece, taking a sodium metal piece as a negative pole and 1mol/L NaClO 4 The button cell was assembled in an argon-filled glove box using an Ethylene Carbonate (EC)/dimethyl carbonate (DMC) (volume ratio 1.
Compared with the prior art, the invention has the following advantages:
firstly, the preparation of the precursor is improved on the basis of the coprecipitation preparation method, the cyclic utilization rate of equipment can be improved, the process is simpler and environment-friendly, the preparation can be completed by one step, the synthesis method is simple and easy to operate, the synthesis period is short, and the method is suitable for large-scale production.
And secondly, the low nickel (the capacity of the anode material in the prior art is low, so the capacity needs to be improved by improving the addition amount of the nickel), the transmission channel of sodium ions is enlarged by introducing copper, the copper-manganese-based precursor has good ionic conductivity, the discharge specific capacity is improved), the nickel with a low proportion is used, the raw material cost is reduced, and the prepared anode material has a more stable structure. The introduction of copper enlarges the transmission channel of sodium ions, has good ionic conductivity, improves the specific discharge capacity, and solves the problems of poor electronic conductivity and low ion diffusion rate in the prior art. And the applicant finds that the electrochemical properties such as capacity, cycle and the like are not better than those of the low-nickel material when more nickel is added under the process condition.
Thirdly, the low-nickel copper manganese-based precursor is mixed with the carbon nano tube and then mixed with sodium salt for sintering, which can obviously hinder the promotion of the grain boundary of the active substance in the reaction process, maintain the stable structure of the crystal phase, reduce the contact between the anode material and the electrolyte by the sintered carbon nano tube, inhibit the occurrence of side reaction, have stable structure under the condition of high voltage, and improve the cycle performance of the material.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image and an element surface scanning image of the cathode material of the low-nickel copper manganese-based sodium-ion battery prepared in example 1;
FIG. 2 is a cycle chart of the cathode material for the low-nickel Cu-Mn-based Na-ion battery prepared in example 1;
FIG. 3 is a graph showing the rate performance of the cathode materials for low-nickel CuMnMn-based Na-ion batteries prepared in examples 1-6 and comparative examples 1-2.
Detailed Description
It should be noted that, in the present application, the embodiments and features of the embodiments may be combined with each other without conflict. For a further understanding of the invention, reference is made to the following description and specific preferred examples, which are not intended to limit the scope of the invention as claimed.
Example 1
The embodiment provides a low-nickel copper manganese-based sodium ion battery positive electrode material, and a preparation method of the positive electrode material comprises the following steps:
weighing nickel sulfate, copper oxide and manganese sulfate according to a molar ratio of 0.02; preparing 2.3mol/L ammonium bicarbonate as a precipitator and a complexing agent solution; preparing 1.7mol/L ammonium bicarbonate solution as a base solution. And adding the mixed metal solution and the ammonium bicarbonate supersaturated solution into the base solution through a peristaltic pump, controlling the proportion of the mixed metal salt to the ammonium bicarbonate precipitator to be 1. And (3) carrying out coprecipitation reaction for 15h, and carrying out suction filtration, hot water washing and drying after the reaction is finished to obtain a carbonate precursor.
And (2) uniformly mixing the precursor with 5% of carbon nano tubes, then adding 67% of sodium bicarbonate, uniformly mixing, heating the mixture from room temperature to 900 ℃ at the speed of 3 ℃/min in the air atmosphere, keeping the temperature for 5 hours, naturally cooling to room temperature, crushing, and sieving to obtain the low-nickel copper manganese-based sodium-ion battery cathode material.
Fig. 1 is a Scanning Electron Microscope (SEM) image and an elemental surface scan image of the cathode material for the low nickel copper manganese-based sodium ion battery prepared in example 1.
Example 2
Weighing the raw materials of nickel sulfate, copper sulfate and manganous-manganic oxide according to the molar ratio of 0.05; preparing 2.3mol/L ammonium bicarbonate as a precipitator and a complexing agent solution; 1.7mol/L ammonium bicarbonate solution is prepared as a base solution. And (2) adding the mixed metal solution and the ammonium bicarbonate supersaturated solution into the base solution through a peristaltic pump, controlling the proportion of the mixed metal salt to the ammonium bicarbonate precipitator to be 1. And (3) carrying out coprecipitation reaction for 15h, and carrying out suction filtration, hot water washing and drying after the reaction is finished to obtain a carbonate precursor.
