CN114447300B - Preparation method of sodium ion battery positive electrode material with tunnel phase and lamellar phase composite structure, prepared material and application thereof - Google Patents
Preparation method of sodium ion battery positive electrode material with tunnel phase and lamellar phase composite structure, prepared material and application thereof Download PDFInfo
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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- 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 discloses a preparation method of a sodium ion battery anode material with a tunnel phase and lamellar phase composite structure, which relates to the technical field of sodium ion battery anode materials and comprises the following steps: (1) Mixing a sodium source compound and a manganese source compound according to a molar ratio, wherein the molar ratio of sodium to manganese is 0.52-0.55, and the sodium is excessive by 3% based on the molar ratio; (2) Sintering the mixed powder twice, wherein the temperature of the first sintering is 400-600 ℃, and the temperature of the second sintering is 800-1000 ℃. The invention also provides the anode material prepared by the method and application. The invention has the beneficial effects that: the invention only needs a sodium source and a manganese source, does not need to be doped with other elements, forms a two-phase structure by regulating the content of sodium, takes a tunnel phase as a main phase in the synthesized material, has fewer lamellar phases, decomposes the manganese source into an oxide by the first sintering, and better forms a phase by the second sintering to form the sodium-manganese oxide anode material with a two-phase composite structure.
Description
Technical Field
The invention relates to the technical field of sodium-ion battery anode materials, in particular to a preparation method of a sodium-ion battery anode material with a tunnel phase and lamellar phase composite structure, a prepared material and application thereof.
Background
With the use and consumption of fossil fuels, energy crisis and various environmental problems have come along, and the development of renewable energy sources has received a great deal of attention, and energy storage devices are an important part of them.
The sodium ion battery has the advantages of low cost and rich sodium source reserves, and has a working principle similar to that of a lithium ion battery, so that the sodium ion battery is considered to be suitable for a large-scale energy storage system, but at present, a suitable sodium ion battery anode material is lacked, and among various anode materials, the sodium ion battery anode material with a tunnel phase structure has good cycle stability but not high discharge capacity, and the sodium ion battery anode material with a lamellar phase structure has high discharge capacity but not good cycle stability, so that the sodium ion battery anode material with good stability, high discharge capacity and excellent multiplying power performance needs to be prepared.
For example, patent application publication No. CN113140724A discloses a method for synthesizing a tunnel lamellar intergrown phase sodium ion battery cathode material, the content of lamellar phase in the synthesized material is high, and fluorine is required to be doped to replace oxygen in the synthesis process to form a two-phase structure, so the preparation method is complex.
Disclosure of Invention
The invention aims to provide a preparation method of a sodium-ion battery anode material which is simple in preparation method and has a main tunnel phase in the material, the prepared material and application thereof.
The invention solves the technical problems through the following technical means:
the preparation method of the sodium ion battery anode material with the tunnel phase and lamellar phase composite structure comprises the following steps:
(1) Mixing a sodium source compound and a manganese source compound according to a molar ratio to obtain mixed powder, wherein the molar ratio of sodium to manganese is 0.52-0.55, and the sodium is excessive by 3% on the basis of the molar ratio;
(2) And (2) sintering the mixed powder obtained in the step (1) twice, wherein the temperature of the first sintering is 400-600 ℃, and the temperature of the second sintering is 800-1000 ℃.
Has the advantages that: according to the invention, only a sodium source and a manganese source are needed, other elements are not needed to be doped, a two-phase structure is formed by regulating and controlling the content of sodium, the sodium source is excessive by 3% on the basis of the needed molar ratio to make up for the volatilization of sodium in high-temperature sintering, a tunnel phase in the synthesized material is a main phase, the content of a lamellar phase is low, the manganese source is decomposed into an oxide through first sintering, and the phase can be better formed during second sintering to form the sodium-manganese oxide anode material with the two-phase composite structure.
