CN114229902B - Manganese sulfide containing gamma/alpha heterogeneous junction and preparation method and application thereof - Google Patents
Manganese sulfide containing gamma/alpha heterogeneous junction and preparation method and application thereof Download PDFInfo
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Abstract
The application belongs to the field of rechargeable batteries, relates to a preparation method of an electrode material for a sodium ion battery, and particularly relates to manganese sulfide containing gamma/alpha heterogeneous junctions, and a preparation method and application thereof. The single-phase manganese sulfide is prepared by a simple liquid phase method, then incomplete phase transformation of the manganese sulfide is induced by simple heat treatment, and the manganese sulfide containing gamma/alpha heterogeneous junction is prepared and used as a negative electrode of a sodium ion battery. The application takes common manganese salt and sulfur source as raw materials, and prepares the manganese sulfide containing gamma/alpha heterogeneous junction through incomplete phase transformation induced by heat treatment, and the manganese sulfide shows excellent electrochemical performance when being used as a sodium ion battery electrode material. The application has the characteristics of novel thought, simple and convenient process, excellent comprehensive electrochemical performance of the product and the like.
Description
Technical Field
The application belongs to the field of rechargeable batteries, relates to a preparation method of an electrode material for a sodium ion battery, and particularly relates to manganese sulfide containing gamma/alpha heterogeneous junctions, and a preparation method and application thereof.
Background
The metal sulfide anode material in the sodium ion battery anode material has the advantages of high specific capacity, wide raw material sources and the like. Manganese sulfide is a typical metal sulfide negative electrode material, has higher theoretical specific capacity (660 mA h/g) when used as a negative electrode of a sodium ion battery, and is a potential sodium ion battery electrode material.
Although the manganese sulfide anode has a plurality of advantages, the first-circle charge-discharge efficiency is lower and the cycle life is poorer because of the problems of larger crystal structure change, serious particle pulverization and the like of the material in the charge-discharge process; meanwhile, as the ionic conductivity of the manganese sulfide is lower, the multiplying power performance of the material is poorer when the battery is charged and discharged with large current. In recent years, researchers have tried various modification methods (heteroatom doping, cladding/recombination, nanocrystallization, etc.) in an attempt to improve the electrochemical performance of the manganese sulfide sodium storage anode.
However, these conventional modification methods still fail to achieve satisfactory overall electrochemical properties, particularly coexistence of high specific capacity, long cycle life, and excellent rate capability. In addition, the manganese sulfide has few modification strategy types, mainly comprising carbon coating and nano-scale. Some methods are complex, expensive or severely polluted, which is not beneficial to the large-scale industrialized application of materials. Therefore, a simpler, more convenient and effective modification strategy must be developed to improve the comprehensive sodium storage performance of manganese sulfide, thereby promoting the industrialized application process thereof.
Disclosure of Invention
Aiming at the problems or improvement demands in the practical application of a manganese sulfide sodium storage cathode, the application provides a manganese sulfide containing gamma/alpha heterogeneous junction, a preparation method and an application thereof, wherein a single-phase manganese sulfide hollow sphere is prepared by a liquid phase method, and incomplete phase transformation of manganese sulfide is induced to form heterogeneous junction at a proper heat treatment temperature. When used as a negative electrode material of a sodium ion battery, the manganese sulfide heterogeneous junction shows comprehensive electrochemical performance superior to that of a single phase. The manganese sulfide heterogeneous junction modification strategy provided by the work has the advantages of simplicity in operation, uniformity in components, avoidance of new problems and the like.
The technical scheme of the application is realized as follows:
a preparation method of manganese sulfide containing gamma/alpha heterogeneous junction comprises the following steps: the method is characterized in that manganese salt and a sulfur source are used as raw materials, a liquid phase method is used for preparing single-phase manganese sulfide hollow spheres, and the single-phase manganese sulfide is converted into manganese sulfide containing gamma/alpha heterogeneous junction through an incomplete phase conversion process induced by heat treatment.
The method comprises the following specific steps:
(1) Dissolving manganese salt in a solvent I, stirring until the manganese salt is dissolved, adding a sulfur source and a surfactant, then placing the mixture into a reaction kettle for reaction, and washing and drying after the reaction is finished to obtain single-phase manganese sulfide hollow spheres;
(2) And (3) placing the manganese sulfide hollow spheres prepared in the step (1) into a tube furnace, heating to a certain temperature under the protection of inert atmosphere, preserving heat for a period of time, and then cooling to room temperature to obtain the manganese sulfide containing gamma/alpha heterogeneous junction.
