CN113437277B - Bi 2 S 3 /NiS 2 @ C negative electrode material, sodium ion battery and preparation method of sodium ion battery - Google Patents
Bi 2 S 3 /NiS 2 @ C negative electrode material, sodium ion battery and preparation method of sodium ion battery Download PDFInfo
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Abstract
The invention discloses a Bi 2 S 3 /NiS 2 @ C negative electrode material, sodium ion battery and preparation method thereof, and Bi 2 S 3 /NiS 2 The preparation method of the @ C negative electrode material comprises the following steps: s1, calcining a metal organic framework with nickel as a metal ion and trimesic acid as an organic ligand to obtain NiO; s2, mixing NiO, trihydroxymethyl aminomethane, dopamine hydrochloride and a solvent, drying to obtain NiO @ Ppy, and then calcining to obtain NiO @ C; the molar ratio of NiO, trihydroxymethyl aminomethane and dopamine hydrochloride is (1-2): (1-3): (0.3 to 1); s3, uniformly mixing NiO @ C, a bismuth source and an organic solvent, carrying out hydrothermal reaction, and cleaning and drying after the reaction is finished to obtain an intermediate product; the mass ratio of the NiO @ C to the bismuth source is (70-200): (200-500); s4, calcining the intermediate product and sulfur in an inert atmosphere to obtain Bi 2 S 3 /NiS 2 @ C; the mass ratio of the intermediate product to sulfur is (1-3): (5-10). Bi of the invention 2 S 3 /NiS 2 The @ C negative electrode material has high cycle capacity and excellent cycle stability, and can be widely applied to preparation of sodium-ion batteries.
Description
Technical Field
The invention relates to the field of sodium ion batteries, in particular to Bi 2 S 3 /NiS 2 The @ C negative electrode material, the sodium ion battery and the preparation method thereof.
Background
With the continuous decrease of fossil fuels and the continuous rise of energy storage demand, it is necessary to develop a secondary battery having high energy density and long life. The lithium ion battery has the advantages of high energy density, environmental friendliness, no memory and the like, and is widely applied to the fields of electric automobiles, wearable electronic equipment, smart phones and the like. However, lithium ion batteries face a great challenge for future applications due to the shortage of global lithium resources and the disadvantage of uneven distribution. Since electrochemical reaction mechanisms of sodium and lithium are similar and sodium resources are abundant, sodium ion batteries are considered as next-generation secondary batteries that are highly likely to replace lithium ion batteries. However, since sodium has a larger ionic radius than lithium, the electrode material will be subjected to a large volume strain during charge/discharge, causing active species to be detached from the current collector after many cycles, eventually resulting in rapid degradation of battery capacity. On the other hand, a larger ionic radius causes a slow kinetic process, resulting in poor cycling performance of the battery at high current densities. Therefore, it is necessary to develop a high-performance anode material suitable for storing sodium ions.
In recent years, metal sulfides have received much attention due to their higher theoretical capacity. The metal-sulfur bond of transition metal sulfides is more easily broken than transition metal oxides, and thus kinetically favors the intercalation and deintercalation of sodium ions. Among the numerous metal sulfides, NiS 2 Due to the high theoretical capacity and excellent thermal stability, studies are being continued. Chinese invention patent CN111048752A discloses a negative electrode material, which has a granular structure, and sequentially comprises from inside to outside: hollow graphene oxide layer and NiS coated on surface of graphene oxide layer 2 Layer and cladding NiS 2 Poly-dopamine layer on surface of layer, and conventional NiS 2 Negative electrode materials in comparison, the negative electrode materials described in the patent are at low current density (125mAh g) -1 ) Has higher circulation capacity (the capacity is 512mAh g after 500 times of circulation -1 ) However, the cycle capacity at high current density is to be improved.
Disclosure of Invention
The invention aims to overcome the problem of low cycle capacity of the conventional negative electrode material under high current density, and provides Bi 2 S 3 /NiS 2 The preparation method of the @ C negative electrode material comprises the step of preparing the negative electrode material at 1A g -1 Electricity (D) fromUnder the current density, after circulating for 500 times, the capacity exceeds 500mAh g -1 。
Another object of the present invention is to provide a Bi 2 S 3 /NiS 2 @ C negative electrode material.
It is a further object of the present invention to provide a sodium ion battery.