The raw materials used in the method are low in price and easy to obtain, the anode material with the two-phase structure can be obtained without adding other materials, and the synthesis method is simple and suitable for large-scale production.
The appearance of the sodium ion battery anode material with the tunnel phase and lamellar phase composite structure is rod-shaped and sheet-shaped composite, the anode material obtained by the invention is assembled into a battery, the first discharge capacity is 119.9mAh/g under the current density of 1.5-4.3V and 200mA/g, and the capacity retention rate can reach 78.3% after 300 cycles; under the current densities of 20mA/g, 40mA/g, 100mA/g, 200mA/g, 400mA/g, 1000mA/g and 2000mA/g respectively, the first discharge capacity can reach 123.9mAh/g, 117.0mAh/g, 115.2mAh/g, 112.1mAh/g, 106.9mAh/g, 90.8mAh/g and 47.2mAh/g respectively.
Preferably, the sodium source compound is selected from one or more of sodium acetate, sodium carbonate, sodium oxalate and sodium nitrate.
Preferably, the manganese source compound is selected from one or more of manganese acetate, manganese dioxide, manganese carbonate and manganese nitrate.
Preferably, the heating rate of the first sintering is 1-5 ℃/min, the temperature is raised to 400-600 ℃, the temperature is kept for 4-6 h, and the sintering atmosphere is air.
Preferably, the temperature rise rate of the second sintering is 1-5 ℃/min, the temperature is raised to 800-1000 ℃, the temperature is kept for 12-18 h, and the sintering atmosphere is air.
The sodium ion battery anode material with the tunnel phase and lamellar phase composite structure prepared by the preparation method is adopted.
Has the advantages that: the appearance of the sodium ion battery anode material with the tunnel phase and lamellar phase composite structure is rod-shaped and sheet-shaped composite, the anode material obtained by the invention is assembled into a battery, the first discharge capacity is 119.9mAh/g under the current density of 1.5-4.3V and 200mA/g, and the capacity retention rate can reach 78.3% after 300 cycles; under the current densities of 20mA/g, 40mA/g, 100mA/g, 200mA/g, 400mA/g, 1000mA/g and 2000mA/g respectively, the first discharge capacity can reach 123.9mAh/g, 117.0mAh/g, 115.2mAh/g, 112.1mAh/g, 106.9mAh/g, 90.8mAh/g and 47.2mAh/g respectively.
The positive plate of the sodium ion battery is mainly prepared by dissolving the positive material, the conductive additive and the adhesive in an organic solvent, uniformly mixing and coating the mixture on an aluminum foil.
Has the beneficial effects that: the positive electrode material obtained by the invention is applied to a sodium ion battery positive plate and assembled into a battery, the first discharge capacity is 119.9mAh/g under the current density of 1.5-4.3V and 200mA/g, and the capacity retention rate can reach 78.3% after circulating for 300 circles; under the current densities of 20mA/g, 40mA/g, 100mA/g, 200mA/g, 400mA/g, 1000mA/g and 2000mA/g respectively, the first discharge capacity can reach 123.9mAh/g, 117.0mAh/g, 115.2mAh/g, 112.1mAh/g, 106.9mAh/g, 90.8mAh/g and 47.2mAh/g respectively.
Preferably, the conductive additive is Super C65, the binder is PVDF (polyvinylidene fluoride), and the organic solvent is NMP (N-methylpyrrolidone).
A sodium ion battery mainly comprises the positive plate, a diaphragm, organic electrolyte and a metal sodium plate.
Has the beneficial effects that: the sodium ion battery has the first discharge capacity of 119.9mAh/g under the current density of 1.5-4.3V and 200mA/g, and the capacity retention rate can reach 78.3% after circulating for 300 circles; under the current densities of 20mA/g, 40mA/g, 100mA/g, 200mA/g, 400mA/g, 1000mA/g and 2000mA/g respectively, the first discharge capacity can reach 123.9mAh/g, 117.0mAh/g, 115.2mAh/g, 112.1mAh/g, 106.9mAh/g, 90.8mAh/g and 47.2mAh/g respectively.
