CN114906881A - Preparation method of cation-substituted modified spherical-like sodium nickel manganese oxide positive electrode material - Google Patents
Preparation method of cation-substituted modified spherical-like sodium nickel manganese oxide positive electrode material Download PDFInfo
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Abstract
The invention relates to the technical field of preparation of solid electrolyte materials of sodium ion batteries, in particular to a preparation method of cation-substituted modified spherical-like sodium nickel manganese oxide. The invention discloses a preparation method of cation-substituted modified nickel sodium manganate, which comprises the steps of carrying out coprecipitation reaction on soluble nickel manganese metal salt, soluble substituted metal M salt and a carbonate precipitation complexing agent to obtain a sphere-like carbonate precursor, calcining the carbonate precursor to obtain a layered oxide precursor, uniformly mixing the layered oxide precursor with sodium salt, and calcining to obtain the cation-substituted nickel sodium manganate anode material. The substituted and modified sodium nickel manganese oxide anode material prepared by the method has excellent cycle performance, rate capability and high specific discharge capacity.
Description
Technical Field
The invention relates to the technical field of preparation of solid electrolyte materials of sodium ion batteries, in particular to cation-substituted modified spherical-like sodium nickel manganese oxide (Na) 0.67 Ni 0.33 Mn 0.67 O 2 ) The preparation method of (1).
Background
Although the lithium ion battery is the main mode of electrochemical energy storage at present, the lithium ion battery has the characteristics of high energy density, good cycle performance, energy conservation, environmental protection, no memory effect and the like, so that the lithium ion battery is favored by the market and has wide application. Although the development prospect of the lithium ion battery is far, the market demand is increasing day by day, the shortage of domestic lithium resources and the rising of price are a big problem to be faced in the future, and a novel efficient and low-price new energy storage system is required to be searched. And sodium has similar physical and chemical properties with lithium, is rich in reserve and low in cost, and is expected to replace the large-scale application of lithium ion batteries in the energy storage field with low energy density requirements. In addition, the electrode potential of the sodium ion battery is relatively high, so that the selection range of the electrolyte is wider, and the electrolyte solvent and the electrolyte salt with lower decomposition potential can be utilized; the use of sodium ion batteries has more stable electrochemical performance relative to lithium ion batteries.
However, since the radius of the sodium ions is larger than that of the lithium ions, the sodium ion battery will experience more resistance to the deintercalation of the sodium ions during the charge and discharge cycles. It is therefore important to find suitable electrode materials. Among them, as a typical representative material of the transition metal layered oxide, a P2-type layered oxide has attracted much attention because of its advantages such as high operating voltage, high specific capacity, and stable structure. But irreversible phase change can be generated during the circulation process of the oxide, and the capacity and the circulation performance are further attenuated. At present, research on improving the electrochemistry of materials mainly focuses on methods such as doping substitution, morphological structure design, coating and the like.
CN113845158A discloses a preparation method of a porous spherical nickel sodium manganate anode material, and the porous spherical nickel sodium manganate (Na) is prepared x Ni y Mn 1-y O 2 ) The anode material improves the large-rate discharge stability of the material, but the material is carried out in a low-voltage interval (2-4.15V), and the first discharge specific capacity is lower than 100mAh/g under the 1C rate. According to the invention, cation substitution modification is carried out during synthesis of the precursor by a coprecipitation method, the process is simple and controllable, the repeatability is high, large-scale production can be realized, coating modification is not required after sintering, and the prepared modified sodium nickel manganese oxide anode material has excellent cycle performance, rate capability and high specific discharge capacity. Has good reference value for large-scale production of the positive electrode material of the sodium-ion battery.
