CN112563484A - Sodium-ion battery positive electrode material, preparation method thereof and sodium-ion battery - Google Patents
Sodium-ion battery positive electrode material, preparation method thereof and sodium-ion battery Download PDFInfo
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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Abstract
The invention provides a positive electrode material of a sodium-ion battery, a preparation method of the positive electrode material and the sodium-ion battery, wherein the chemical formula of the positive electrode material of the sodium-ion battery is NaxNiyM1‑yO2Wherein x is more than 0.5 and less than 1, y is more than 0.1 and less than 0.5, and M is selected from at least one of Mn, Fe, Co, V, Cu, Cr and Ti; the positive electrode material of the sodium-ion battery is spherical-like particles, and the positive electrode material of the sodium-ion battery has a layered structure. The positive electrode material of the sodium ion battery has good charge-discharge specific capacity and cycle performance; the preparation method controls the precursor mixed liquid inThe reaction is carried out under the conditions of high temperature and high pressure, the interlayer oxygen content of the layered structure of the positive electrode material of the sodium ion battery is effectively reduced, and the cycle performance of the material is obviously improved. The preparation process has simple steps, easily obtained raw materials, easy realization and suitability for large-scale production and application.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a sodium ion battery positive electrode material, a preparation method thereof and a sodium ion battery.
Background
In recent years, the output and sales of China new energy automobiles are continuously increased and stably live at the first place in the world. However, the traditional lead-acid battery and nickel-cadmium battery have low energy efficiency and serious pollution, the lithium ion battery has high cost and needs to be improved in safety, and the market demand of new energy automobiles is increased rapidly, so that the market demand is difficult to meet. The sodium ion battery has the advantages of high safety, low cost, environmental friendliness and the like, is favored by researchers, and promotes the application of the sodium ion battery in the aspect of power batteries. The anode and cathode materials, the electrolyte and the diaphragm are important components of the sodium ion battery, wherein the anode material plays a vital role.
Typical positive electrode materials of sodium-ion batteries include layered transition metal oxides, prussian blue analogues, polyanion positive electrode materials and the like. The Prussian blue analogue has a three-dimensional sodium ion intercalation and deintercalation channel, so that sodium ions with larger ionic radius can be intercalated and deintercalated, but a large number of vacancies exist in the material, and the vacancies can cause the collapse of the material structure in the process of intercalating and deintercalating the sodium ions in the material; in addition, a large amount of coordinated water exists in the material, and the water molecules also influence the performance of the material. The polyanion material has a stable framework structure and excellent structural stability, and the polyanion induction effect can further improve the working voltage of the material; however, polyanionic three-dimensional structure cannot provide more Na+Intercalation into sites, resulting in a lower specific capacity of such materials, and in addition Na+Migration in three-dimensional tunnels also exhibits slower reaction kinetics.
Oxidation of layered transition metalsThe substance has reversible ion-disintercalation capability and stable layered structure, and is beneficial to inserting other ions or molecules between layers, so that the substance is one of the research hotspots of the positive electrode material of the sodium ion battery at present, although the layered oxide positive electrode material has high theoretical specific capacity and Na+Two-dimensional diffusion in the layer is fast, but the material has poor electrochemical cycling performance. Therefore, the finding of a sodium ion battery cathode material with better cycle performance is of great significance to the field.
Disclosure of Invention
The invention aims to solve the problems and provides a positive electrode material of a sodium ion battery, a preparation method thereof and the sodium ion battery, wherein the positive electrode material of the sodium ion battery has a layered structure, is spherical-like particles, has higher specific surface area and tap density, higher charge-discharge specific capacity and energy density and excellent cycle performance; according to the preparation method, the precursor mixed solution is controlled to react under the conditions of high temperature and high pressure, so that the interlayer oxygen content of the layered structure of the positive electrode material of the sodium-ion battery is effectively reduced, and the cycle performance of the material is obviously improved.
According to one aspect of the application, a positive electrode material of a sodium-ion battery is provided, wherein the chemical formula of the positive electrode material of the sodium-ion battery is NaxNiyM1-yO2Wherein x is more than 0.5 and less than 1, y is more than 0.1 and less than 0.5, and M is selected from at least one of Mn, Fe, Co, V, Cu, Cr and Ti;
the positive electrode material of the sodium-ion battery is spherical-like particles, and the positive electrode material of the sodium-ion battery has a layered structure.