Preferably, the membrane is GF/F (Whatman); the organic electrolyte is Propylene Carbonate (PC) electrolyte, and the solute is sodium perchlorate (NaClO) 4 ) The concentration of the electrolyte was 1mol/L.
The sodium ion battery is applied to an energy storage device.
The principle of the invention is as follows: the invention forms a two-phase structure by regulating the sodium content, and the tunnel phase in the synthesized material is a main phase, the lamellar phase has less content, and the tunnel phase and the lamellar phase generate synergistic effect, so that the sodium-ion battery anode material with the tunnel phase and lamellar phase composite structure not only has the characteristic of good circulation stability of the tunnel phase structure, but also has the characteristic of high discharge capacity of the lamellar phase structure, and also has excellent multiplying power performance.
The invention has the advantages that: according to the invention, only a sodium source and a manganese source are needed, other elements are not needed to be doped, a two-phase structure is formed by regulating and controlling the content of sodium, the sodium source is excessive by 3% on the basis of the needed molar ratio to make up for the volatilization of sodium in high-temperature sintering, a tunnel phase in the synthesized material is a main phase, the content of a lamellar phase is low, the manganese source is decomposed into an oxide through first sintering, and the phase can be better formed during second sintering to form the sodium-manganese oxide anode material with the two-phase composite structure.
The raw materials used by the method are low in price and easy to obtain, the anode material with the two-phase structure can be obtained without adding other materials, and the synthesis method is simple and suitable for large-scale production.
The appearance of the sodium ion battery anode material with the tunnel phase and lamellar phase composite structure is rod-shaped and sheet-shaped composite, the anode material obtained by the invention is assembled into a battery, the first discharge capacity is 119.9mAh/g under the current density of 1.5-4.3V and 200mA/g, and the capacity retention rate can reach 78.3% after 300 cycles; under the current densities of 20mA/g, 40mA/g, 100mA/g, 200mA/g, 400mA/g, 1000mA/g and 2000mA/g respectively, the first discharge capacity can reach 123.9mAh/g, 117.0mAh/g, 115.2mAh/g, 112.1mAh/g, 106.9mAh/g, 90.8mAh/g and 47.2mAh/g respectively.
Drawings
FIG. 1 is an XRD pattern of the positive electrode material of the sodium ion battery obtained in examples 1 to 6 of the present invention;
FIG. 2 is an SEM image of the positive electrode material of the sodium-ion battery with the tunnel phase and the lamellar phase composite structure obtained in example 3 of the invention;
FIG. 3 is a TEM image of the positive electrode material of the sodium-ion battery with the composite structure of the tunnel phase and the lamellar phase obtained in example 3 of the invention;
FIG. 4 is a comparison graph of capacity cycles of the positive electrode materials of the sodium-ion batteries with the tunnel phase and the lamellar phase composite structure obtained in examples 2 to 4 of the invention and comparative example 3 at a current density of 20 mA/g;
FIG. 5 is a charge-discharge curve of the positive electrode material of the sodium-ion battery with the tunnel phase structure obtained in comparative example 1 of the present invention at a current density of 20 mA/g;
FIG. 6 is a charge-discharge curve of the positive electrode material of the Na-ion battery with the lamellar phase structure obtained in comparative example 2 of the invention at a current density of 20 mA/g;
FIG. 7 is a charge-discharge curve of the sodium-ion battery positive electrode material with the tunnel phase and the lamellar phase composite structure, obtained in example 3, at a current density of 20 mA/g;
FIG. 8 is a graph showing the comparison of the capacity cycles of the positive electrode material of a sodium-ion battery having a tunnel phase and a lamellar phase composite structure obtained in example 3 of the present invention with those of comparative example 1 and comparative example 2 at a current density of 200 mA/g;
FIG. 9 is a graph showing the comparison of the rate performance of the positive electrode material of the sodium-ion battery having a composite structure of the tunnel phase and the lamellar phase obtained in inventive example 3 with those of comparative example 1 and comparative example 2 at different current densities (20 mA/g, 40mA/g, 100mA/g, 200mA/g, 400mA/g, 1000mA/g, 2000 mA/g).