And (2) uniformly mixing the precursor with 3% of carbon nano tubes, then adding 67% of sodium bicarbonate, uniformly mixing, heating the mixture from room temperature to 800 ℃ at the speed of 3 ℃/min in the air atmosphere, keeping the temperature for 6 hours, naturally cooling to room temperature, crushing, and sieving to obtain the low-nickel copper manganese-based sodium-ion battery cathode material.
Example 3
Weighing the nickel sulfate, the copper oxide and the manganese sulfate according to a molar ratio of 0.02 to 0.53, dissolving the raw materials in pure water to prepare a solution with a solid content of 30%, and performing sand grinding and refining, wherein the rotation speed of a sand mill is 2000rpm, and the time is 1.5h; preparing 2.1mol/L ammonium bicarbonate as a precipitator and a complexing agent solution; 1.7mol/L ammonium carbonate solution is prepared as a base solution. And adding the mixed metal solution and the ammonium bicarbonate supersaturated solution into the base solution through a peristaltic pump, controlling the proportion of the mixed metal salt to the ammonium bicarbonate precipitator to be 1. And (3) coprecipitation reaction is carried out for 5 hours, and after the reaction is finished, a carbonate precursor is obtained through suction filtration, hot water washing and drying.
And (2) uniformly mixing the precursor with 1% glucose, adding 100% sodium bicarbonate, uniformly mixing, heating the mixture from room temperature to 500 ℃ at the speed of 5 ℃/min in the air atmosphere, keeping the temperature for 10 hours, naturally cooling to room temperature, crushing, and sieving to obtain the low-nickel copper manganese-based sodium-ion battery positive electrode material.
Example 4
Weighing the raw materials of nickel sulfate, copper oxide and manganese sulfate according to a molar ratio of 0.1 to 0.23, dissolving the raw materials in pure water to prepare a solution with a solid content of 40%, and performing sand grinding and refining, wherein the rotation speed of a sand mill is 2000rpm, and the time is 0.5h; preparing 2.6mol/L ammonium bicarbonate as a precipitator and a complexing agent solution; preparing 2.0mol/L ammonium bicarbonate solution as a base solution. And (2) adding the mixed metal solution and the ammonium bicarbonate supersaturated solution into the base solution through a peristaltic pump, controlling the proportion of the mixed metal salt to the ammonium bicarbonate precipitator to be 1.5, controlling the particle size to be 10 mu m, controlling the pH value to be about 8, stirring at 900rpm, and controlling the temperature to be 80 ℃. And (3) carrying out coprecipitation reaction for 25h, and carrying out suction filtration, hot water washing and drying after the reaction is finished to obtain a carbonate precursor.
And (2) uniformly mixing the precursor with 10% of sucrose, adding 33% of sodium carbonate, uniformly mixing, heating the mixture from room temperature to 1100 ℃ at the speed of 4 ℃/min in the air atmosphere, keeping the temperature for 3 hours, naturally cooling to room temperature, crushing, and sieving to obtain the low-nickel copper manganese-based sodium-ion battery cathode material.
Example 5
Weighing the raw materials of nickel sulfate, copper oxide and manganese chloride according to a molar ratio of 0.1 to 0.05, dissolving the raw materials in pure water to prepare a solution with a solid content of 50%, and performing sand grinding and refining, wherein the rotation speed of a sand mill is 1500rpm, and the time is 2.5h; preparing 2.4mol/L ammonium bicarbonate as a precipitator and a complexing agent solution; preparing 1.0mol/L ammonium bicarbonate solution as a base solution. And adding the mixed metal solution and the ammonium bicarbonate supersaturated solution into the base solution through a peristaltic pump, controlling the proportion of the mixed metal salt to the ammonium bicarbonate precipitator to be 1. And (3) carrying out coprecipitation reaction for 30h, and carrying out suction filtration, hot water washing and drying after the reaction is finished to obtain a carbonate precursor.