The above object of the present invention is achieved by the following technical solutions:
bi 2 S 3 /NiS 2 The preparation method of the @ C negative electrode material comprises the following steps:
s1, calcining a metal organic framework with nickel as a metal ion and trimesic acid as an organic ligand to obtain NiO;
s2, mixing NiO, trihydroxymethyl aminomethane, dopamine hydrochloride and a solvent, drying to obtain NiO @ Ppy, and then calcining to obtain NiO @ C; the molar ratio of NiO, trihydroxymethyl aminomethane and dopamine hydrochloride is (1-2): (1-3): (0.3-1);
s3, uniformly mixing NiO @ C, a bismuth source and an organic solvent, carrying out hydrothermal reaction, and cleaning and drying after the reaction is finished to obtain an intermediate product; the mass ratio of the NiO @ C to the bismuth source is (70-200): (200-500);
s4, calcining the intermediate product and sulfur in an inert atmosphere to obtain Bi 2 S 3 /NiS 2 @ C; the mass ratio of the intermediate product to sulfur is (1-3): (5-10).
Bi prepared by the method of the invention 2 S 3 /NiS 2 @ C negative electrode material having Bi 2 S 3 /NiS 2 Composite material layer and coating Bi 2 S 3 /NiS 2 A carbon layer on the surface of the composite layer.
Bi 2 S 3 /NiS 2 The composite material layer can change the internal electric field to improve the conductivity of the material, accelerate charge transmission and improve Na + The reaction kinetics of the catalyst are improved, and the circulation capacity and the rate capability under high current density are further improved; the outer hard carbon layer obtained by the high-temperature pyrolysis of dopamine hydrochloride can improve the structural stability of the composite material, inhibit structural collapse and active substancesAnd (4) falling off, so that the circulation stability of the material is improved. In addition, the outer hard carbon layer further improves the conductivity of the composite material and improves the cycle performance of the composite material.
Preferably, in the step S1, trimesic acid, a nickel source, and an organic solvent are mixed uniformly, reacted at 160-190 ℃ for 6-12 hours, and then calcined to obtain NiO.
The nickel source and the organic solvent are selected from the nickel source and the organic solvent which are conventional in the field. Preferably, the nickel source is selected from nickel nitrate and the organic solvent is selected from N-N dimethylformamide.
Preferably, in step S1, the calcination is carried out at 300-450 ℃ for 2-4 h.
Preferably, in step S2, the calcination is performed at 400-600 ℃ for 1-4 h.
Preferably, in the step S3, the hydrothermal reaction temperature is 150 to 180 ℃ and the time is 6 to 12 hours.
The bismuth source is selected from one or more of bismuth nitrate, bismuth acetate and bismuth chloride.
Preferably, in the step S3, the cleaning is performed by cleaning with N-N dimethylformamide for 2-4 times, and then cleaning with absolute ethanol for 2-4 times.
Preferably, in the step S3, the drying temperature is 60-80 ℃ and the time is 12-24 h.
Preferably, in step S4, the calcination is carried out at 300-600 ℃ for 1-4 h.
Bi 2 S 3 /NiS 2 The @ C negative electrode material is prepared by the method.
The invention also provides a sodium ion battery which comprises the Bi 2 S 3 /NiS 2 @ C negative electrode material.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a Bi 2 S 3 /NiS 2 Preparation method of @ C negative electrode material and Bi prepared by method 2 S 3 /NiS 2 @ C negative electrode material having Bi 2 S 3 /NiS 2 Composite material layer and coating Bi 2 S 3 /NiS 2 Carbon layer on surface of composite layer, Bi 2 S 3 /NiS 2 The composite material layer can change the internal electric field to improve the conductivity of the material, accelerate charge transmission and improve Na + The reaction kinetics of the anode material are improved, so that the anode material has higher cycle capacity and rate capability under high current density; the outer hard carbon layer obtained by the high-temperature pyrolysis of dopamine hydrochloride can improve the structural stability of the composite material, inhibit structural collapse and active substance falling off, and enable the material to have excellent cycle stability.
Drawings
FIG. 1 is an SEM photograph of Ni-BTC prepared in example 1.
Fig. 2 is an SEM image (a) and a TEM image (b) of NiO prepared in example 1.
FIG. 3 is an SEM image of NiO @ Ppy prepared in example 1.
FIG. 4 is an SEM image of NiO @ C prepared in example 1.
FIG. 5 shows Bi as a final product obtained in example 1 2 S 3 /NiS 2 SEM picture of @ C.