Further, x is more than 0.6 and less than 0.9, y is more than 0.2 and less than 0.4, and M is selected from at least one of Mn, Fe, Co and Cr;
preferably, 0.8 < x < 0.85, 0.3 < y < 0.35, and M is Mn.
Further, the particle size of the spheroidal particles is 0.5-10 μm; preferably, the particle size of the spheroidal particles is 1-5 μm; preferably, the specific surface area of the positive electrode material of the sodium-ion battery is 0.6-1.0 m2(ii)/g; preferably, the tap density of the positive electrode material of the sodium-ion battery is 1.0-1.3 m2(ii)/g; superior foodOptionally, the phase of the positive electrode material of the sodium-ion battery is a P2 phase.
According to another aspect of the present application, there is also provided a method for preparing the positive electrode material for sodium-ion batteries, the method comprising the following steps:
(1) mixing the salt solutions of sodium salt, nickel salt and M salt to obtain a precursor mixed solution; wherein the molar ratio of sodium atoms, nickel atoms and M atoms in the sodium salt, the nickel salt and the M salt is 0.5-1: 0.1-0.5: 0.5 to 0.9; m is selected from at least one of Mn, Fe, Co, V, Cu, Cr and Ti;
(2) reacting the precursor mixed solution for 5-20 h at the pressure of 5-50 MPa and the temperature of 120-200 ℃ to obtain a product;
(3) and calcining the product to obtain the positive electrode material of the sodium-ion battery.
The precursor is reacted under the conditions of high temperature and high pressure, oxygen ions in the material are in an active state under the conditions of high temperature, and the reaction system is in a high-pressure state, so that the oxygen ions are easy to dissociate from the layers and the defects of the material to form oxygen, the oxygen content between the layers is effectively reduced, the interaction between the oxygen ions and the oxygen ions is weakened, and a stable product is formed.
Further, in the step (1), the sodium salt is at least one selected from sodium carbonate, sodium nitrate and sodium acetate;
preferably, the nickel salt is selected from divalent nickel salts;
preferably, the divalent nickel salt is selected from at least one of nickel sulfate, nickel chloride and nickel nitrate;
preferably, the M salt is selected from at least one of a sulfate, a chloride and a nitrate;
preferably, the solvent in the salt solution is selected from at least one of water, ethanol and acetone.
Further, in the step (2), reacting the precursor mixed solution for 8-15 hours at the pressure of 10-25 MPa and the temperature of 150-180 ℃;
preferably, in the step (2), the precursor mixed solution is reacted for 10-12 hours under the pressure of 15-20 MPa and the temperature of 160-170 ℃.
Further, in the step (2), the precursor mixed solution is placed in a high-pressure reaction kettle with the pressure of 5-50 MPa, the high-pressure reaction kettle is sealed, and then the high-pressure reaction kettle is heated to 120-200 ℃ to react the precursor mixed solution;
preferably, the heating is selected from at least one of electric heating and oil bath heating;
preferably, the heating is oil bath heating.
Further, the step (3) further comprises a step of washing and drying the product before calcining the product;
preferably, the washing comprises washing with deionized water and ethanol for multiple times;
preferably, the drying temperature is 80-100 ℃, and the drying time is 5-10 min.
Further, in the step (3), the calcining temperature is 600-1000 ℃ and the time is 5-15 h;
preferably, the calcining temperature is 700-800 ℃, and the time is 6-10 h;
preferably, the calcining atmosphere is a compressed air atmosphere;
preferably, in the calcining process, the temperature is increased to 600-1000 ℃ at the speed of 2-5 ℃/min;
preferably, step (3) further comprises cooling the calcined product;
preferably, the cooling is natural cooling to room temperature.
According to another aspect of the application, a sodium-ion battery is also provided, wherein the sodium-ion battery comprises at least one of the sodium-ion battery positive electrode material described in any one of the above and the sodium-ion battery positive electrode material prepared by the preparation method described in any one of the above.
According to another aspect of the application, the application of the graphene-coated graphite material as a lithium ion battery negative electrode material is also provided.