And (2) uniformly mixing the precursor with 9% glucose, adding 67% sodium carbonate, uniformly mixing, heating the mixture from room temperature to 900 ℃ at the speed of 2 ℃/min in the air atmosphere, keeping the temperature for 6h, naturally cooling to room temperature, crushing, and sieving to obtain the low-nickel copper manganese-based sodium-ion battery cathode material.
Example 6
Weighing nickel nitrate, copper oxide and manganese sulfate according to a molar ratio of 0.005; preparing 1.8mol/L ammonium bicarbonate as a precipitator and a complexing agent solution; preparing 1.5mol/L ammonium bicarbonate solution as a base solution. And adding the mixed metal solution and the ammonium bicarbonate supersaturated solution into the base solution through a peristaltic pump, controlling the proportion of the mixed metal salt to the ammonium bicarbonate precipitator to be 1. And (3) carrying out coprecipitation reaction for 15h, and carrying out suction filtration, hot water washing and drying after the reaction is finished to obtain a carbonate precursor.
And (2) uniformly mixing the precursor with 6% of carbon nano tubes, adding 75% of sodium carbonate, uniformly mixing, heating the mixture from room temperature to 800 ℃ at the speed of 3 ℃/min in the air atmosphere, keeping the temperature for 7h, naturally cooling to room temperature, crushing, and sieving to obtain the low-nickel copper manganese-based sodium ion battery cathode material.
Comparative example 1
The comparative example differs from example 1 only in that no nickel source was added during compounding, and the specific experimental conditions are as follows.
Weighing raw materials of copper oxide and manganese sulfate according to a molar ratio of 0.31 to 0.69, dissolving the raw materials in pure water to prepare a solution with a solid content of 40%, and carrying out sand grinding and refining, wherein the rotation speed of a sand mill is 2000rpm, and the time is 1.0h; preparing 2.3mol/L ammonium bicarbonate as a precipitator and a complexing agent solution; 1.7mol/L ammonium bicarbonate solution is prepared as a base solution. And adding the mixed metal solution and the ammonium bicarbonate supersaturated solution into the base solution through a peristaltic pump, controlling the proportion of the mixed metal salt to the ammonium bicarbonate precipitator to be 1. And (3) carrying out coprecipitation reaction for 15h, and carrying out suction filtration, hot water washing and drying after the reaction is finished to obtain a carbonate precursor.
And (2) uniformly mixing the precursor with 5% of carbon nanotubes, adding 67% of sodium bicarbonate, uniformly mixing, heating the mixture from room temperature to 900 ℃ at the speed of 3 ℃/min in the air atmosphere, keeping the temperature for 5 hours, naturally cooling to room temperature, crushing, and sieving to obtain the copper-manganese-based sodium-ion battery positive electrode material.
Comparative example 2
This comparative example differs from example 1 only in that no copper source was added at the time of compounding, and the specific experimental conditions are as follows.
Weighing raw materials according to a molar ratio of 0.02 to 0.98, dissolving the raw materials in pure water to prepare a solution with a solid content of 40%, and carrying out sand grinding and refining, wherein the rotation speed of a sand grinder is 2000rpm, and the time is 1.0h; preparing 2.3mol/L ammonium bicarbonate as a precipitator and a complexing agent solution; preparing 1.7mol/L ammonium bicarbonate solution as a base solution. And adding the mixed metal solution and the ammonium bicarbonate supersaturated solution into the base solution through a peristaltic pump, controlling the proportion of the mixed metal salt to the ammonium bicarbonate precipitator to be 1. And (3) carrying out coprecipitation reaction for 15 hours, and carrying out suction filtration, hot water washing and drying after the reaction is finished to obtain a carbonate precursor.
And (2) uniformly mixing the precursor with 5% of carbon nano tubes, adding 67% of sodium bicarbonate, uniformly mixing, heating the mixture from room temperature to 900 ℃ at the speed of 3 ℃/min in the air atmosphere, keeping the temperature for 5 hours, naturally cooling to room temperature, crushing, and sieving to obtain the low-nickel manganese-based sodium-ion battery cathode material.