Disclosure of Invention
The invention hopes to provide a preparation method of a cation-substituted modified spherical-like sodium nickel manganese oxide positive electrode material, and the specific scheme is as follows:
a preparation method of a cation-substituted modified spherical-like sodium nickel manganese oxide positive electrode material comprises the following steps:
(1) dissolving soluble nickel salt, manganese salt and substituted metal M salt in pure water according to a certain proportion to obtain a mixed salt solution A; dissolving carbonate in pure water to obtain a solution B;
(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 spheroidal carbonate precursor; during the coprecipitation reaction, the particle size is controlled to be 3-20um, the reaction temperature is controlled to be 40-70 ℃, the stirring speed is 400-1200rpm, the reaction pH is 7-9, and the reaction time is 50-120 h; before the particles are 10 mu m, controlling the pH value to be 7.5 +/-0.2 in the reaction process, controlling the reaction temperature to be 50 ℃ and controlling the stirring speed to be 550 r/min; when the particle size is between 10 and 20 mu m, controlling the pH value in the reaction process to be 8.0 +/-0.2, the reaction temperature to be 60 ℃, and the stirring speed to be 700 r/min;
(3) calcining the sphere-like carbonate precursor obtained in the step (2) to obtain a layered oxide precursor;
(4) uniformly mixing the oxide precursor obtained in the step (3) with sodium salt, and calcining to obtain the substituted and modified sodium nickel manganese oxide anode material;
the structural formula of the sodium nickel manganese oxide cathode material is Na 0.67 Ni 0.33 Mn 0.67 O 2 。
The soluble nickel salt in the step (1) is one or more of nickel sulfate, nickel chloride, nickel nitrate or nickel acetate.
The manganese salt in the step (1) is one or more of manganese sulfate, manganese nitrate, manganese chloride or manganese acetate.
The substituted metal M salt in the step (1) is one or more of copper sulfate/cobalt/yttrium/magnesium/molybdenum, copper nitrate/cobalt/yttrium/magnesium/molybdenum and copper chloride/cobalt/yttrium/magnesium/molybdenum.
The carbonate precipitant is ammonium bicarbonate.
The concentration of the metal ions in the solution A in the step (1) is 0.1-1mol/L, the molar ratio of nickel, manganese and the substituted metal cations M is (0.33-x):0.67: x, wherein x is 0.02-0.2, and the carbonate in the obtained solution B is a supersaturated solution with the concentration of about 2.7 mol/L.
The base solution in the step (2) is ammonium bicarbonate, and the concentration of the ammonium bicarbonate is 0.1-1.0 mol/L.
And (3) controlling the molar ratio of the metal salt to the carbonate to be 1:2 during the coprecipitation reaction in the step (2).
The sodium salt in the step (4) is one or more of sodium carbonate, sodium bicarbonate and sodium hydroxide.
The invention mainly provides cation (M) substituted modified sodium nickel manganese oxide (Na) 0.67 Ni 0.33 Mn 0.67 O 2 ) A preparation method of the cathode material. According to the method, soluble nickel manganese metal salt, soluble substituted metal M salt and carbonate precipitation complexing agent are subjected to coprecipitation reaction to obtain a spherical-like carbonate precursor, the carbonate precursor is calcined to obtain a layered oxide precursor, and the layered oxide precursor and sodium salt are uniformly mixed and calcined to obtain the required nickel sodium manganate anode material. The method has simple and controllable process and high repeatability, can be used for large-scale production, and the prepared sodium nickel manganese oxide cathode material has excellent cycle performance, rate capability and high energy density. Has good reference value for large-scale production of the positive electrode material of the sodium-ion battery.
Compared with the prior art, the invention has the advantages that:
firstly, the shape of the sodium nickel manganese oxide anode material in the prior art is mostly irregular block-shaped, the tap density of the material is lower, and the multiplying power performance of the material with a hollow shape is poorer. The sodium nickel manganese oxide cathode material with the spherical-like structure prepared by the invention has high tap density, is easy to produce in a large scale, has high mechanical strength, has a stable structure in the charge-discharge cycle process, and is not easy to have the phenomena of structural collapse or pulverization and the like, namely the material has good cycle performance. Specifically, the invention controls the coprecipitation regulation and the particle size between 10-20um, so that the degree of crystallinity of the sphere-like inner crystal nucleus is higher than 80%, and the degree of crystallinity of the outer layer is slightly lower than 50% under the influence of the particle size on the basis of the crystal nucleus.
Secondly, the nickel manganese acid is partially replaced by metal elementsOne or more of nickel and manganese in sodium can change charge distribution in the material and destroy Na + The ordering of the vacancy and the inhibition of the occurrence of phase change enable the material to have good cycle stability under a high voltage platform (2-4.5V), good rate capability and high specific discharge capacity. For example, the specific discharge capacity of 101.98mAh/g is still remained after 100 cycles of circulation at 0.5C (1C is 170mA/g) in the range of 2-4.5V, and the first specific discharge capacity is as high as 134.18 mAh/g.