The manganese salt in the step (1) is one or two of manganese nitrate and manganese acetate; the solvent I is one or two of water and glycol.
The sulfur source is one or two of elemental sulfur and thiourea; the surfactant is one or two of polyvinylpyrrolidone and triethanolamine.
The reaction condition in the step (1) is that the reaction temperature is 100-200 ℃ and the reaction time is 5-24h.
In the step (2), the certain temperature is 300-600 ℃, and the heat preservation time is 1-24h.
The manganese sulfide containing the gamma/alpha heterogeneous junction prepared by the method is of a hollow sphere structure, gamma-phase manganese sulfide with high specific capacity and poor structural stability is arranged in the hollow sphere structure, alpha-phase manganese sulfide with good stability is arranged on the surface of the hollow sphere structure, and the gamma-phase manganese sulfide and the alpha-phase manganese sulfide are combined through the gamma/alpha heterogeneous junction.
The anode material prepared by the manganese sulfide containing the gamma/alpha heterogeneous junction is used.
The sodium ion battery containing the negative electrode material has a specific capacity of 362.9 mA h/g after 1000 cycles of current density of 5000 mA/g and a specific capacity of 261.6 mA h/g at current density of 10000 mA/g.
The application has the following beneficial effects:
1. the application prepares the hollow spherical manganese sulfide single-phase precursor by using a simple liquid phase method, prepares the manganese sulfide material with gamma/alpha heterogeneous junction through a simple heat treatment induced incomplete phase transition process, and is applied to a sodium ion battery system. Preparing a hollow spherical manganese sulfide single-phase precursor by adopting a liquid phase method; and (3) inducing incomplete phase transition of manganese sulfide at a specific temperature through heat treatment to prepare the manganese sulfide electrode material with gamma/alpha heterogeneous junction.
2. The application converts gamma-phase manganese sulfide precursor into manganese sulfide with gamma/alpha heterogeneous junction. The heterogeneous junction optimization strategy of the manganese sulfide material enhances the sodium ion adsorption capacity of the surface of the manganese sulfide material. The specific capacity of the electrode optimized by using the out-of-phase junction strategy can reach 491.5 mA h/g in the first circle.
3. The application converts gamma-phase manganese sulfide precursors to manganese sulfide containing gamma/alpha heterogeneous junctions. A layer of alpha-phase manganese sulfide with good structural stability is constructed on the surface of gamma-phase manganese sulfide with high specific capacity and poor structural stability, and a gamma/alpha heterogeneous junction is formed, so that electrode structural collapse caused by the damage to the crystal structure of the manganese sulfide in the charge and discharge process is reduced, and the structural stability of the electrode is improved. The specific capacity of the electrode after being optimized by using the heterogeneous junction strategy can reach 446 mA h/g after being cycled for 80 circles under the current density of 100 mA/g, and the cycle performance is superior to that of gamma-phase manganese sulfide.
4. The application converts gamma-phase manganese sulfide precursor into manganese sulfide with gamma/alpha heterogeneous junction. Since the electron conductivity at the interface of the gamma/alpha heterogeneous junction of manganese sulfide is higher than that of gamma-phase manganese sulfide, the ion diffusion energy barrier is lower than that of gamma-phase manganese sulfide. Therefore, the modified electrode material has smaller overall impedance and better multiplying power performance. The specific capacity of the electrode optimized by using the heterogeneous junction strategy can reach 261.6 mA h/g under 10000 mA/g current density, and the multiplying power performance is superior to that of gamma-phase manganese sulfide.
5. The manganese source used in the application is common manganese salt and the sulfur source is common sulfur-containing substance, so the method has the advantages of wide raw material source, simplicity, easiness in obtaining and the like, and the method uses incomplete phase transition induced by simple heat treatment to prepare the manganese sulfide hollow sphere with gamma/alpha heterogeneous junction, has simple process and low requirement on equipment, and can realize large-scale continuous production.
Drawings
In order to more clearly illustrate the embodiments of the application or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope image of a sample prepared in example 2 of the present application.
FIG. 2 is an X-ray diffraction pattern of a sample prepared in example 4 of the present application.
FIG. 3 is a lattice fringe of a sample prepared in example 4 of the present application under a transmission electron microscope.