Comparative example 3
This comparative example differs from example 1 only in that no carbon nanotubes were added before the precursor was mixed with the sodium source, and the specific experimental conditions were as follows.
Weighing the raw materials of nickel sulfate, copper oxide and manganese sulfate according to a molar ratio of 0.02; preparing 2.3mol/L ammonium bicarbonate as a precipitator and a complexing agent solution; 1.7mol/L ammonium bicarbonate solution is prepared as a base solution. And (2) adding the mixed metal solution and the ammonium bicarbonate supersaturated solution into the base solution through a peristaltic pump, controlling the proportion of the mixed metal salt to the ammonium bicarbonate precipitator to be 1. And (3) carrying out coprecipitation reaction for 15 hours, and carrying out suction filtration, hot water washing and drying after the reaction is finished to obtain a carbonate precursor.
And (3) uniformly mixing the precursor with 67% sodium bicarbonate, heating the mixture from room temperature to 900 ℃ at the speed of 3 ℃/min in the air atmosphere, preserving the heat for 5 hours, naturally cooling to room temperature, crushing, and sieving to obtain the low-nickel copper manganese-based sodium-ion battery anode material.
Comparative example 4
The comparative example is different from example 1 only in that the carbon nanotubes are added after the precursor and the sodium source are uniformly mixed, and the specific experimental conditions are as follows.
Weighing the raw materials of nickel sulfate, copper oxide and manganese sulfate according to a molar ratio of 0.02; preparing 2.3mol/L ammonium bicarbonate as a precipitator and a complexing agent solution; preparing 1.7mol/L ammonium bicarbonate solution as a base solution. And adding the mixed metal solution and the ammonium bicarbonate supersaturated solution into the base solution through a peristaltic pump, controlling the proportion of the mixed metal salt to the ammonium bicarbonate precipitator to be 1. And (3) carrying out coprecipitation reaction for 15h, and carrying out suction filtration, hot water washing and drying after the reaction is finished to obtain a carbonate precursor.
And (2) uniformly mixing the precursor with 67% sodium bicarbonate, adding 5% carbon nanotubes, uniformly mixing, heating the mixture from room temperature to 900 ℃ at the speed of 3 ℃/min in the air atmosphere, keeping the temperature for 5 hours, naturally cooling to room temperature, crushing, and sieving to obtain the low-nickel copper manganese-based sodium-ion battery cathode material.
TABLE 1
| Numbering | Specific capacity for first charge (mAh/g) | Specific capacity of first discharge (mAh/g) | First charge-discharge efficiency (%) |
| Example 1 | 140.61 | 128.71 | 91.54 |
| Example 2 | 136.42 | 116.09 | 85.10 |
| Example 3 | 134.51 | 113.69 | 84.52 |
| Example 4 | 135.12 | 107.66 | 79.68 |
| Example 5 | 120.44 | 97.86 | 81.25 |
| Example 6 | 101.91 | 88.14 | 86.49 |
| Comparative example 1 | 96.14 | 82.43 | 85.74 |
| Comparative example 2 | 82.43 | 71.49 | 86.73 |
| Comparative example 3 | 73.64 | 58.55 | 79.51 |
| Comparative example 4 | 80.13 | 65.18 | 81.34 |
The button cells prepared from the positive electrode materials in examples 1-6 and comparative examples 1-4 were tested by a blue tester with a voltage range of 2.0-4.5v and a charge-discharge activation cycle of 0.1c to obtain a first charge-discharge specific capacity and a first coulombic efficiency, and the test results are shown in table 1. And then, charging at a constant current and a constant voltage of 0.5C, discharging at a constant current of 0.05C at a cut-off current of 1C, and circulating for 50 circles to respectively obtain related data of parameters such as the discharge capacity at the 50 th circle, the capacity retention rate at the 50 th circle and the like. The test results are shown in fig. 2. Multiplying power tests are carried out on the button cells prepared from the positive electrode materials in the examples 1-6 and the comparative examples 1-2 by using a blue tester, the voltage range is 2.0-4.5V, constant-current and constant-voltage charging is carried out at the current of 0.5C, and the charging cut-off current is 0.05C; constant current discharge was performed at 0.1C, 0.2C, 0.5C, 1C, 5C, 10C, and 0.1C currents, respectively, with a discharge cutoff voltage of 2V. The test results are shown in fig. 3.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (7)