And thirdly, the modified precursor is prepared by adopting a preparation method based on commercial coprecipitation, so that the synthesis cost is low, the process is simple, continuous production can be realized, the method is suitable for large-scale production, and the method has a commercial prospect for large-scale production of the sodium-ion battery anode material.
Drawings
FIG. 1 is an SEM image of a sodium nickel manganese oxide cathode material prepared in a comparative example;
FIG. 2 is an XRD pattern of comparative example and examples 1-5;
FIG. 3 is a graph showing short cycle curves of button cells composed of the sodium nickel manganese oxide positive electrode materials prepared in comparative example and examples 1-6 at different multiplying factors within a voltage range of 2-4.5V;
fig. 4 is a graph comparing the cycling curves of button cells composed of the sodium nickel manganese oxide positive electrode material prepared in comparative example and example 1 in the voltage interval of 2-4.5V and at 0.5C.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and all the technologies realized based on the above subject matter of the present invention are within the scope of the present invention.
Comparative example 1
Weighing raw materials of manganese sulfate and nickel sulfate according to a molar ratio of 2:1, and dissolving the raw materials in pure water to prepare 2mol/L mixed metal salt solution; preparing 2.7mol/L ammonium bicarbonate supersaturated solution as a precipitator and a complexing agent solution; preparing 0.7mol/L ammonium bicarbonate solution as a base solution. And adding the mixed metal salt solution and the ammonium bicarbonate supersaturated solution into the mixed base solution through a peristaltic pump, controlling the ratio of the mixed metal salt to the ammonium bicarbonate precipitator to be 1:2, controlling the pH value to be about 8, stirring at the speed of 900r/min and the temperature to be 50 ℃. And (3) carrying out coprecipitation reaction for 100h, and carrying out suction filtration, hot water washing and drying after the reaction is finished to obtain the spherical nickel-manganese binary carbonate precursor.
And (3) heating the precursor from room temperature to 600 ℃ at the heating rate of 5 ℃/min, and calcining for 5h to obtain the nickel-manganese binary oxide precursor. Then uniformly mixing the sieved oxide precursor and sodium carbonate according to the molar ratio of 1:1.05, putting the mixture into a muffle furnace, heating the mixture from room temperature to 600 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 5 hours, heating the mixture to 900 ℃, and calcining the mixture for 12 hours to obtain the spherical sodium nickel manganese oxide cathode material (Na) 0.67 Ni 0.33 Mn 0.67 O 2 )。
Comparative example 2
Weighing raw materials of manganese sulfate and nickel sulfate according to a molar ratio of 1:2, and dissolving the raw materials in pure water to prepare 2mol/L mixed metal salt solution; preparing 2.7mol/L ammonium bicarbonate supersaturated solution as a precipitator and a complexing agent solution; preparing 0.7mol/L ammonium bicarbonate solution as a base solution. And adding the mixed metal salt solution and the ammonium bicarbonate supersaturated solution into the mixed base solution through a peristaltic pump, controlling the ratio of the mixed metal salt to the ammonium bicarbonate precipitator to be 1:2, controlling the pH value to be about 8, stirring at the speed of 900r/min and the temperature to be 50 ℃. And (3) carrying out coprecipitation reaction for 100h, and carrying out suction filtration, hot water washing and drying after the reaction is finished to obtain the spherical nickel-manganese binary carbonate precursor.