FIG. 4 is a scanning electron microscope image of a sample prepared in example 5 of the present application.
FIG. 5 is a scanning electron microscope image of a sample prepared in example 7 of the present application.
FIG. 6 is a theoretical calculation of electron density contrast for gamma-phase manganese sulfide, and manganese sulfide containing gamma/alpha heterogeneous junctions.
FIG. 7 is a comparison of the diffusion energy barriers of sodium ions at the interface of gamma-phase manganese sulfide and manganese sulfide containing gamma/alpha heterogeneous junctions calculated by theory.
Fig. 8 is a comparison of electrochemical impedance when gamma-phase manganese sulfide, a sample prepared in example 4 of the present application, was used as a negative electrode material.
Fig. 9 is a comparison of cycle performance of gamma-phase manganese sulfide, a sample prepared in example 4 of the present application, as a negative electrode material.
Fig. 10 is a comparison of rate performance of gamma-phase manganese sulfide, a sample prepared in example 4 of the present application, as a negative electrode material.
Detailed Description
The technical solutions of the present application will be clearly and completely described in conjunction with the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without any inventive effort, are intended to be within the scope of the application.
Example 1
The preparation method of the manganese sulfide containing the gamma/alpha heterogeneous junction comprises the following steps:
(1) Weighing 0.49. 0.49 g manganese acetate tetrahydrate, dissolving in 25 mL ethylene glycol, and stirring until the manganese acetate tetrahydrate is completely dissolved; then 0.256 g sublimed sulfur powder and 0.3 g polyvinylpyrrolidone are weighed and added into the solution; placing the obtained solution into a reaction kettle, heating to 150 ℃, and preserving heat for 24 hours; cooling the reaction kettle to room temperature after the reaction is finished, taking out a sample, washing a reaction product by using an ethanol/water (volume ratio is 1:1) mixture, and placing the reaction product in a vacuum oven for drying;
(2) And (3) placing the sample obtained in the step (1) in a tube furnace, introducing nitrogen flow for 30min to remove oxygen in the tube, heating to 300 ℃ at a speed of 3 ℃/min under the protection of nitrogen, preserving heat for 24h, and cooling to room temperature after heating to obtain a reaction end product.
Example 2
The preparation method of the manganese sulfide containing the gamma/alpha heterogeneous junction comprises the following steps:
(1) Weighing 0.49. 0.49 g manganese acetate tetrahydrate, dissolving in 25 mL ethylene glycol, and stirring until the manganese acetate tetrahydrate is completely dissolved; then 0.256 g sublimed sulfur powder and 0.3 g polyvinylpyrrolidone are weighed and added into the solution; placing the obtained solution into a reaction kettle, heating to 180 ℃, and preserving heat for 24 hours; cooling the reaction kettle to room temperature after the reaction is finished, taking out a sample, washing a reaction product by using an ethanol/water (volume ratio is 1:1) mixture, and placing the reaction product in a vacuum oven for drying;
(2) And (3) placing the sample obtained in the step (1) in a tube furnace, introducing nitrogen flow for 30min to remove oxygen in the tube, heating to 600 ℃ at a speed of 3 ℃/min under the protection of nitrogen, preserving heat for 1h, and cooling to room temperature after heating to obtain a reaction end product.
Example 3
The preparation method of the manganese sulfide containing the gamma/alpha heterogeneous junction comprises the following steps:
(1) Weighing 0.49. 0.49 g manganese acetate tetrahydrate, dissolving in 25 mL ethylene glycol, and stirring until the manganese acetate tetrahydrate is completely dissolved; then 0.128 g sublimed sulfur powder and 0.3 g polyvinylpyrrolidone are weighed and added into the solution; placing the obtained solution into a reaction kettle, heating to 200 ℃, and preserving heat for 12 hours; cooling the reaction kettle to room temperature after the reaction is finished, taking out a sample, washing a reaction product by using an ethanol/water (volume ratio is 1:1) mixture, and placing the reaction product in a vacuum oven for drying;
(2) And (3) placing the sample obtained in the step (1) in a tube furnace, introducing nitrogen flow for 30min to remove oxygen in the tube, heating to 500 ℃ at a speed of 3 ℃/min under the protection of nitrogen, preserving heat for 10h, and cooling to room temperature after heating to obtain a reaction end product.