The beneficial effects of the invention include but are not limited to:
(1) the positive electrode material of the sodium-ion battery provided by the invention has a layered structure, is spherical-like particles, has a higher specific surface area and tap density, and has higher charge-discharge specific capacity, energy density and excellent cycle performance.
(2) According to the preparation method of the sodium-ion battery anode material, provided by the invention, the precursor mixed solution is controlled to react under the conditions of high temperature and high pressure, so that the specific surface area and the tap density of the layered structure of the sodium-ion battery anode material are improved, the interlayer oxygen content of the layered structure of the sodium-ion battery anode material is effectively reduced, and the cycle performance of the material is obviously improved.
(3) The preparation method of the sodium-ion battery anode material provided by the invention has the advantages of simple process steps, easily obtained raw materials, easiness in realization and suitability for large-scale production and application.
Drawings
FIG. 1 is an SEM image of the positive electrode material of a sodium-ion battery obtained in example 1 of the present invention;
FIG. 2 is an XRD pattern of the positive electrode material of the sodium-ion battery obtained in example 1 of the present invention;
FIG. 3 is an EDS diagram of a positive electrode material for a sodium-ion battery obtained in example 1 of the present invention;
FIG. 4 is an EDS diagram of a positive electrode material for a sodium-ion battery obtained in comparative example 1 of the present invention;
FIG. 5 is a first charge-discharge curve of a battery assembled by the positive electrode material of the sodium-ion battery obtained in example 1 of the present invention;
fig. 6 is a cycle curve of a sodium-ion battery positive electrode material obtained in example 1 of the present invention assembled into a battery.
Detailed Description
In order to more clearly explain the overall concept of the present application, the following detailed description is given by way of example. In the following description, numerous specific details are set forth in order to provide a more thorough understanding of the present application. It will be apparent, however, to one skilled in the art, that the present application may be practiced without one or more of these specific details. In other instances, well-known features of the art have not been described in order to avoid obscuring the present application.
Unless otherwise specified, the starting materials and reagents in the following examples are all commercially available.
Example 1
The invention adopts the following method to prepare the positive electrode material of the sodium-ion battery:
(1) adding 55g of CH3COONa、82.1g(CH3COO)2Ni·4H2O and 164.2g (CH)3COO)2Mn·4H2Adding O (the molar ratio of Na to Ni to Mn is 0.67:0.33:0.67) into 1L of ethanol respectively to obtain a sodium acetate solution, a nickel acetate solution and a manganese acetate solution; then uniformly mixing the sodium acetate solution, the nickel acetate solution and the manganese acetate solution, placing the mixture into a high-pressure reaction kettle, and sealing the high-pressure reaction kettle;
(2) controlling the pressure of the high-pressure reaction kettle to be 15MPa, and reacting the high-pressure reaction kettle in an oil bath kettle at the temperature of 160 ℃ for 10 hours;
(3) washing the resultant with water and ethanol for three times respectively, and drying at 80 deg.C for 10min in a spray dryer; after the product is washed by water and alcohol, the residual alkali of the product is effectively reduced, and the stability of the material in the air is improved;
(4) placing the sagger containing the cleaned product in a muffle furnace, calcining at 700 ℃ at a heating rate of 3.5 ℃/min for 8h in the atmosphere of compressed air, and naturally cooling to room temperature to obtain the positive electrode material P2-Na of the sodium-ion battery0.67Ni0.33Mn0.67O2。
The positive electrode material of the sodium-ion battery has a layered structure, and is spherical-like particles with the particle size of 1-5 mu m as shown in figure 1; the tap density of the positive electrode material of the sodium-ion battery is 1.2g/cm3The specific surface area is 0.833m2/g。
The XRD pattern of the positive electrode material of the sodium-ion battery is shown in figure 2. As can be seen from fig. 2, the peak of the prepared product is strong and free of miscellaneous peaks; the EDS diagram of the positive electrode material of the sodium-ion battery is shown in figure 3.