FIG. 6 shows Bi as a final product obtained in example 1 2 S 3 /NiS 2 XRD pattern of @ C.
FIG. 7 shows Bi as a final product obtained in example 1 2 S 3 /NiS 2 EDS diagram of @ C.
FIG. 8 shows Bi as a final product obtained in example 1 2 S 3 /NiS 2 @ C at 1A g -1 Turn 1, turn 100, turn 200 and turn 300 at the current density.
FIG. 9 shows Bi as a final product obtained in example 1 2 S 3 /NiS 2 @ C at 1A g -1 The current density of (a).
Detailed Description
In order to more clearly and completely describe the technical scheme of the invention, the invention is further described in detail by the specific embodiments, and it should be understood that the specific embodiments described herein are only used for explaining the invention, and are not used for limiting the invention, and various changes can be made within the scope defined by the claims of the invention.
Example 1
Bi 2 S 3 /NiS 2 The preparation method of the @ C negative electrode material comprises the following steps:
s1, adding 1mmol of nickel nitrate and 1mmol of trimesic acid into 60ml of N-N dimethylformamide, stirring for 0.5h at the speed of 400r/min, transferring to a high-pressure reaction kettle after stirring, reacting for 8h at 180 ℃, respectively centrifugally cleaning for 3 times by using deionized water and absolute ethyl alcohol after reaction, and then preserving heat at 80 ℃ for 12h to obtain Ni-BTC (metal organic framework of nickel); heating Ni-BTC in air at a heating rate of 5 ℃/min to 400 ℃ and calcining for 2h to obtain black spherical NiO particles;
s2, adding 1mmol of spherical NiO particles, 1mmol of tris (hydroxymethyl) aminomethane and 0.3mmol of dopamine hydrochloride into a mixed solution containing 50mL of deionized water and 50mL of ethanol, continuously stirring for 12h at a stirring speed of 400r/min, centrifugally cleaning for 3 times after stirring is finished, preserving heat for 12h at 80 ℃ in a vacuum state, and drying to obtain NiO @ Ppy (polydopamine-coated NiO); placing the NiO @ Ppy in an argon atmosphere, heating to 500 ℃ at a heating rate of 2 ℃/min, and calcining for 2h to obtain NiO @ C (carbon-coated NiO);
s3, adding 70mg of NiO @ C and 200mg of bismuth nitrate into 60mL of N-N dimethylformamide, performing ultrasonic treatment for 0.5h, stirring for 1h at a rotating speed of 400r/min, transferring the uniformly stirred mixed solution into a high-pressure reaction kettle, reacting for 6h at 160 ℃, centrifugally cleaning for 3 times by using deionized water and ethanol respectively after the reaction is finished, preserving heat of the precipitate obtained by centrifugation for 12h at 80 ℃ in a vacuum state, and drying to obtain a black intermediate product;
s4, heating 0.1g of black intermediate product and 0.5g of sublimed sulfur to 500 ℃ at a heating rate of 2 ℃/min under an argon atmosphere, preserving heat for 2 hours, and obtaining a final product Bi after calcination 2 S 3 /NiS 2 @C。
Example 2
Bi 2 S 3 /NiS 2 The preparation method of the @ C negative electrode material comprises the following steps:
s1, adding 1mmol of nickel nitrate and 2mmol of trimesic acid into 70ml of N-N dimethylformamide, stirring for 0.5h at the speed of 500r/min, transferring to a high-pressure reaction kettle after stirring, reacting for 12h at 160 ℃, respectively centrifugally cleaning for 3 times by using deionized water and absolute ethyl alcohol after the reaction is finished, and then preserving heat for 12h at 80 ℃ to obtain Ni-BTC; heating Ni-BTC in air at a heating rate of 5 ℃/min to 300 ℃ and calcining for 1h to obtain black spherical NiO particles;
s2, adding 1mmol of spherical NiO particles, 2mmol of tris (hydroxymethyl) aminomethane and 0.5mmol of dopamine hydrochloride into a mixed solution containing 50mL of deionized water and 50mL of ethanol, continuously stirring for 12h at a stirring speed of 500r/min, centrifugally cleaning for 3 times after stirring is finished, preserving heat for 12h at 80 ℃ in a vacuum state, and drying to obtain NiO @ Ppy; heating NiO @ Ppy to 400 ℃ at a heating rate of 2 ℃/min in an argon atmosphere, and calcining for 4h to obtain NiO @ C;
s3, adding 70mg of NiO @ C and 300mg of bismuth nitrate into 60mLN-N dimethylformamide, performing ultrasonic treatment for 1 hour, stirring for 1 hour at the rotating speed of 500r/min, transferring the uniformly stirred mixed solution into a high-pressure reaction kettle, reacting for 6 hours at 170 ℃, centrifugally cleaning for 3 times by using deionized water and ethanol respectively after the reaction is finished, preserving heat of the precipitate obtained by centrifugation for 12 hours at 80 ℃ in a vacuum state, and drying to obtain a black intermediate product;