Example 4
The preparation method of the manganese sulfide containing the gamma/alpha heterogeneous junction comprises the following steps:
(1) Weighing 0.49. 0.49 g manganese acetate tetrahydrate, dissolving in 25 mL ethylene glycol, and stirring until the manganese acetate tetrahydrate is completely dissolved; then 0.128 g sublimed sulfur powder and 0.3 g polyvinylpyrrolidone are weighed and added into the solution; placing the obtained solution into a reaction kettle, heating to 180 ℃, and preserving heat for 24 hours; cooling the reaction kettle to room temperature after the reaction is finished, taking out a sample, washing a reaction product by using an ethanol/water (volume ratio is 1:1) mixture, and placing the reaction product in a vacuum oven for drying;
(2) And (3) placing the sample obtained in the step (1) in a tube furnace, introducing nitrogen flow for 30min to remove oxygen in the tube, heating to 400 ℃ at a speed of 3 ℃/min under the protection of nitrogen, preserving heat for 1h, and cooling to room temperature after heating to obtain a reaction end product.
Example 5
The preparation method of the manganese sulfide containing the gamma/alpha heterogeneous junction comprises the following steps:
(1) Weighing 0.50 g manganese nitrate tetrahydrate, dissolving in 25 mL water, and stirring until the manganese nitrate tetrahydrate is completely dissolved; then 0.256 g sublimed sulfur powder and 0.3 g polyvinylpyrrolidone are weighed and added into the solution; placing the obtained solution into a reaction kettle, heating to 150 ℃, and preserving heat for 24 hours; cooling the reaction kettle to room temperature after the reaction is finished, taking out a sample, washing a reaction product by using an ethanol/water (volume ratio is 1:1) mixture, and placing the reaction product in a vacuum oven for drying;
(2) And (3) placing the sample obtained in the step (1) in a tube furnace, introducing nitrogen flow for 30min to remove oxygen in the tube, heating to 400 ℃ at a speed of 3 ℃/min under the protection of nitrogen, preserving heat for 2h, and cooling to room temperature after heating to obtain a reaction end product.
Example 6
The preparation method of the manganese sulfide containing the gamma/alpha heterogeneous junction comprises the following steps:
(1) Weighing 0.49. 0.49 g tetrahydrate manganese nitrate, dissolving in 25 mL ethylene glycol, and stirring until the tetrahydrate manganese nitrate is completely dissolved; adding 0.30 g thiourea and 2mL of triethanolamine into the solution; placing the obtained solution into a reaction kettle, heating to 100 ℃, and preserving heat for 5 hours; cooling the reaction kettle to room temperature after the reaction is finished, taking out a sample, washing a reaction product by using an ethanol/water (volume ratio is 1:1) mixture, and placing the reaction product in a vacuum oven for drying;
(2) And (3) placing the sample obtained in the step (1) in a tube furnace, introducing nitrogen flow for 30min to remove oxygen in the tube, heating to 500 ℃ at a speed of 3 ℃/min under the protection of nitrogen, preserving heat for 12h, and cooling to room temperature after heating to obtain a reaction end product.
Example 7
The preparation method of the manganese sulfide containing the gamma/alpha heterogeneous junction comprises the following steps:
(1) Weighing 0.49. 0.49 g manganese acetate tetrahydrate, dissolving in 25 mL ethylene glycol, and stirring until the manganese acetate tetrahydrate is completely dissolved; then 0.256 g sublimed sulfur powder and 0.3 g polyvinylpyrrolidone are weighed and added into the solution; placing the obtained solution into a reaction kettle, heating to 180 ℃, and preserving heat for 12 hours; cooling the reaction kettle to room temperature after the reaction is finished, taking out a sample, washing a reaction product by using an ethanol/water (volume ratio is 1:1) mixture, and placing the reaction product in a vacuum oven for drying;
(2) And (3) placing the sample obtained in the step (1) in a tube furnace, introducing nitrogen flow for 30min to remove oxygen in the tube, heating to 300 ℃ at a speed of 3 ℃/min under the protection of nitrogen, preserving heat for 1h, and cooling to room temperature after heating to obtain a reaction end product.