Example 2
The invention adopts the following method to prepare the positive electrode material of the sodium-ion battery:
(1) 72.25g NaNO3、105.2g NiSO4·6H2O and 174.6g Co (NO)3)2(the molar ratio of Na, Ni and Co is 0.85:0.4:0.6) are respectively added into 1L of ethanol to obtain a sodium nitrate solution, a nickel sulfate solution and a cobalt nitrate solution; then uniformly mixing the sodium nitrate solution, the nickel sulfate solution and the cobalt nitrate solution, placing the mixture into a high-pressure reaction kettle, and sealing the high-pressure reaction kettle;
(2) controlling the pressure of the high-pressure reaction kettle to be 20MPa, and reacting the high-pressure reaction kettle in an oil bath kettle at the temperature of 170 ℃ for 12 hours;
(3) washing the resultant with water and ethanol twice, respectively, and drying at 100 deg.C for 5min in a spray dryer;
(4) placing the sagger containing the cleaned product in a muffle furnace, calcining at 600 deg.C at a heating rate of 2 deg.C/min for 10 hr in the atmosphere of compressed air, and naturally cooling to room temperature to obtain positive electrode material P2-Na of sodium ion battery0.85Ni0.4Co0.6O2。
The positive electrode material of the sodium-ion battery has a layered structure, and is spherical-like particles with the particle size of 1-5 mu m; the tap density of the positive electrode material of the sodium-ion battery is 1.0g/cm3The specific surface area is 0.786m2/g。
Example 3
The invention adopts the following method to prepare the positive electrode material of the sodium-ion battery:
(1) 68g NaNO3、54.8g Ni(NO3)2With 88.1g MnCl2(the molar ratio of Na, Ni and Mn is 0.8:0.3:0.7) are respectively added into 1L of ethanol to obtain a sodium nitrate solution, a nickel nitrate solution and a manganese chloride solution; then uniformly mixing the sodium nitrate solution, the nickel nitrate solution and the manganese chloride solution, placing the mixture into a high-pressure reaction kettle, and sealing the high-pressure reaction kettle;
(2) controlling the pressure of the high-pressure reaction kettle to be 10MPa, and reacting the high-pressure reaction kettle in an oil bath kettle at the temperature of 180 ℃ for 8 hours;
(3) washing the resultant with water and ethanol for three times respectively, and drying in a spray dryer at 90 deg.C for 8 min;
(4) placing the sagger containing the cleaned product in a muffle furnace, calcining at 800 ℃ at a heating rate of 3 ℃/min for 6h in the atmosphere of compressed air, and naturally cooling to room temperature to obtain the positive electrode material P2-Na of the sodium-ion battery0.8Ni0.3Mn0.7O2。
The positive electrode material of the sodium-ion battery has a layered structure, and is spherical-like particles with the particle size of 1-5 mu m; the tap density of the positive electrode material of the sodium-ion battery is 1.1g/cm3The specific surface area is 0.815m2/g。
Example 4
The invention adopts the following method to prepare the positive electrode material of the sodium-ion battery:
(1) 35.5g of Na2CO3、42.8g NiCl2And 159.47g Cr (NO)3)2(the molar ratio of Na, Ni and Cr is 0.67:0.33:0.67) are respectively added into 1L of ethanol to obtain a sodium carbonate solution, a nickel chloride solution and a chromium nitrate solution; then uniformly mixing the sodium carbonate solution, the nickel chloride solution and the chromium nitrate solution, placing the mixture into a high-pressure reaction kettle, and sealing the high-pressure reaction kettle;
(2) controlling the pressure of the high-pressure reaction kettle to be 25MPa, and reacting the high-pressure reaction kettle in an oil bath kettle at the temperature of 150 ℃ for 15 hours;
(3) washing the resultant with water and ethanol for three times respectively, and drying at 80 deg.C for 10min in a spray dryer;
(4) placing the sagger containing the cleaned product in a muffle furnace, calcining at 600 ℃ at the heating rate of 4 ℃/min for 15h in the atmosphere of compressed air, and naturally cooling to room temperature to obtain the positive electrode material P2-Na of the sodium-ion battery0.67Ni0.33Cr0.67O2。
