CN112803017A - Hollow spherical bimetal chalcogenide, preparation method thereof and sodium battery cathode - Google Patents
Hollow spherical bimetal chalcogenide, preparation method thereof and sodium battery cathode Download PDFInfo
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Abstract
The invention discloses a hollow spherical bimetal chalcogenide (Ni)0.33Co0.67SSe), a preparation method thereof and a sodium battery cathode, belonging to the technical field of secondary battery electrode material preparation. Firstly, preparing a nickel cobalt glycerate precursor, mixing the nickel cobalt glycerate precursor with sodium sulfide nonahydrate, and synthesizing hollow spherical NiCo through hydrothermal reaction2S4Nano material, finally, sulfurizing the sulfurized NiCo2S4Mixing the nano material with selenium powder, and calcining at high temperature to obtain Ni0.33Co0.67SSe materials, which are hollow spherical structures assembled from primary nanoparticles, provide good relief from volume expansion during cyclingThe phenomenon of active material structure collapse is caused, the double anions and the cations can improve the conductivity of the transition metal chalcogenide, and the sodium ion battery cathode prepared by using the double anions and the transition metal chalcogenide as the active material has better cycle stability and has the current density of 5A g‑1The battery capacity is still as high as 534.7mA h g after 2000 cycles‑1(ii) a Even at 20A g‑1Also showed 608.1mA h g at the current density of (2)‑1Excellent rate capability.
Description
Technical Field
The invention belongs to the technical field of negative electrode materials of sodium-ion batteries, and particularly relates to a hollow spherical bimetal chalcogenide compound, a preparation method thereof and a negative electrode material of a sodium battery.
Background
Lithium Ion Batteries (LIBs) have high energy density and excellent cycle stability, and have been widely used in various aspects of human daily life. However, the low lithium content and the uneven distribution of lithium in the earth have prompted the search for other energy storage systems that can replace lithium. In next-generation energy storage systems, Sodium Ion Batteries (SIBs) have attracted considerable attention due to low cost and abundant natural resources. In addition, the basic mechanism of the electrochemical reaction of sodium is similar to that of LIBs systems. However, a larger sodium metal ion radius generally results in slow reaction kinetics, instability of the solid electrolyte interphase layer, and collapse of the host material crystal structure, resulting in reduced electrochemical performance. In this case, it is highly desirable to search for a suitable anode material having high capacity and cycle stability.
Over the past few years, several classical negative electrode materials for storing alkali metal ions have been investigated, such as carbon materials, traditional intercalation compounds, metal compounds, and the like. Low Na with insertion type material+Compared to storage capacity, the transformed materials can offer higher theoretical capacities, thus showing great potential. In particular, transition metal chalcogenides exhibit excellent rate capability and good cycling stability due to relatively high electron conductivity. However, most of them still suffer from inherently low conductivity and inevitable volume changes during long cycling, which will result in poor rate performance and rapid capacity fade.
Cobalt selenide (CoSe)2) Has high theoretical capacity (495mA h g-1) Considered as one of the promising anode materials for SIB. However, during the repeated charge and discharge process, the defects of rapid degradation of the powdering capacity of the electrode material caused by volume expansion, irreversible capacity loss, slow kinetics and the like still exist.
Disclosure of Invention
Technical problem to be solved
In order to solve the problems, the invention provides a hollow spherical bimetallic chalcogenide compound, a preparation method thereof and a sodium battery cathode material. Firstly, preparing a nickel cobalt glycerate precursor through solvothermal reaction; then, the obtained precursor is mixed with sodium sulfide nonahydrate and synthesized into hollow graded porous nano spherical NiCo through hydrothermal reaction2S4A material; finally, NiCo is added2S4And selenium powder is placed in a silicon dioxide glazed ceramic boat and selenized in a tube furnace. After selenization, the final Ni0.33Co0.67SSe products in N2Ambient annealing to increase the crystallinity of the sample. The obtained hollow spherical bimetallic chalcogenide (Ni)0.33Co0.67SSe) is a hollow graded porous spherical structure with the diameter of about 410nm, and the structure can well relieve the phenomenon of active material structure collapse caused by volume expansion in the process of repeated charge and discharge; in addition, the adopted anion-cation double substitution strategy can adjust the electronic structure of the transition metal chalcogenide and improve the carrier concentration, so that the conductivity is improved, and the cycle performance of the sodium ion battery is improved.