And (3) heating the precursor from room temperature to 600 ℃ at the heating rate of 5 ℃/min, and calcining for 5h to obtain the nickel-manganese binary oxide precursor. Then uniformly mixing the sieved oxide precursor and sodium carbonate according to the molar ratio of 1:1.05, putting the mixture into a muffle furnace, heating the mixture from room temperature to 600 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 5h, heating the mixture to 900 ℃, and calcining the mixture for 12h to obtain the spherical-structure sodium nickel manganese oxide positive electrode material (Na) 0.67 Ni 0.33 Mn 0.67 O 2 )。
Example 1
Weighing raw materials of manganese sulfate, nickel sulfate and copper sulfate according to the molar ratio of Mn, Ni and Cu metal elements of 0.67 to 0.26 to 0.07, and dissolving the raw materials in pure water to prepare 2mol/L mixed metal salt solution; preparing 2.7mol/L ammonium bicarbonate supersaturated solution as precipitant solution; 0.7mol/L ammonium bicarbonate solution is prepared as a base solution. And adding the mixed metal salt solution and the ammonium bicarbonate precipitant solution into the mixed base solution by a peristaltic pump, controlling the ratio of the mixed metal salt to the ammonium bicarbonate precipitant solution to be 1:2, controlling the pH value to be about 8, stirring at the speed of 900r/min and the temperature to be 50 ℃. Carrying out coprecipitation reaction for 100h, controlling the particle size to be 10-20um, controlling the reaction temperature to be 50-70 ℃, controlling the stirring speed to be 400-1200rpm, controlling the reaction pH to be 7-9, controlling the reaction process pH to be 7.5 +/-0.2 when the reaction time is 4-20h before the particles are 10 mu m, controlling the reaction temperature to be 50 ℃ and controlling the stirring speed to be 550 r/min; when the particle size is between 10 and 20 mu m, controlling the pH value in the reaction process to be 8.0 +/-0.2, the reaction temperature to be 60 ℃, the stirring speed to be 700r/min, and obtaining the spherical nickel-copper-manganese carbonate precursor after the reaction is finished through suction filtration, hot water washing and drying.
And (3) heating the precursor from room temperature to 600 ℃ at the heating rate of 5 ℃/min, and calcining for 5h to obtain the nickel-copper-manganese oxide precursor. Then uniformly mixing the sieved oxide precursor and sodium carbonate according to the molar ratio of 1:1.05, putting the mixture into a muffle furnace, heating the mixture from room temperature to 600 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 5h, heating the mixture to 900 ℃, and calcining the mixture for 12h to obtain the copper-partially-substituted and modified sodium nickel manganese oxide positive electrode material (Na) 0.67 Ni 0.26 Cu 0.07 Mn 0.67 O 2 )。
Example 2
Weighing raw materials of manganese sulfate, nickel sulfate and magnesium sulfate according to the molar ratio of Mn, Ni and Mg metal elements of 0.67 (0.21:0.12), and dissolving the raw materials in pure water to prepare 2mol/L mixed metal salt solution; preparing 2.7mol/L ammonium bicarbonate supersaturated solution as precipitant solution; preparing 0.7mol/L ammonium bicarbonate solution as a base solution. And adding the mixed metal salt solution and the ammonium bicarbonate precipitant solution into the mixed base solution by a peristaltic pump, controlling the ratio of the mixed metal salt to the ammonium bicarbonate precipitant solution to be 1:2, controlling the pH value to be about 8, stirring at the speed of 900r/min and the temperature to be 50 ℃. Carrying out coprecipitation reaction for 100h, controlling the particle size to be 10-20um, controlling the reaction temperature to be 50-70 ℃, controlling the stirring speed to be 400-1200rpm, controlling the reaction pH to be 7-9, controlling the reaction process pH to be 7.5 +/-0.2 when the reaction time is 4-20h before the particles are 10 mu m, controlling the reaction temperature to be 50 ℃ and controlling the stirring speed to be 550 r/min; when the particle size is between 10 and 20 mu m, controlling the pH value in the reaction process to be 8.0 +/-0.2, the reaction temperature to be 60 ℃, the stirring speed to be 700r/min, and obtaining the spherical nickel-copper-manganese carbonate precursor after the reaction is finished through suction filtration, hot water washing and drying.
And (3) heating the precursor from room temperature to 600 ℃ at the heating rate of 5 ℃/min, and calcining for 5h to obtain the nickel-copper-manganese oxide precursor. Then uniformly mixing the sieved oxide precursor and sodium carbonate according to the molar ratio of 1:1.05, putting the mixture into a muffle furnace, heating the mixture from room temperature to 600 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 5h, heating the mixture to 900 ℃, and calcining the mixture for 12h to obtain the nickel sodium manganate positive electrode material (Na) with Mg partially substituted and modified 0.67 Ni 0.21 Mg 0.12 Mn 0.67 O 2 )。
Example 3
Weighing raw materials of manganese sulfate, cobalt sulfate and nickel sulfate according to the molar ratio (0.56:0.11) to 0.33 of Mn, Al and Ni metal elements, and dissolving the raw materials in pure water to prepare 2mol/L mixed metal salt solution; preparing 2.7mol/L ammonium bicarbonate supersaturated solution as precipitant solution; preparing 0.7mol/L ammonium bicarbonate solution as a base solution. And adding the mixed metal salt solution and the ammonium bicarbonate precipitant solution into the mixed base solution by a peristaltic pump, controlling the ratio of the mixed metal salt to the ammonium bicarbonate precipitant solution to be 1:2, controlling the pH value to be about 8, stirring at the speed of 900r/min and the temperature to be 50 ℃. The coprecipitation reaction is carried out for 100 hours, the particle size is controlled to be 10-20um, the reaction temperature is controlled to be 50-70 ℃, the stirring speed is 400-1200rpm, the reaction pH is 7-9, the reaction time is 4-20 hours before the particle size is 10 um, the reaction process pH is controlled to be 7.5 +/-0.2, the reaction temperature is 50 ℃, and the stirring speed is 550 r/min; when the particle size is between 10 and 20 mu m, controlling the pH value to be 8.0 +/-0.2 in the reaction process, controlling the reaction temperature to be 60 ℃, stirring at 700r/min, and after the reaction is finished, carrying out suction filtration, hot water washing and drying to obtain the spherical nickel-copper-manganese carbonate precursor.