s4, heating 0.2g of black intermediate product and 0.7g of sublimed sulfur to 500 ℃ at a heating rate of 2 ℃/min under an argon atmosphere, preserving heat for 2 hours, and obtaining a final product Bi after calcination 2 S 3 /NiS 2 @C。
Example 3
S1, adding 1mmol of nickel nitrate and 3mmol of trimesic acid into 80ml of N-N dimethylformamide, stirring for 1h at the speed of 600r/min, transferring to a high-pressure reaction kettle after stirring, reacting for 10h at 170 ℃, respectively centrifugally cleaning for 3 times by using deionized water and absolute ethyl alcohol after the reaction is finished, and then preserving heat at 80 ℃ for 12h to obtain Ni-BTC; heating Ni-BTC in air at the heating rate of 2 ℃/min to 600 ℃ and calcining for 1h to obtain black spherical NiO particles;
s2, adding 2mmol of spherical NiO particles, 3mmol of tris (hydroxymethyl) aminomethane and 0.7mmol of dopamine hydrochloride into a mixed solution containing 50mL of deionized water and 50mL of ethanol, continuously stirring for 12h at a stirring speed of 600r/min, centrifugally cleaning for 3 times after stirring is finished, preserving heat for 12h at 80 ℃ in a vacuum state, and drying to obtain NiO @ Ppy; heating NiO @ Ppy to 600 ℃ at a heating rate of 2 ℃/min in an argon atmosphere, and calcining for 1h to obtain NiO @ C;
s3, adding 140mg of NiO @ C and 300mg of bismuth nitrate into 70mLN-N dimethylformamide, performing ultrasonic treatment for 1 hour, stirring for 1 hour at the rotating speed of 600r/min, transferring the uniformly stirred mixed solution into a high-pressure reaction kettle, reacting for 6 hours at 180 ℃, centrifugally cleaning for 3 times by using deionized water and ethanol respectively after the reaction is finished, preserving heat of the precipitate obtained by centrifugation for 12 hours at 80 ℃ in a vacuum state, and drying to obtain a black intermediate product;
s4, heating 0.2g of black intermediate product and 0.8g of sublimed sulfur to 500 ℃ at a heating rate of 2 ℃/min under an argon atmosphere, preserving heat for 2 hours, and obtaining a final product Bi after calcination 2 S 3 /NiS 2 @C。
Example 4
Bi 2 S 3 /NiS 2 The preparation method of the @ C negative electrode material comprises the following steps:
s1, adding 3mmol of nickel nitrate and 2mmol of trimesic acid into 80ml of N-N dimethylformamide, stirring for 1h at the speed of 400r/min, transferring to a high-pressure reaction kettle after stirring, reacting for 6h at 190 ℃, respectively centrifugally cleaning for 3 times by using deionized water and absolute ethyl alcohol after the reaction is finished, and then preserving heat at 80 ℃ for 12h to obtain Ni-BTC; heating Ni-BTC in air at a heating rate of 2 ℃/min to 500 ℃ and calcining for 1h to obtain black spherical NiO particles;
s2, adding 2mmol of spherical NiO particles, 3mmol of tris (hydroxymethyl) aminomethane and 1mmol of dopamine hydrochloride into a mixed solution containing 40mL of deionized water and 60mL of ethanol, continuously stirring for 12h at a stirring speed of 400r/min, centrifugally cleaning for 3 times after stirring is finished, preserving heat for 12h at 80 ℃ in a vacuum state, and drying to obtain NiO @ Ppy; heating NiO @ Ppy to 400 ℃ at a heating rate of 2 ℃/min in an argon atmosphere, and calcining for 4h to obtain NiO @ C;
s3, adding 200mg of NiO @ C and 500mg of bismuth nitrate into 80mLN-N dimethylformamide, performing ultrasonic treatment for 2 hours, stirring for 1 hour at a rotating speed of 400r/min, transferring the uniformly stirred mixed solution into a high-pressure reaction kettle, reacting for 12 hours at 150 ℃, centrifugally cleaning for 3 times by using deionized water and ethanol respectively after the reaction is finished, preserving heat of the precipitate obtained by centrifugation for 12 hours at 80 ℃ in a vacuum state, and drying to obtain a black intermediate product;
s4, heating 0.3g of black intermediate product and 1g of sublimed sulfur to 400 ℃ at a heating rate of 2 ℃/min under an argon atmosphere for calcining for 2h, and obtaining a final product Bi after the calcining is finished 2 S 3 /NiS 2 @C。
Example 5
This example is a fifth example of the present invention, and is different from example 1 in that the calcination temperature in this example S2 is 450 ℃ and the calcination time is 4 hours.