The invention provides a hollow spherical Ni0.33Co0.67The sodium ion battery cathode prepared by SSe as an active material has excellent cycle stability and rate capability and has the current density of 5A g-1The battery capacity is still as high as 534.7mA h g after 2000 cycles-1(ii) a Even at 20A g-1Also showed 608.1mA h g at the current density of (2)-1Excellent rate capability.
(II) technical scheme
The technical scheme adopted by the invention is as follows:
a preparation method of a hollow spherical bimetallic chalcogenide material comprises the steps of firstly, dissolving two metal nitrate hydrates in a mixed solution of glycerol and isopropanol by adopting a solvothermal method to obtain a precursor solution; then sulfurizing the precursor through anion exchange; finally, selenizing and annealing to obtain the hollow spherical bimetal chalcogenide compound; the preparation method comprises the following steps:
step (1) adding Co (NO)3)2·6H2O and Ni (NO)3)2·6H2O is dissolved in the mixed solution of glycerol and isopropanol, and forms a transparent pink solution after being stirred for a certain time. Then carrying out hydrothermal reaction, and after the reaction is finished, centrifuging, washing and drying to obtain the nano solid spherical NiCo-glycerate precursor.
Dispersing the nano solid spherical NiCo-glycerate precursor powder in deionized water, adding sodium sulfide nonahydrate into the deionized water, stirring and mixing the mixture uniformly, then carrying out hydrothermal reaction, and after the reaction is finished, centrifuging, washing and drying the precipitate to obtain the hollow nano spherical NiCo2S4。
Step (3) preparing NiCo2S4And selenium powder were placed on opposite corners of a silica-glazed ceramic boat and covered with aluminum foil, followed by calcination in an Ar atmosphere for a period of time. After selenization, the final Ni0.33Co0.67SSe products in N2And annealing under the environment to improve the crystallinity of the sample.
Further, in the step (1), the mass ratio of the cobalt source to the nickel source is 2: 1; the volumes of the glycerol and the isopropanol are respectively 5-10 mL and 35-40 mL; the conditions of the hydrothermal reaction are as follows: the reaction is carried out for 6h at 180 ℃.
Preferably, the volumes of the glycerol and the isopropanol are 8mL and 40mL respectively;
preferably, the hydrothermal reaction is carried out at 180 ℃ for 6 hours.
Further, in the step (2), the mass ratio of the NiCo-glycerate precursor powder to the sodium sulfide nonahydrate is 1: 5-1: 16; the volume of the deionized water is 30 mL; the hydrothermal reaction is carried out for 4-10 h at the temperature of 120-180 ℃.
In the step (2), preferably, the mass ratio of the NiCo-glycerate precursor powder to the sodium sulfide nonahydrate is 3: 16;
preferably, the volume of the deionized water is 30 mL;
the hydrothermal reaction condition is preferably 160 ℃ and the reaction time is 8 h.
In the step (3), the hollow nano spherical NiCo2S4The mass ratio of the selenium powder to the selenium powder is 1: 1-1: 4; preferably 1: 2;
preferably, the annealing is carried out for 4 hours in an argon atmosphere at 400 ℃; then annealing is carried out for 90min in a nitrogen environment at 300 ℃.
Further, the hollow spherical bimetallic chalcogenide material prepared by the method has a hierarchical nano structure formed by assembling primary nano particles, the inner part of the bimetallic chalcogenide material is in a spherical shape with a cavity, the diameter of the bimetallic chalcogenide material is 400-450 nanometers, and the average thickness of a hollow shell is 50 nanometers; the structural formula of the bimetal chalcogenide is Ni0.33Co0.67SSe。
Furthermore, the material is a graded nano hollow sphere structure assembled by primary nano particles, and the molecular formula is Ni0.33Co0.67SSe。
The sodium ion battery cathode contains the hollow spherical bimetallic chalcogenide material, and the sodium ion battery cathode contains the hollow spherical bimetallic chalcogenide material; and uniformly mixing the material, the conductive agent and the binder in proportion, adding a polar solution, uniformly stirring to form viscous fluid slurry, coating the fluid slurry on a current collector, and drying to obtain the negative electrode of the sodium-ion battery.