And (3) heating the precursor from room temperature to 600 ℃ at the heating rate of 5 ℃/min, and calcining for 5h to obtain the nickel-copper-manganese oxide precursor. Then uniformly mixing the sieved oxide precursor and sodium carbonate according to the molar ratio of 1:1.05, putting the mixture into a muffle furnace, heating the mixture from room temperature to 600 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 5h, heating the mixture to 900 ℃, and calcining the mixture for 12h to obtain the Co partially substituted and modified sodium nickel manganese oxide cathode material (Na) 0.67 Ni 0.33 Mn 0.56 Al 0.11 O 2 )。
Example 4
Weighing raw materials of manganese sulfate, aluminum sulfate and nickel sulfate according to the molar ratio of Mn, Co and Ni metal elements of 0.67 (0.165:0.165), and dissolving the raw materials in pure water to prepare 2mol/L mixed metal salt solution; preparing 2.7mol/L ammonium bicarbonate supersaturated solution as precipitant solution; preparing 0.7mol/L ammonium bicarbonate solution as a base solution. And adding the mixed metal salt solution and the ammonium bicarbonate precipitant solution into the mixed base solution by a peristaltic pump, controlling the ratio of the mixed metal salt to the ammonium bicarbonate precipitant solution to be 1:2, controlling the pH value to be about 8, stirring at the speed of 900r/min and the temperature to be 50 ℃. The coprecipitation reaction is carried out for 100 hours, the particle size is controlled to be 10-20um, the reaction temperature is controlled to be 50-70 ℃, the stirring speed is 400-1200rpm, the reaction pH is 7-9, the reaction time is 4-20 hours before the particle size is 10 um, the reaction process pH is controlled to be 7.5 +/-0.2, the reaction temperature is 50 ℃, and the stirring speed is 550 r/min; when the particle size is between 10 and 20 mu m, controlling the pH value in the reaction process to be 8.0 +/-0.2, the reaction temperature to be 60 ℃, the stirring speed to be 700r/min, and obtaining the spherical nickel-copper-manganese carbonate precursor after the reaction is finished through suction filtration, hot water washing and drying.
And (3) heating the precursor from room temperature to 600 ℃ at the heating rate of 5 ℃/min, and calcining for 5h to obtain the nickel-copper-manganese oxide precursor. Then uniformly mixing the sieved oxide precursor and sodium carbonate according to the molar ratio of 1:1.05, putting the mixture into a muffle furnace, heating the mixture from room temperature to 600 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 5h, heating the mixture to 900 ℃, and calcining the mixture for 12h to obtain the Al partially substituted and modified sodium nickel manganese oxide cathode material (Na) 0.67 Ni 0.165 Co 0.165 Mn 0.33 O 2 )。
Example 5
Weighing raw materials of manganese sulfate, aluminum sulfate and nickel sulfate according to the molar ratio (0.56:0.11) to (0.165:0.165) of Mn, Al, Ni and Co metal elements, and dissolving the raw materials in pure water to prepare 2mol/L mixed metal salt solution; preparing 2.7mol/L ammonium bicarbonate supersaturated solution as precipitant solution; preparing 0.7mol/L ammonium bicarbonate solution as a base solution. And adding the mixed metal salt solution and the ammonium bicarbonate precipitant solution into the mixed base solution by a peristaltic pump, controlling the ratio of the mixed metal salt to the ammonium bicarbonate precipitant solution to be 1:2, controlling the pH value to be about 8, stirring at the speed of 900r/min and the temperature to be 50 ℃. Carrying out coprecipitation reaction for 100h, controlling the particle size to be 10-20um, controlling the reaction temperature to be 50-70 ℃, controlling the stirring speed to be 400-1200rpm, controlling the reaction pH to be 7-9, controlling the reaction process pH to be 7.5 +/-0.2 when the reaction time is 4-20h before the particles are 10 mu m, controlling the reaction temperature to be 50 ℃ and controlling the stirring speed to be 550 r/min; when the particle size is between 10 and 20 mu m, controlling the pH value in the reaction process to be 8.0 +/-0.2, the reaction temperature to be 60 ℃, the stirring speed to be 700r/min, and obtaining the spherical nickel-copper-manganese carbonate precursor after the reaction is finished through suction filtration, hot water washing and drying.