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Comparative example 1
The preparation method of the positive electrode material of the sodium-ion battery specifically comprises the following steps:
(1) 0.11135g (3% excess of sodium source based on 0.00102 mol) of sodium carbonate (relative molecular mass: 105.99) was weighed, 0.4598g (0.004 mol) of manganese carbonate (relative molecular mass: 114.95) was weighed, and the weighed powders were uniformly mixed using a mortar to obtain a mixed powder. Sodium and manganese molar ratio 0.51.
(2) Transferring the mixed powder obtained in the step (1) into a muffle furnace, heating to 500 ℃ at a heating rate of 1 ℃/min for heat preservation for 5 hours in an air atmosphere, continuing heating to 900 ℃ at a heating rate of 1 ℃/min for heat preservation for 15 hours after heat preservation is finished, and obtaining a sodium-ion battery anode material Na with a tunnel phase structure 0.51 MnO 2 。
Example 1
The preparation method of the positive electrode material of the sodium-ion battery specifically comprises the following steps:
(1) 0.11354g (0.00104 mol, 3% excess of sodium source) of sodium carbonate (relative molecular mass 105.99) was weighed, 0.4598g (0.004 mol) of manganese carbonate (relative molecular mass 114.95) was weighed, and the weighed powders were uniformly mixed using a mortar to obtain a mixed powder. Sodium and manganese molar ratio 0.52.
(2) Transferring the mixed powder obtained in the step (1) into a muffle furnace, heating to 500 ℃ at a heating rate of 1 ℃/min for heat preservation for 5 hours in an air atmosphere, continuing heating to 900 ℃ at a heating rate of 1 ℃/min for heat preservation for 15 hours after heat preservation is finished, and obtaining the Na anode material of the sodium-ion battery with a tunnel phase and lamellar phase composite structure 0.52 MnO 2 。
Example 2
The preparation method of the positive electrode material of the sodium-ion battery specifically comprises the following steps:
(1) 0.11572g (0.00106 mol, 3% excess of sodium source) of sodium carbonate (relative molecular mass 105.99) was weighed, 0.4598g (0.004 mol) of manganese carbonate (relative molecular mass 114.95) was weighed, and the above weighed powders were uniformly mixed using a mortar to obtain a mixed powder. Sodium and manganese molar ratio 0.53.
(2) Transferring the mixed powder obtained in the step (1) into a muffle furnace, heating to 500 ℃ at a heating rate of 1 ℃/min for heat preservation for 5 hours in an air atmosphere, continuing heating to 900 ℃ at a heating rate of 1 ℃/min for heat preservation for 15 hours after heat preservation is finished, and obtaining the Na anode material of the sodium-ion battery with a tunnel phase and lamellar phase composite structure 0.53 MnO 2 。
Example 3
The preparation method of the positive electrode material of the sodium-ion battery specifically comprises the following steps:
(1) 0.11790g (0.00108 mol, 3% excess of sodium source) of sodium carbonate (relative molecular mass 105.99) was weighed, 0.4598g (0.004 mol) of manganese carbonate (relative molecular mass 114.95) was weighed, and the weighed powders were uniformly mixed using a mortar to obtain a mixed powder. Sodium and manganese molar ratio 0.54.