Example 8
The preparation method of the manganese sulfide containing the gamma/alpha heterogeneous junction comprises the following steps:
(1) Weighing 0.49. 0.49 g manganese acetate tetrahydrate, dissolving in 25. 25 mL water, and stirring until the manganese acetate tetrahydrate is completely dissolved; adding 0.256 g sublimed sulfur powder and 2mL of triethanolamine into the solution; placing the obtained solution into a reaction kettle, heating to 150 ℃, and preserving heat for 24 hours; cooling the reaction kettle to room temperature after the reaction is finished, taking out a sample, washing a reaction product by using an ethanol/water (volume ratio is 1:1) mixture, and placing the reaction product in a vacuum oven for drying;
(2) And (3) placing the sample obtained in the step (1) in a tube furnace, introducing nitrogen flow for 30min to remove oxygen in the tube, heating to 600 ℃ at a speed of 3 ℃/min under the protection of nitrogen, preserving heat for 1h, and cooling to room temperature after heating to obtain a reaction end product.
FIGS. 1, 4 and 5 are scanning electron microscope images of samples prepared in examples 2, 5 and 7, respectively. Although examples 2, 5 and 7 each used different process conditions, the prepared samples all exhibited distinct nanosphere characteristics with diameters varying from 100 to 500 nm. Furthermore, the hollow nature of the interior of the nanospheres is evident from the small number of breaks in the nanospheres illustrated in the inset of FIG. 4.
FIG. 2 is an X-ray diffraction pattern of a sample prepared in example 4 of the present application. From the position and intensity of diffraction peak in the graph, the sample mainly consists of two crystal forms of gamma-phase manganese sulfide and alpha-phase manganese sulfide. Wherein the number and intensity of diffraction peaks of gamma-phase manganese sulfide are higher than those of alpha-phase manganese sulfide, which indicates that the gamma-phase manganese sulfide is the main component in the sample.
FIG. 3 is a lattice fringe pattern of a sample under a transmission electron microscope prepared in example 4 of the present application. It is apparent from the figure that the lattice fringes ascribed to the gamma-phase manganese sulfide (103) crystal plane and the lattice fringes ascribed to the alpha-phase manganese sulfide (220) crystal plane are closely combined to form a stable heterogeneous structure.
FIG. 6 is a comparison of calculated results of theoretical calculations on gamma-phase manganese sulfide and electron density of manganese sulfide containing gamma/alpha heterogeneous junctions. As can be seen from fig. 6a, the electron number near the fermi level of gamma-phase manganese sulfide is close to 0, indicating that its intrinsic electron conductivity is low, which is detrimental to its rate capability. In contrast, the electron number near the fermi level of manganese sulfide containing the gamma/alpha heterogeneous junction (fig. 6 b) is obviously not 0, which shows that the intrinsic electron conductivity is superior to that of gamma-phase manganese sulfide, and the rate capability of manganese sulfide is improved.
FIG. 7 is a comparison of the diffusion energy barriers of sodium ions at the interface of gamma-phase manganese sulfide and manganese sulfide containing gamma/alpha heterogeneous junctions calculated by theory. From the graph, the diffusion energy barrier of sodium ions containing gamma/alpha heterogeneous junction manganese sulfide is obviously lower than that of gamma-phase manganese sulfide, which shows that the diffusion resistance of sodium ions at an interface is smaller, the damage to surrounding grain boundaries is smaller, and the multiplying power and the cycle performance of manganese sulfide are improved.
Examples of the effects
The electrode sheet is coated with the material prepared in the above embodiment, and after being assembled into a button sodium ion battery, the electrochemical performance test is performed, and the steps are as follows:
1. preparation of electrode sheet
Mixing and grinding the sample prepared in the embodiment with ketjen black and polyvinylidene fluoride according to the mass ratio of 7:2:1, adding a nitrogen-methyl pyrrolidone solvent to prepare slurry, coating the slurry on a copper foil current collector, and placing the copper foil current collector in a vacuum drying oven to bake for 10 hours at 80 ℃. The dried pole piece is punched into a circular piece with the diameter of 8 mm, and the loaded active substance loading (the active substance surface density is about 1-2 mg/cm) is weighed and calculated 2 ）。
2. Assembly of sodium ion battery
The electrode sheet of the above example was punched into a disk having a diameter of 8 mm, and the active material loading (active material areal density of about 1-2 mg/cm) was weighed and calculated 2 ). The CR-2032 button cell was assembled in an argon-protected glove box using the wafer electrode as the working electrode, a self-made sodium sheet as the counter electrode (diameter of about 12 mm and thickness of about 2 mm), a glass fiber filter membrane as the membrane, and 1 mol/L NaSO 3 CF 3 The solution is electrolyte (the solvent is diethylene glycol dimethyl ether), and the packaging machine is used for packaging after the assembly is completed. After the battery is assembled, the battery is kept stand for 8 h and then subjected to electrochemical performance test.