The conductive agent and the binder of the negative electrode of the sodium ion battery are Super P, Styrene Butadiene Rubber (SBR) and carboxymethyl cellulose (CMC) respectively; the ratio of active material, conductive agent and binder is 7: 2: 0.5: 0.5; deionized water is used as a solvent to be prepared into uniform slurry.
Hollow spherical bimetallic sulfur family compound Ni prepared by the method0.33Co0.67When the SSe material is used as a negative electrode active material of a sodium ion battery, smaller crystal domains can be realized by introducing other transition metals, and the diffusion path of sodium metal ions is reduced; while the hollow structure of the transition metal compound solid solution can be obtained by a vulcanization process, the hollow structure can beThe volume expansion is relieved, the pulverization and the shedding of the active material are slowed down, and finally the excellent electrochemical performance is shown.
Compared with other prior art, the invention has the following outstanding advantages:
1. the graded morphology not only greatly expands the contact area between the electrode and the electrolyte, but also shortens the charging time due to the optimized network resistance, and the hollow structure can effectively adapt to the volume change during the electrochemical reaction.
2. The double anions can adjust the electronic structure of the transition metal chalcogenide and improve the carrier concentration, so that the conductivity is improved, and the dynamic property of sodium ions is enhanced.
3. The preparation method of the invention has the advantages of low preparation cost, good repeatability, simple operation and easy control.
Drawings
FIG. 1 is a scanning electron micrograph of a NiCo-glycerate precursor prepared in example 1;
FIG. 2 is a hollow spherical NiCo prepared in example 12S4Scanning electron micrographs and transmission images of the material; wherein: (a) scanning an electron microscope image; (b) and (5) transmitting pictures.
FIG. 3 is a hollow spherical Ni prepared in example 10.33Co0.67Scanning electron microscopy and transmission microscopy of SSe material; wherein: (a) scanning an electron microscope image; (b) and (5) transmitting pictures.
FIG. 4 is a hollow spherical NiCo prepared in example 22S4Scanning electron micrographs of the material;
FIG. 5 is a hollow spherical NiCo prepared in example 32S4Scanning electron micrographs of the material;
FIG. 6 is a hollow spherical NiCo prepared in example 42S4Scanning electron micrographs of the material;
FIG. 7 is a hollow spherical Ni prepared in example 50.33Co0.67An X-ray diffraction pattern of an SSe material;
FIG. 8 is a hollow spherical Ni prepared in example 10.33Co0.67An X-ray diffraction pattern of an SSe material;
FIG. 9 shows an embodiment of the present invention1 is hollow spherical Ni0.33Co0.67SSe is a negative electrode material, and electrolyte is sodium ion ether-based electrolyte, and the cycle performance test and the rate performance test of the 2032 button cell are carried out; wherein: (a) ni0.33Co0.67SSe electrode at Current Density 5A g-1Testing the cycle performance of the test; (b) ni0.33Co0.67SSe electrode at 0.2A g-1、0.5A g-1、1A g-1、2A g-1、5A g-1、10A g-1And 20A g-1And (5) carrying out rate performance test under current density.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. The following examples are presented merely to further understand and practice the present invention and are not to be construed as further limiting the claims of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
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 drawings in the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The present invention will be described in detail with reference to examples.
Example 1:
a preparation method of a hollow spherical bimetal chalcogenide material comprises the following steps:
(1) 0.25mmol of Co (NO)3)2·6H2O and 0.125mmol of Ni (NO)3)2·6H2O dissolved in 8mL of glycerol and 40mL of isopropanolA clear pink solution was formed. The solution was then transferred to an autoclave and held at 180 ℃ for 6 h. After natural cooling to room temperature, the brown precipitate was separated by centrifugation, washed several times with deionized water and ethanol, and dried in an oven at 80 ℃. Finally, NiCo-glycerate precursor is obtained, and the SEM picture is shown in the attached figure 1.
(2) Dissolving 30mg of NiCo-glycerate precursor prepared in the step (1) in 30mL of deionized water, vigorously stirring for about 30min, and adding 160mg of Na2S·9H2Adding O, and stirring for 15-20min to obtain black solution. The solution was then transferred to an autoclave and held at 160 ℃ for 8 h. After natural cooling to room temperature, the black precipitate was separated by centrifugation, washed several times with ethanol and dried in an oven at 80 ℃ to give NiCo2S4The hollow nanospheres, their SEM and TEM are shown in figure 2.