The positive electrode material of the sodium-ion battery has a layered structure, and is spherical-like particles with the particle size of 1-5 mu m; the tap density of the positive electrode material of the sodium-ion battery is1.2g/cm3The specific surface area is 0.763m2/g。
Example 5
The invention adopts the following method to prepare the positive electrode material of the sodium-ion battery:
(1) 56.95g NaNO3、60.3g Ni(NO3)2And 133.95g Fe2(SO4)3Respectively adding the mixture (the molar ratio of Na to Ni to Fe is 0.67:0.33:0.67) into 1L of ethanol to respectively obtain a sodium nitrate solution, a nickel nitrate solution and a ferric sulfate solution; then uniformly mixing the sodium nitrate solution, the nickel nitrate solution and the ferric sulfate solution, placing the mixture into a high-pressure reaction kettle, and sealing the high-pressure reaction kettle;
(2) controlling the pressure of the high-pressure reaction kettle to be 5MPa, and reacting the high-pressure reaction kettle in an oil bath kettle at the temperature of 120 ℃ for 20 hours;
(3) washing the resultant with water and ethanol for three times respectively, and drying in spray dryer at 85 deg.C for 6 min;
(4) placing the sagger containing the cleaned product in a muffle furnace, calcining at 1000 deg.C and at a heating rate of 5 deg.C/min for 5 hr in the atmosphere of compressed air, and naturally cooling to room temperature to obtain positive electrode material P2-Na of sodium ion battery0.67Ni0.33Fe0.67O2。
The positive electrode material of the sodium-ion battery has a layered structure, and is spherical-like particles with the particle size of 1-5 mu m; the tap density of the positive electrode material of the sodium-ion battery is 1.2g/cm3The specific surface area is 0.802m2/g。
Example 6
The invention adopts the following method to prepare the positive electrode material of the sodium-ion battery:
(1) 35.5g of Na2CO3、60.3g Ni(NO3)2And 87g of CoCl2(the molar ratio of Na, Ni and Mn is 0.67:0.33:0.67) are respectively added into 1L of ethanol to obtain a sodium carbonate solution, a nickel nitrate solution and a cobalt chloride solution; then uniformly mixing the sodium carbonate solution, the nickel nitrate solution and the cobalt chloride solution, and placing the mixture into a high-pressure reaction kettleSealing the high-pressure reaction kettle;
(2) controlling the pressure of the high-pressure reaction kettle to be 50MPa, and reacting the high-pressure reaction kettle in an oil bath kettle at the temperature of 120 ℃ for 10 hours;
(3) washing the resultant with water and ethanol twice, respectively, and drying at 90 deg.C for 5min in a spray dryer;
(4) placing the sagger containing the cleaned product in a muffle furnace, calcining at 700 ℃ at a heating rate of 2.5 ℃/min for 8h in the atmosphere of compressed air, and naturally cooling to room temperature to obtain the positive electrode material P2-Na of the sodium-ion battery0.67Ni0.33Co0.67O2。
The positive electrode material of the sodium-ion battery has a layered structure, and is spherical-like particles with the particle size of 1-5 mu m; the tap density of the positive electrode material of the sodium-ion battery is 1.1g/cm3The specific surface area is 0.731m2/g。
Comparative example 1
The invention adopts the following method to prepare the positive electrode material of the sodium-ion battery:
(1)55g CH3COONa、82.1g(CH3COO)2Ni·4H2o and 164.2g (CH)3COO)2Mn·4H2Adding O (the molar ratio of Na to Ni to Mn is 0.67:0.33:0.67) into 1L of ethanol respectively to obtain a sodium acetate solution, a nickel acetate solution and a manganese acetate solution; then uniformly mixing the sodium acetate solution, the nickel acetate solution and the manganese acetate solution, and placing the mixture into a reaction kettle;
(2) the reaction kettle is put into an oil bath kettle at 160 ℃ for reaction for 10 hours;
(3) the resultant was washed with water and ethanol three times, respectively, and dried in a spray dryer at 80 ℃ for 10 min.