1. The preparation method of the low-nickel copper manganese-based sodium ion battery positive electrode material is characterized by comprising the following steps of:
(1) Adding a nickel source, a manganese source and a copper source into pure water, and performing sand grinding and refining to obtain a mixed solution A; dissolving carbonate in pure water to obtain a solution B; the sanding rotating speed is 1800-2500rpm, and the sanding time is 0.5-2h; the proportion of the nickel source, the copper source and the manganese source is (0.01-0.03): (0.20-0.40): 0.60-0.80);
(2) Adding the solution A and the solution B in the step (1) into a reaction kettle filled with a base solution for coprecipitation reaction to obtain a carbonate precursor; during the coprecipitation reaction, the particle size is controlled to be 2-8um, the reaction temperature is controlled to be 40-70 ℃, the stirring speed is 400-800rpm, the reaction pH is 7-9, and the reaction time is 10-20h;
(3) Uniformly mixing the carbonate precursor obtained in the step (2) with CNTs, adding a sodium source, and calcining the mixture to obtain the anode material; the adding amount of the carbon source is 3-8% of the mass of the precursor;
the general formula of the cathode material is Na x Ni a Cu b Mn (1-a-b) O 2 @ CNTs, where x is 0.5. Ltoreq.<1，0.01≤a<0.03，0.2<b<0.4。
2. The method for preparing the positive electrode material of the low-nickel copper manganese-based sodium-ion battery according to claim 1, which is characterized by comprising the following steps of: the nickel source in the step (1) is one or more of nickel sulfate, nickel chloride, nickel nitrate or nickel acetate; the manganese source is one or more of manganese sulfate, manganese nitrate, manganese chloride, mangano-manganic oxide or manganese acetate; the copper source is one or more of copper sulfate, copper oxide, cuprous oxide, copper chloride, copper nitrate or copper acetate; the carbonate precipitant is one or more of ammonium bicarbonate, sodium bicarbonate, ammonium carbonate and sodium carbonate.
3. The method for preparing the positive electrode material of the low-nickel copper manganese-based sodium-ion battery according to claim 1, which is characterized by comprising the following steps of: in the step (1), the solid content of the material liquid used for sanding and refining is 20-60%; the carbonate in the solution B is supersaturated solution, and the concentration is 2.0-2.5mol/L.
4. The method for preparing the positive electrode material of the low-nickel copper manganese-based sodium-ion battery according to claim 1, which is characterized by comprising the following steps of: the base solution in the step (2) is ammonium bicarbonate, and the concentration of the ammonium bicarbonate is 1.4-1.8mol/L.
5. The method for preparing the positive electrode material of the low-nickel copper manganese-based sodium-ion battery according to claim 1, which is characterized by comprising the following steps of: in the step (3), the sodium source is any one or more of sodium hydroxide, sodium carbonate, sodium oxalate, sodium nitrite, disodium hydrogen phosphate, sodium bicarbonate, sodium citrate or sodium lactate.
6. The method for preparing the positive electrode material of the low-nickel copper manganese-based sodium-ion battery according to claim 1, which is characterized by comprising the following steps of: the adding amount of the carbon source in the step (3) is 3-8% of the mass of the precursor; the addition amount of the sodium source is 50-80% of the mass of the precursor.
7. The method for preparing the positive electrode material of the low-nickel copper manganese-based sodium-ion battery according to claim 1, which is characterized by comprising the following steps of: in the step (3), the sintering is carried out at the temperature rising rate of 2-4 ℃/min to 700-1000 ℃ and the heat preservation time is 4-6h.
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| CN116885198A (en) * | 2023-09-08 | 2023-10-13 | 浙江帕瓦新能源股份有限公司 | Precursor, preparation method, positive electrode material and sodium ion battery |
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| CN116885198B (en) * | 2023-09-08 | 2023-12-08 | 浙江帕瓦新能源股份有限公司 | Precursor, preparation method, positive electrode material and sodium ion battery |
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