(2) Transferring the mixed powder obtained in the step (1) into a muffle furnace, heating to 500 ℃ at a heating rate of 1 ℃/min for heat preservation for 5h in an air atmosphere, continuing heating to 900 ℃ at a heating rate of 1 ℃/min for heat preservation for 15h after heat preservation is finished, and obtaining the Na anode material of the sodium-ion battery with the tunnel phase and lamellar phase composite structure 0.54 MnO 2 。
Example 4
The preparation method of the positive electrode material of the sodium-ion battery specifically comprises the following steps:
(1) 0.12009g (0.00110 mol, 3% excess of sodium source) of sodium carbonate (relative molecular mass 105.99) was weighed, 0.4598g (0.004 mol) of manganese carbonate (relative molecular mass 114.95) was weighed, and the weighed powders were uniformly mixed using a mortar to obtain a mixed powder. Sodium and manganese molar ratio 0.55.
(2) Transferring the mixed powder obtained in the step (1) into a muffle furnace, heating to 500 ℃ at a heating rate of 1 ℃/min for heat preservation for 5h in an air atmosphere, continuing heating to 900 ℃ at a heating rate of 1 ℃/min for heat preservation for 15h after heat preservation is finished, and obtaining the Na anode material of the sodium-ion battery with the tunnel phase and lamellar phase composite structure 0.55 MnO 2 。
Comparative example 2
The preparation method of the positive electrode material of the sodium-ion battery specifically comprises the following steps:
(1) 0.12227g (0.00112 mol, 3% excess of sodium source) of sodium carbonate (relative molecular mass 105.99) was weighed, 0.4598g (0.004 mol) of manganese carbonate (relative molecular mass 114.95) was weighed, and the weighed powders were uniformly mixed using a mortar to obtain a mixed powder. Sodium and manganese molar ratio 0.56.
(2) Transferring the mixed powder obtained in the step (1) into a muffle furnace, heating to 500 ℃ at a heating rate of 1 ℃/min for heat preservation for 5 hours in an air atmosphere, continuing heating to 900 ℃ at a heating rate of 1 ℃/min for heat preservation for 15 hours after heat preservation is finished, and obtaining a sodium-ion battery positive electrode material Na with a lamellar phase structure 0.56 MnO 2 。
Comparative example 3
(1) 0.09607g (0.00088 mol, 3% excess of sodium source) of sodium carbonate (relative molecular mass 105.99) was weighed, 0.4598g (0.004 mol) of manganese carbonate (relative molecular mass 114.95) was weighed, and the weighed powders were uniformly mixed using a mortar to obtain a mixed powder. Sodium and manganese molar ratio 0.44.
(2) Transferring the mixed powder obtained in the step (1) into a muffle furnace, heating to 500 ℃ at a heating rate of 1 ℃/min for heat preservation for 5 hours in an air atmosphere, continuing heating to 900 ℃ at a heating rate of 1 ℃/min for heat preservation for 15 hours after heat preservation is finished, and obtaining a sodium-ion battery anode material Na with a tunnel phase structure 0.44 MnO 2 。
Comparative example 4
(1) 0.14629g (0.00134 mol, 3% excess of sodium source) of sodium carbonate (relative molecular mass 105.99) was weighed, 0.4598g (0.004 mol) of manganese carbonate (relative molecular mass 114.95) was weighed, and the weighed powders were uniformly mixed using a mortar to obtain a mixed powder. Sodium and manganese molar ratio 0.67.
(2) Transferring the mixed powder obtained in the step (1) into a muffle furnace, heating to 500 ℃ at a heating rate of 1 ℃/min under an air atmosphere, preserving heat for 5 hours, continuing heating to 900 ℃ at a heating rate of 1 ℃/min after heat preservation, and preserving heat for 15 hours to obtain a sodium-ion battery anode material Na with a lamellar phase structure 0.67 MnO 2 。
Comparative example 5
(1) 0.11572g (0.00106 mol, 3% excess of sodium source) of sodium carbonate (relative molecular mass 105.99) was weighed, 0.4598g (0.004 mol) of manganese carbonate (relative molecular mass 114.95) was weighed, and the weighed powders were uniformly mixed using a mortar to obtain a mixed powder. Sodium and manganese molar ratio 0.53.