(4) Placing the sagger containing the cleaned product in a muffle furnace, calcining at 700 ℃ at a heating rate of 3.5 ℃/min for 8h in the atmosphere of compressed air, and naturally cooling to room temperature to obtain the positive electrode material P2-Na of the sodium-ion battery0.67Ni0.33Mn0.67O2The positive electrode of the sodium ion batteryThe tap density of the material was 0.9g/cm3The specific surface area is 0.528m2(ii)/g; the EDS diagram of the positive electrode material of the sodium-ion battery is shown in fig. 4, and is combined with fig. 3, which shows that the oxygen content of the positive electrode material of the sodium-ion battery in example 1 of the present application is reduced, indicating that the high voltage of the present application can significantly reduce the oxygen content of the positive electrode material of the sodium-ion battery.
Comparative example 2
The invention adopts the following method to prepare the positive electrode material of the sodium-ion battery:
(1)55g CH3COONa、82.1g(CH3COO)2Ni·4H2o and 164.2g (CH)3COO)2Mn·4H2Adding O (the molar ratio of Na to Ni to Mn is 0.67:0.33:0.67) into 1L of ethanol respectively to obtain a sodium acetate solution, a nickel acetate solution and a manganese acetate solution; then uniformly mixing the sodium acetate solution, the nickel acetate solution and the manganese acetate solution, placing the mixture into a high-pressure reaction kettle, and sealing the high-pressure reaction kettle;
(2) controlling the pressure of the high-pressure reaction kettle to be 15MPa, and reacting the high-pressure reaction kettle in an oil bath kettle at the temperature of 50 ℃ for 10 hours;
(3) the resultant was washed with water and ethanol three times, respectively, and dried in a spray dryer at 80 ℃ for 10 min.
(4) Placing the sagger containing the cleaned product in a muffle furnace, calcining at 700 ℃ at a heating rate of 3.5 ℃/min for 8h in a compressed air atmosphere, and naturally cooling to room temperature to obtain the positive electrode material of the sodium-ion battery; the tap density of the positive electrode material of the sodium-ion battery is 0.8g/cm3The specific surface area is 0.583m2/g。
The positive electrode materials of the sodium ion batteries prepared in examples 1 to 6 and comparative examples 1 to 2 were assembled into a sodium ion battery, and electrochemical performance tests were performed thereon. And testing the charge-discharge specific capacity of the lithium ion battery under the conditions that the voltage range is 1.0-4.2V and the current density is 0.1C. The discharge test is performed in a voltage range of 1.0-4.2V and a current density of 1C for 100 cycles, and the test structure is shown in Table 1. P2-Na obtained in example 10.67Ni0.33Mn0.67O2First charge and discharge of assembled sodium ion batteryThe curves and the cycle curves are shown in fig. 5 and 6, respectively.
TABLE 1 Battery Performance test results
As can be seen from table 1, the sodium ion battery assembled by the positive electrode material of the sodium ion battery prepared in the embodiment of the present application has higher charge/discharge specific capacity and energy density, and compared with comparative examples 1 to 2, the capacity retention rate after 100 cycles is significantly improved, and particularly the capacity retention rate after 100 cycles in embodiment 1 reaches 103.5%. The tap density and the specific surface area of the positive electrode material of the sodium-ion battery are improved and the interlayer oxygen content of the positive electrode material of the sodium-ion battery is reduced due to the high-temperature and high-pressure conditions, so that the electrochemical cycle performance of the material is improved.
The embodiments in the present specification are described in a progressive manner, and the same and similar parts among the embodiments are referred to each other, and each embodiment focuses on the differences from the other embodiments. In particular, for the system embodiment, since it is substantially similar to the method embodiment, the description is simple, and for the relevant points, reference may be made to the partial description of the method embodiment.
The above description is only an example of the present application, and the protection scope of the present application is not limited by these specific examples, but is defined by the claims of the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the technical idea and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. The positive electrode material of the sodium-ion battery is characterized in that sodiumThe chemical formula of the anode material of the ion battery is NaxNiyM1-yO2Wherein x is more than 0.5 and less than 1, y is more than 0.1 and less than 0.5, and M is selected from at least one of Mn, Fe, Co, V, Cu, Cr and Ti;
the positive electrode material of the sodium-ion battery is spherical-like particles, and the positive electrode material of the sodium-ion battery has a layered structure.
2. The positive electrode material for sodium-ion batteries according to claim 1, wherein 0.6 < x < 0.9, 0.2 < y < 0.4, and M is at least one selected from Mn, Fe, Co and Cr;
preferably, 0.8 < x < 0.85, 0.3 < y < 0.35, and M is Mn.