And (3) heating the precursor from room temperature to 600 ℃ at the heating rate of 5 ℃/min, and calcining for 5 hours to obtain the nickel-copper-manganese oxide precursor. Then uniformly mixing the sieved oxide precursor and sodium carbonate according to the molar ratio of 1:1.05, putting the mixture into a muffle furnace, heating the mixture from room temperature to 600 ℃ at the speed of 5 ℃/min, keeping the temperature for 5h, heating the mixture to 900 ℃, and calcining the mixture for 12h to obtain the Co and Al Co-substituted modified sodium nickel manganese oxide cathode material (Na) 0.67 Ni 0.165 Co 0.165 Mn 0.56 Al 0.11 O 2 )。
Example 6
Weighing raw materials of manganese sulfate, nickel sulfate and copper sulfate according to the molar ratio of Mn, Ni and Cu metal elements of 0.67 (0.20:0.13), and dissolving the raw materials in pure water to prepare 2mol/L mixed metal salt solution; preparing 2.7mol/L ammonium bicarbonate supersaturated solution as precipitant solution; preparing 0.7mol/L ammonium bicarbonate solution as a base solution. And adding the mixed metal salt solution and the ammonium bicarbonate precipitant solution into the mixed base solution by a peristaltic pump, controlling the ratio of the mixed metal salt to the ammonium bicarbonate precipitant solution to be 1:2, controlling the pH value to be about 8, stirring at the speed of 900r/min and the temperature to be 50 ℃. Carrying out coprecipitation reaction for 100h, controlling the particle size to be 10-20um, controlling the reaction temperature to be 50-70 ℃, controlling the stirring speed to be 400-1200rpm, controlling the reaction pH to be 7-9, controlling the reaction process pH to be 7.5 +/-0.2 when the reaction time is 4-20h before the particles are 10 mu m, controlling the reaction temperature to be 50 ℃ and controlling the stirring speed to be 550 r/min; when the particle size is between 10 and 20 mu m, controlling the pH value in the reaction process to be 8.0 +/-0.2, the reaction temperature to be 60 ℃, the stirring speed to be 700r/min, and obtaining the spherical nickel-copper-manganese carbonate precursor after the reaction is finished through suction filtration, hot water washing and drying.
And (3) heating the precursor from room temperature to 600 ℃ at the heating rate of 5 ℃/min, and calcining for 5h to obtain the nickel-copper-manganese oxide precursor. Then uniformly mixing the sieved oxide precursor and sodium carbonate according to the molar ratio of 1:1.02, putting the mixture into a muffle furnace, heating the mixture from room temperature to 600 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 4h, heating the mixture to 900 ℃, and calcining the mixture for 8h to obtain the copper-partially-substituted and modified sodium nickel manganese oxide positive electrode material (Na) 0.67 Ni 0.26 Cu 0.07 Mn 0.67 O 2 )。
Assembling the button cell: mixing the sodium nickel manganese oxide cathode material prepared in the comparative example and the embodiment, a conductive agent and a binder according to the mass ratio of 8:1:1 to prepare a cathode, and assembling the cathode in a vacuum glove box, wherein a sodium sheet is a cathode, a diaphragm is a glass fiber diaphragm, and electrolyte is 1mol/LNaClO 4 (EC: DMC in a volume ratio of 1: 1). The first charge-discharge and cycle performance is tested in a voltage range of 2.0-4.5V, the rate performance of the material is tested under different rate conditions (0.1C, 0.2, 0.5C, 1C, 3C and 5C), and the results are shown in Table 1, the performance is improved after the substitution modification, and the performance of the co-substituted nickel sodium manganate anode material is the best. The results are also shown in fig. 3 and 4, and the substituted and modified sodium nickel manganese oxide positive electrode material has a reduced first discharge specific capacity, but has improved rate capability and cycle stability.