(2) Transferring the mixed powder obtained in the step (1) into a muffle furnace, heating to 900 ℃ at a heating rate of 1 ℃/min in an air atmosphere, and preserving heat for 15 hours to obtain a sodium-ion battery anode material Na with a tunnel phase and lamellar phase composite structure 0.53 MnO 2 。
FIG. 1 is an XRD pattern of positive electrode materials of sodium ion batteries obtained in comparative example 1, comparative example 2 and examples 1 to 4 of the present invention; FIG. 2 is an SEM image of the positive electrode material of the sodium-ion battery with the tunnel phase and the lamellar phase composite structure obtained in example 2 of the invention; fig. 3 is a TEM image of the sodium ion battery cathode material with the tunnel phase and the lamellar phase composite structure obtained in example 2 of the present invention, and it can be seen that the cathode material obtained in example 3 is composed of two phases in structure and morphology.
Assembling the battery: weighing 0.032g of the obtained positive electrode material of the sodium ion battery, adding 0.004g of Super C65 as a conductive agent and 0.004g of PVDF (polyvinylidene fluoride) as a binder, dissolving the powder in NMP (N-methylpyrrolidone), uniformly mixing, coating the mixture on an aluminum foil to prepare a positive electrode plate, taking a sodium plate as a negative electrode, taking GF/F (Whatman) as a diaphragm, and 1mol/L sodium perchlorate (NaClO) 4 ) Dissolved in Propylene Carbonate (PC) as an electrolyte, assembling CR2016 button cells.
Fig. 4 is a graph showing the capacity cycle comparison of the positive electrode material of the sodium-ion battery with the tunnel phase and the lamellar phase composite structure obtained in examples 1 to 3 and comparative example 5 of the present invention at a current density of 20mA/g, and it can be seen that the initial capacity of the obtained positive electrode material gradually increases with the increase of the sodium content, but the cycle stability also decreases, and the performance of example 2 obtained by two times of sintering is better than that of comparative example 5 obtained by only one time of sintering, and the electrochemical performance of example 2 is the best in view of the discharge capacity and the cycle stability.
FIGS. 5 to 7 are charge and discharge curves of the positive electrode materials of the sodium ion batteries of the tunnel phase structures obtained in comparative example 3, comparative example 4 and example 2 of the present invention at a current density of 20mA/g, respectively; FIG. 8 is a graph showing a comparison of capacity cycles of positive electrode materials of sodium ion batteries obtained in comparative example 3, comparative example 4 and example 2 of the present invention at a current density of 200 mA/g; fig. 9 is a graph comparing the rate performance of the positive electrode materials of the sodium ion batteries obtained in comparative example 3, comparative example 4 and example 2 at different current densities.
It can be seen that the positive electrode material Na of the sodium-ion battery with the tunnel phase structure in the comparative example 3 0.44 MnO 2 The battery is assembled, the first discharge capacity is 109.2mAh/g within the voltage range of 1.5-4.3V and under the current density of 200mA/g, and after 300 cycles, the capacity retention rate is 67.1%; under the current densities of 20mA/g, 40mA/g, 100mA/g, 200mA/g, 400mA/g, 1000mA/g and 2000mA/g, the first discharge capacities are respectively 116.9mAh/g, 107.1mAh/g, 98.1mAh/g, 89.8mAh/g, 72.9mAh/g, 10.3mAh/g and 0.6mAh/g.
Positive electrode material Na for sodium-ion battery having lamellar phase structure in comparative example 4 0.67 MnO 2 The battery is assembled, the first discharge capacity is 146.3mAh/g within the voltage range of 1.5-4.3V and under the current density of 200mA/g, and after 300 cycles, the capacity retention rate is 9.3%; under the current densities of 20mA/g, 40mA/g, 100mA/g, 200mA/g, 400mA/g, 1000mA/g and 2000mA/g respectively, the first discharge capacities are 169.0mAh/g, 117.7mAh/g, 103.2mAh/g, 94.9mAh/g, 77.7mAh/g, 54.4mAh/g and 30.6mAh/g respectively.