(3) The NiCo prepared in the step (2) is added2S4Mixing with Se powder according to the proportion of 1: 2, calcining in a tubular furnace, annealing for 4 hours at 400 ℃ in an Ar atmosphere, wherein the heating rate is 4 ℃/min at the beginning, and 2 ℃/min at the last half hour; finally in N2Annealing at 300 ℃ for 90min in the atmosphere at the heating rate of 2 ℃/min to obtain the graded hollow nano spherical Ni0.33Co0.67SSe materials, SEM and TEM are shown in FIG. 3.
As can be seen from fig. 1-3, NiCo-glycerate precursor nanoparticles have smooth surfaces and are solid nanospheres with an average particle size of 410 nm; after vulcanization, the size and the appearance of the nano particles are not obviously changed, the surface is rough, the nano particles are assembled by nano sheets, and a hollow structure is generated due to anion exchange; finally, the average particle size of the selenized nano particles is still 410nm, and the surface granulation is particularly obvious.
For the hollow spherical Ni of example 10.33Co0.67The SSe material is subjected to X-ray diffraction characterization and Rietveld refinement, as shown in FIG. 8, the result shows that the sample has a Pa-3 space group (JCPDS 09-0234), no impurity peak error peak appears, the peak shape is relatively sharp, and the hollow spherical Ni of the invention is illustrated0.33Co0.67SSe has good crystallinity.
Example 2:
graded spherical NiCo2S4The preparation of the nano material comprises the following steps:
(1) 0.25mmol of Co (NO)3)2·6H2O and 0.125mmol of Ni (NO)3)2·6H2O was dissolved in 8mL of glycerol and 40mL of isopropanol to form a clear pink solution. The solution was then transferred to an autoclave and held at 180 ℃ for 6 h. After natural cooling to room temperature, the brown precipitate was separated by centrifugation, washed several times with deionized water and ethanol, and dried in an oven at 80 ℃. Finally, NiCo-glycerate precursor is obtained, and the SEM picture is shown in the attached figure 1.
(2) Dissolving 30mg of NiCo-glycerate precursor prepared in the step (1) in 30mL of deionized water, vigorously stirring for about 30min, and adding 160mg of Na2S·9H2Adding O, and stirring for 15-20min to obtain black solution. The solution was then transferred to an autoclave and held at 120 ℃ for 8 h. After natural cooling to room temperature, the black precipitate was separated by centrifugation, washed several times with ethanol and dried in an oven at 80 ℃ to give NiCo2S4The hollow nanospheres, their SEM and TEM are shown in figure 4.
Example 3:
graded spherical NiCo2S4The preparation of the nano material comprises the following steps:
(1) 0.25mmol of Co (NO)3)2·6H2O and 0.125mmol of Ni (NO)3)2·6H2O was dissolved in 8mL of glycerol and 40mL of isopropanol to form a clear pink solution. The solution was then transferred to an autoclave and held at 180 ℃ for 6 h. After natural cooling to room temperature, the brown precipitate was separated by centrifugation, washed several times with deionized water and ethanol, and dried in an oven at 80 ℃. Finally, NiCo-glycerate precursor is obtained, and the SEM picture is shown in the attached figure 1.
(2) Dissolving 30mg of NiCo-glycerate precursor prepared in the step (1) in 30mL of deionized water, vigorously stirring for about 30min, and adding 160mg of Na2S·9H2Adding O, and stirring for 15-20min to obtain black solution. Then the solution is transferred toThe autoclave was removed and kept at 180 ℃ for 8 h. After natural cooling to room temperature, the black precipitate was separated by centrifugation, washed several times with ethanol and dried in an oven at 80 ℃ to give NiCo2S4The hollow nanospheres, their SEM and TEM are shown in figure 5.