3. The positive electrode material for sodium-ion batteries according to claim 1, wherein the particle diameter of said spheroidal particles is 0.5 to 10 μm,
preferably, the particle size of the spheroidal particles is 1-5 μm;
preferably, the phase of the positive electrode material of the sodium-ion battery is a P2 phase;
preferably, the specific surface area of the positive electrode material of the sodium-ion battery is 0.6-1.0 m2/g；
Preferably, the tap density of the positive electrode material of the sodium-ion battery is 1.0-1.3 m2/g。
4. A method for preparing a positive electrode material for a sodium-ion battery according to any one of claims 1 to 3, comprising the steps of:
(1) mixing the salt solutions of sodium salt, nickel salt and M salt to obtain a precursor mixed solution; wherein the molar ratio of sodium atoms, nickel atoms and M atoms in the sodium salt, the nickel salt and the M salt is 0.5-1: 0.1-0.5: 0.5-0.9, wherein M is at least one selected from Mn, Fe, Co, V, Cu, Cr and Ti;
(2) reacting the precursor mixed solution for 5-20 h at the pressure of 5-50 MPa and the temperature of 120-200 ℃ to obtain a product;
(3) and calcining the product to obtain the positive electrode material of the sodium-ion battery.
5. The method for preparing a positive electrode material for a sodium-ion battery according to claim 4, wherein in the step (1), the sodium salt is at least one selected from the group consisting of sodium carbonate, sodium nitrate and sodium acetate;
preferably, the nickel salt is selected from divalent nickel salts;
preferably, the divalent nickel salt is selected from at least one of nickel sulfate, nickel chloride and nickel nitrate;
preferably, the M salt is selected from at least one of a sulfate, a chloride and a nitrate;
preferably, the solvent in the salt solution is selected from at least one of water, ethanol and acetone.
6. The method for preparing the positive electrode material of the sodium-ion battery according to claim 4, wherein in the step (2), the precursor mixed solution is reacted for 8-15 hours at a pressure of 10-25 MPa and a temperature of 150-180 ℃;
preferably, in the step (2), the precursor mixed solution is reacted for 10-12 hours under the pressure of 15-20 MPa and the temperature of 160-170 ℃.
7. The method for preparing the positive electrode material of the sodium-ion battery according to claim 4, wherein in the step (2), the precursor mixed solution is placed in a high-pressure reaction kettle with the pressure of 5-50 MPa, the high-pressure reaction kettle is sealed, and then the high-pressure reaction kettle is heated to 120-200 ℃ to react the precursor mixed solution;
preferably, the heating is selected from at least one of electric heating and oil bath heating;
preferably, the heating is oil bath heating.
8. The method for producing a positive electrode material for a sodium-ion battery according to claim 4, wherein the step (3) further comprises a step of washing and drying the product before calcining the product;
preferably, the washing comprises washing with deionized water and ethanol for multiple times;
preferably, the drying temperature is 80-100 ℃, and the drying time is 5-10 min.
9. The preparation method of the positive electrode material of the sodium-ion battery according to claim 4, wherein in the step (3), the calcining temperature is 600-1000 ℃ and the calcining time is 5-15 h;
preferably, the calcining temperature is 700-800 ℃, and the time is 6-10 h;
preferably, the calcining atmosphere is a compressed air atmosphere;
preferably, in the calcining process, the temperature is increased to 600-1000 ℃ at the speed of 2-5 ℃/min;
preferably, step (3) further comprises cooling the calcined product;
preferably, the cooling is natural cooling to room temperature.
10. A sodium ion battery, characterized in that the sodium ion battery comprises at least one of the positive electrode material for sodium ion battery of any one of claims 1 to 3 and the positive electrode material for sodium ion battery prepared by the preparation method of any one of claims 4 to 9.
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| PCT/CN2021/096811 WO2022105175A1 (en) | 2020-11-19 | 2021-05-28 | Positive electrode material of sodium ion battery, preparation method therefor, and sodium ion battery |
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| WO2022105175A1 (en) | 2022-05-27 |
| CN112563484B (en) | 2022-08-19 |
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