The positive electrode material Na of the sodium-ion battery with the composite structure of the tunnel phase and the lamellar phase in the embodiment 2 0.53 MnO 2 The battery is assembled, the first discharge capacity is 119.9mAh/g within the voltage range of 1.5-4.3V and under the current density of 200mA/g, and after 300 cycles, the capacity retention rate can reach 78.3%; under the current densities of 20mA/g, 40mA/g, 100mA/g, 200mA/g, 400mA/g, 1000mA/g and 2000mA/g respectively, the first discharge capacity can reach 123.9mAh/g, 117.0mAh/g, 115.2mAh/g, 112.1mAh/g, 106.9mAh/g, 90.8mAh/g and 47.2mAh/g respectively.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the sodium ion battery anode material with the tunnel phase and lamellar phase composite structure is characterized by comprising the following steps of: the method comprises the following steps:
(1) Mixing a sodium source compound and a manganese source compound according to a molar ratio to obtain mixed powder, wherein the molar ratio of sodium to manganese is 0.53 to 0.55;
(2) Sintering the mixed powder obtained in the step (1) for two times, wherein the temperature of the first sintering is 400-600 ℃, and the temperature of the second sintering is 800-1000 ℃;
the sodium ion battery anode material with the tunnel phase and layered phase composite structure takes the tunnel phase as a main phase and is in a rod-shaped and sheet-shaped composite shape.
2. The method for preparing the positive electrode material of the sodium-ion battery with the tunnel phase and the lamellar phase composite structure according to claim 1, characterized in that: the sodium source compound is selected from one or more of sodium acetate, sodium carbonate, sodium oxalate and sodium nitrate; the manganese source compound is selected from one or more of manganese acetate, manganese dioxide, manganese carbonate and manganese nitrate.
3. The method for preparing the positive electrode material of the sodium-ion battery with the tunnel phase and the lamellar phase composite structure according to claim 1, characterized in that: the heating rate of the first sintering is 1-5 ℃/min, the temperature is increased to 400-600 ℃, the temperature is kept for 4-6 h, and the sintering atmosphere is air.
4. The preparation method of the sodium-ion battery cathode material with the tunnel phase and lamellar phase composite structure according to claim 1, is characterized in that: the heating rate of the second sintering is 1 to 5 ℃/min, the temperature is increased to 800 to 1000 ℃, the temperature is kept for 12 to 18h, and the sintering atmosphere is air.
5. The sodium-ion battery cathode material with a tunnel phase and lamellar phase composite structure, which is prepared by the preparation method of any one of claims 1 to 4.
6. The utility model provides a positive plate of sodium ion battery which characterized in that: the sodium-ion battery positive electrode material with the tunnel phase and lamellar phase composite structure, which is prepared by the preparation method of any one of claims 1 to 4, a conductive additive and an adhesive are dissolved in an organic solvent, uniformly mixed and coated on an aluminum foil to prepare the sodium-ion battery positive electrode material.
7. The positive plate of the sodium-ion battery according to claim 6, wherein: the conductive additive is Super C65, the adhesive is polyvinylidene fluoride, and the organic solvent is N-methylpyrrolidone.
8. A sodium ion battery, characterized by: the positive plate of the sodium-ion battery, the diaphragm, the organic electrolyte and the metal sodium plate are mainly composed of the positive plate of the sodium-ion battery in claim 7.
9. The sodium-ion battery of claim 8, wherein: the diaphragm is GF/F, the organic electrolyte is propylene carbonate electrolyte, the solute is sodium perchlorate, and the concentration of the electrolyte is 1mol/L.
10. Use of the sodium-ion battery of claim 8 in an energy storage device.
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