Example 4:
graded spherical NiCo2S4The preparation of the nano material comprises the following steps:
(1) 0.25mmol of Co (NO)3)2·6H2O and 0.125mmol of Ni (NO)3)2·6H2O was dissolved in 8mL of glycerol and 40mL of isopropanol to form a clear pink solution. The solution was then transferred to an autoclave and held at 180 ℃ for 6 h. After natural cooling to room temperature, the brown precipitate was separated by centrifugation, washed several times with deionized water and ethanol, and dried in an oven at 80 ℃. Finally, NiCo-glycerate precursor is obtained, and the SEM picture is shown in the attached figure 1.
(2) Dissolving 30mg of NiCo-glycerate precursor prepared in the step (1) in 30mL of deionized water, vigorously stirring for about 30min, and adding 160mg of Na2S·9H2Adding O, and stirring for 15-20min to obtain black solution. The solution was then transferred to an autoclave and held at 160 ℃ for 4 h. After natural cooling to room temperature, the black precipitate was separated by centrifugation, washed several times with ethanol and dried in an oven at 80 ℃ to give NiCo2S4The hollow nanospheres, their SEM and TEM are shown in figure 6.
Example 5:
a preparation method of a hollow spherical bimetal chalcogenide material comprises the following steps:
(1) 0.25mmol of Co (NO)3)2·6H2O and 0.125mmol of Ni (NO)3)2·6H2O was dissolved in 8mL of glycerol and 40mL of isopropanol to form a clear pink solution. The solution was then transferred to an autoclave and held at 180 ℃ for 6 h. After natural cooling to room temperature, the brown precipitate was separated by centrifugation, washed several times with deionized water and ethanol, and dried in an oven at 80 ℃. Finally obtaining NiCo-glyceric acidA salt precursor having an SEM image as shown in figure 1.
(2) Dissolving 30mg of NiCo-glycerate precursor prepared in the step (1) in 30mL of deionized water, vigorously stirring for about 30min, and adding 160mg of Na2S·9H2Adding O, and stirring for 15-20min to obtain black solution. The solution was then transferred to an autoclave and held at 160 ℃ for 8 h. After natural cooling to room temperature, the black precipitate was separated by centrifugation, washed several times with ethanol and dried in an oven at 80 ℃ to give NiCo2S4The hollow nanospheres, their SEM and TEM are shown in figure 2.
(3) The NiCo prepared in the step (2) is added2S4Mixing with Se powder according to the proportion of 1: 4, calcining in a tubular furnace, annealing for 4 hours at 400 ℃ in an Ar atmosphere, wherein the heating rate is 4 ℃/min; finally in N2Annealing at 300 ℃ for 90min in the atmosphere at the heating rate of 2 ℃/min to obtain the graded hollow nano spherical Ni0.33Co0.67SSe material, XRD is shown in figure 7. It can be seen from the figure that the material is not phase-pure, but contains a portion of NiCo2S4。
Example 6: the application of a hollow spherical bimetallic chalcogenide material in a sodium ion battery is as follows:
the graded hollow spherical Ni obtained in example 1 was added0.33Co0.67The SSe3 nano material is used as a negative active material of a sodium ion battery, and the active material is mixed with Super P conductive additive, Styrene Butadiene Rubber (SBR) and carboxymethyl cellulose (CMC) according to the weight ratio of 7: 2: 0.5: 0.5, using deionized water as a solvent to prepare uniform slurry, coating the slurry on a copper foil, drying the copper foil at normal temperature, transferring a sample into a vacuum drying oven, and drying the sample for 12 hours at 60 ℃ in vacuum to prepare Ni0.33Co0.67An electrode slurry of SSe metal sulfoselenide.
Sodium sheet is used as anode, and the electrolyte is 1M NaPF sold in market6The 2032 coin cell of DME solution is used for cycle performance test and rate performance test. The battery has good cycle stability and current density of 5A g-1The battery capacity after 2000 times of circulation is still as high as 534.7mA h g-1(ii) a At current densityIs 20A g-1At lower has 608.1mA h g-1The excellent rate capability of the present invention is shown in fig. 9.
The above detailed description of the method for preparing the bimetallic chalcogenide material in the form of a hollow sphere, the negative electrode of a sodium battery and the battery, with reference to the examples, is illustrative and not restrictive; 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; such modifications and substitutions do not depart from the spirit and scope of the corresponding technical solutions.