TABLE 1 electrochemical Properties of different NiMnaMnO cathode materials
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (9)
1. A preparation method of a cation-substituted modified spherical-like sodium nickel manganese oxide positive electrode material is characterized by comprising the following steps of: the preparation method comprises the following steps:
(1) dissolving soluble nickel salt, manganese salt and substituted metal M salt in pure water according to a certain proportion to obtain a mixed salt solution A; dissolving carbonate in pure water to obtain a solution B;
(2) adding the solution A and the solution B in the step (1) into a reaction kettle filled with a base solution to carry out coprecipitation reaction to obtain a quasi-spherical carbonate precursor; during the coprecipitation reaction, the particle size is controlled to be 3-20um, the reaction temperature is controlled to be 40-70 ℃, the stirring speed is 400-1200rpm, the reaction pH is 7-9, and the reaction time is 50-120 h; before the particle size is 10 mu m, controlling the pH value in the reaction process to be 7.5 +/-0.2, the reaction temperature to be 50 ℃, and the stirring speed to be 550 r/min; when the particle size is between 10 and 20 mu m, controlling the pH value in the reaction process to be 8.0 +/-0.2, the reaction temperature to be 60 ℃, and the stirring speed to be 700 r/min;
(3) calcining the sphere-like carbonate precursor obtained in the step (2) to obtain a layered oxide precursor;
(4) uniformly mixing the oxide precursor obtained in the step (3) with sodium salt, and calcining to obtain the substituted and modified sodium nickel manganese oxide anode material;
the structural formula of the sodium nickel manganese oxide cathode material is Na 0.67 Ni 0.33 Mn 0.67 O 2 。
2. The preparation method of the cation-substituted modified spherical-like sodium nickel manganese oxide positive electrode material according to claim 1, characterized in that: the nickel salt in the step (1) is one or more of nickel sulfate, nickel chloride, nickel nitrate or nickel acetate.
3. The preparation method of the cation-substituted modified spherical-like sodium nickel manganese oxide positive electrode material according to claim 1, characterized in that: the manganese salt in the step (1) is one or more of manganese sulfate, manganese nitrate, manganese chloride or manganese acetate.
4. The preparation method of the cation-substituted modified spherical-like sodium nickel manganese oxide positive electrode material according to claim 1, characterized in that: the substituted metal M salt in the step (1) is one or more of copper sulfate/cobalt/yttrium/magnesium/molybdenum, copper nitrate/cobalt/yttrium/magnesium/molybdenum and copper chloride/cobalt/yttrium/magnesium/molybdenum.
5. The preparation method of the cation-substituted modified spherical-like sodium nickel manganese oxide positive electrode material according to claim 1, characterized in that: the carbonate in the step (1) is ammonium bicarbonate.
6. The preparation method of the cation-substituted modified spherical-like sodium nickel manganese oxide positive electrode material according to claim 1, characterized in that: the concentration of the metal ions in the solution A in the step (1) is 0.1-1mol/L, the molar ratio of nickel, manganese and the substituted metal cations M is (0.33-x):0.67: x, wherein x is 0.02-0.2, and the carbonate in the obtained solution B is a supersaturated solution with the concentration of about 2.7 mol/L.
7. The preparation method of the cation-substituted modified spherical-like sodium nickel manganese oxide positive electrode material according to claim 1, characterized in that: the base solution in the step (2) is ammonium bicarbonate, and the concentration of the ammonium bicarbonate is 0.1-1.0 mol/L.
8. The preparation method of the cation-substituted modified spherical-like sodium nickel manganese oxide positive electrode material according to claim 1, characterized in that: and (3) controlling the molar ratio of the metal salt to the carbonate to be 1:2 during the coprecipitation reaction in the step (2).
9. The preparation method of the cation-substituted modified spherical-like sodium nickel manganese oxide positive electrode material according to claim 1, characterized in that: the sodium salt in the step (4) is one or more of sodium carbonate, sodium bicarbonate or sodium hydroxide.
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