3. Electrochemical performance test
Fig. 8 is a comparison of electrochemical impedance when gamma-phase manganese sulfide, a sample prepared in example 4 of the present application, was used as a negative electrode material. From the graph, the charge transfer impedance of the sample prepared in the embodiment 4 of the application is lower than that of gamma-phase manganese sulfide, which shows that the electrochemical impedance of the manganese sulfide containing gamma/alpha heterogeneous junction in the sodium storage process is smaller, thereby being beneficial to improving the multiplying power performance of the manganese sulfide.
Fig. 9 is a comparison of cycle performance of gamma-phase manganese sulfide, a sample prepared in example 4 of the present application, as a negative electrode material. As can be seen from the graph, the first-circle specific capacity of the sample prepared in the example 4 under the current density of 100 mA/g can reach 437 mA h/g, the specific capacity after 80 circles is 446 mA h/g, the capacity retention rate is 102.1%, the coulomb efficiency is close to 100%, and the overall performance is superior to that of gamma-phase manganese sulfide. The results show that the cycle performance of the manganese sulfide containing the gamma/alpha heterogeneous junction is superior to that of gamma-phase manganese sulfide.
Fig. 10 is a comparison of rate performance of gamma-phase manganese sulfide, a sample prepared in example 4 of the present application, as a negative electrode material. As can be seen from the graph, the specific capacity of the sample prepared in the example 4 can reach 491.5 mA h/g at the current density of 100 mA/g, 261.6 mA h/g at the current density of 10000 mA/g, the capacity retention rate is 53.2%, the specific capacity is still stable when the current density is changed frequently, and the overall performance is superior to that of gamma-phase manganese sulfide. The results show that the rate capability of the manganese sulfide containing the gamma/alpha heterogeneous junction is superior to that of gamma-phase manganese sulfide.
The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the application.
Claims (6)
1. A method for preparing manganese sulfide containing gamma/alpha heterogeneous junction, which is characterized by comprising the following steps:
(1) Dissolving manganese salt in a solvent I, stirring until the manganese salt is dissolved, adding a sulfur source and a surfactant, then placing the mixture into a reaction kettle for reaction, and washing and drying after the reaction is finished to obtain single-phase manganese sulfide hollow spheres; the solvent I is one or two of water and glycol;
(2) Placing the manganese sulfide hollow spheres prepared in the step (1) into a tube furnace, heating to a certain temperature under the protection of inert atmosphere, preserving heat for a period of time, and then cooling to room temperature to obtain manganese sulfide containing gamma/alpha heterogeneous junctions; the surfactant is one or two of polyvinylpyrrolidone and triethanolamine;
the reaction condition in the step (1) is that the reaction temperature is 100-200 ℃ and the reaction time is 5-24h;
in the step (2), the certain temperature is 300-600 ℃, and the heat preservation time is 1-24h.
2. The method for preparing the manganese sulfide containing gamma/alpha heterogeneous junctions according to claim 1, wherein the method comprises the following steps: the manganese salt in the step (1) is one or two of manganese nitrate and manganese acetate.
3. The method for preparing the manganese sulfide containing gamma/alpha heterogeneous junctions according to claim 1, wherein the method comprises the following steps: the sulfur source is one or two of elemental sulfur and thiourea.
4. A manganese sulphide containing a gamma/alpha heterogeneous junction prepared by the process of any one of claims 1 to 3, characterised in that: the manganese sulfide containing the gamma/alpha heterogeneous junction is of a hollow sphere structure, gamma-phase manganese sulfide with high specific capacity and poor structural stability is arranged in the hollow sphere structure, alpha-phase manganese sulfide with good stability is arranged on the surface of the hollow sphere structure, and the gamma-phase manganese sulfide and the alpha-phase manganese sulfide are combined through the gamma/alpha heterogeneous junction.
5. A negative electrode material prepared using the manganese sulfide containing a gamma/alpha heterogeneous junction according to claim 4.
6. A sodium ion battery comprising the negative electrode material of claim 5, characterized in that: the specific capacity of the sodium ion battery reaches 362.9 mA h/g after 1000 circles of circulation under the current density of 5000 mA/g, and the specific capacity of the sodium ion battery reaches 261.6 mA h/g under the current density of 10000 mA/g.
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