While embodiments of the invention have been disclosed above, it is not intended to be limited to the uses set forth in the specification and examples. It can be applied to all kinds of fields suitable for the present invention. Additional modifications will readily occur to those skilled in the art. It is therefore intended that the invention not be limited to the exact details and illustrations described and illustrated herein, but fall within the scope of the appended claims and equivalents thereof.
Claims (9)
1. A preparation method of a hollow spherical bimetal chalcogenide is characterized in that firstly, a solvothermal method is adopted to dissolve two metal nitrate hydrates into a mixed solution of glycerol and isopropanol to obtain a precursor solution; then sulfurizing the precursor through anion exchange; finally, selenizing and annealing to obtain the hollow spherical bimetal chalcogenide compound; the preparation method comprises the following steps:
dissolving a cobalt source and a nickel source in a mixed solution of glycerol and isopropanol, carrying out solvothermal reaction on a supersaturated solution after vigorously stirring for a certain time, and then centrifuging, washing and drying a precipitate to obtain a nano solid spherical NiCo-glycerate precursor;
step (2), uniformly dispersing the nano solid spherical NiCo-glycerate precursor powder in deionized water, then adding sodium sulfide nonahydrate into the deionized water, stirring and uniformly mixing the mixture, and then carrying out water treatmentThermal reaction, after the reaction is finished, centrifuging, washing and drying the precipitate to obtain the graded hollow nano spherical NiCo2S4；
Step (3), mixing NiCo2S4And selenium powder are placed in a tube furnace and calcined for a period of time in Ar environment; after selenization, the final Ni0.33Co0.67SSe products in N2And annealing under the environment to improve the crystallinity of the sample.
2. The method for preparing a hollow globular bimetallic chalcogenide compound as claimed in claim 1, wherein in the step (1), the ratio of the amount of the cobalt source to the amount of the nickel source is 2: 1; the volumes of the glycerol and the isopropanol are respectively 5-10 mL and 35-40 mL; the conditions of the hydrothermal reaction are as follows: the reaction is carried out for 6h at 180 ℃.
3. The method for preparing a hollow spherical bimetallic chalcogenide compound as claimed in claim 1, wherein in the step (2), the mass ratio of the NiCo-glycerate precursor powder to the sodium sulfide nonahydrate is 1: 5-1: 16; the volume of the deionized water is 30 mL; the hydrothermal reaction is carried out for 4-10 h at the temperature of 120-180 ℃.
4. The method for preparing a hollow globular bimetallic chalcogenide compound as claimed in claim 1, wherein in the step (2), the stirring time is 10-30 min.
5. The method for preparing a hollow globular bimetallic chalcogenide compound as claimed in claim 1, wherein in the step (3), the hollow nanosphere NiCo is prepared2S4The mass ratio of the selenium powder to the selenium powder is 1: 1-1: 4; the annealing is to anneal for 4 hours at 400 ℃ in an argon environment and then anneal for 90 minutes at 300 ℃ in a nitrogen environment.
6. Hollow-sphere bimetallic chalcogenide material prepared according to any one of claims 1 to 5, characterized in that said bimetallic chalcogenide is prepared by a processThe compound is a hierarchical nano structure assembled by primary nano particles, the interior of the compound is in a spherical shape with a cavity, the diameter of the compound is 400-450 nanometers, and the average thickness of a hollow shell is 50 nanometers; the structural formula of the bimetal chalcogenide is Ni0.33Co0.67SSe。
7. The hollow-sphere bimetallic chalcogenide material of claim 6, wherein the material has a graded nano-hollow-sphere structure assembled from first-order nanoparticles with a molecular formula of Ni0.33Co0.67SSe。
8. A sodium ion battery negative electrode comprising the hollow spherical bimetallic chalcogenide material of claim 7, wherein: the negative electrode material of the sodium ion battery contains the hollow spherical bimetallic chalcogenide material; and uniformly mixing the material, the conductive agent and the binder in proportion, adding a polar solution, uniformly stirring to form viscous fluid slurry, coating the fluid slurry on a current collector, and drying to obtain the negative electrode of the sodium-ion battery.
9. The sodium-ion battery negative electrode as claimed in claim 8, wherein the conductive agent and the binder are Super P and styrene butadiene rubber, carboxymethyl cellulose, respectively; the ratio of active material, conductive agent and binder is 7: 2: 0.5: 0.5; deionized water is used as a solvent to be prepared into uniform slurry.
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