Example 6
This example is a sixth example of the present invention, and is different from example 1 in that bismuth nitrate is replaced with bismuth acetate in this example S5.
Example 7
This example is a seventh example of the present invention, and differs from example 1 in that bismuth nitrate is replaced with bismuth chloride in this example S5.
Example 8
This example is an eighth example of the present invention, and differs from example 1 in that the calcination temperature in this example S6 is 300 ℃ and the calcination time is 4 hours.
Example 9
This example is a ninth example of the present invention, and differs from example 1 in that the calcination temperature in this example S6 is 600 ℃, and the calcination time is 1 hour.
Comparative example 1
The preparation method of the anode material comprises the following steps:
s1, mixing 2g of SiO 2 Placing the pellets in 2mg/ml graphene oxide aqueous solution, performing self polymerization for 24h, and dissolving the pellets in SiO 2 Forming a graphene oxide layer (a first carbon-containing layer) on the surface of the pellet;
s2, modifying the graphite oxideSiO of the olefinic layer 2 Placing the pellets into a reaction kettle of a mixed solution of nickel chloride hexahydrate and thiourea of 10mg/ml, and reacting for 24 hours at 180 ℃ to obtain NiS growing on the graphene oxide layer uniformly 2 A layer;
s3, growing NiS 2 SiO of layers and graphene oxide layers 2 Placing the mixture in Tris-dopamine hydrochloride aqueous solution of 2mg/ml, and stirring for 12 hours at 25 ℃ to form a poly-dopamine layer;
s4, growing a polydopamine layer NiS 2 SiO of layers and graphene oxide layers 2 Placing in 5 wt% hydrofluoric acid solution, stirring at 0 deg.C for 12 hr to remove SiO 2 The template is further placed in an argon atmosphere for annealing at 600 ℃ for 2 h.
Comparative example 2
The preparation method of the anode material comprises the following steps:
s1, adding 2.96g of glucose, 0.98g of bismuth nitrate and 0.5g of polyvinylpyrrolidone (average molecular weight: 40000) into 10ml of distilled water, stirring for ten minutes, adding 5ml of glacial acetic acid, and stirring vigorously for 0.5 h;
s2, transferring the solution into a reaction kettle, preserving heat for 2 hours at 200 ℃, cooling, and then centrifugally cleaning with ethanol and distilled water to obtain Bi/C core-shell structure pellets;
s3, mixing the Bi/C core-shell structure pellets with sulfur powder according to the weight ratio of 1: 5, and annealing at 550 ℃ for 4 hours in an argon atmosphere.
Characterization of the test
FIG. 1 is an SEM photograph of Ni-BTC prepared in example 1. As can be seen from the figure, the Ni-BTC has a relatively uniform shape and a size distribution of about 500nm to 1 μm.
FIG. 2 is an SEM image (a) and a TEM image (b) of NiO obtained in example 1, wherein the shape of the entire NiO is well maintained, and the special structure of the spheres in the spheres is clearly seen from the SEM image, and the thickness of the outer layer structure is about 70 to 80 nm.
FIG. 3 is an SEM image of NiO @ Ppy prepared in example 1, from which a coated polydopamine layer, about 90nm thick, is clearly seen.
Fig. 4 is an SEM image of NiO @ C prepared in example 1, from which it can be seen that a spherical structure can be clearly seen after coating a carbon layer and high-temperature calcination.
FIG. 5 shows Bi as a final product obtained in example 1 2 S 3 /NiS 2 The SEM image of @ C, the material still maintains a globular structure after solvothermal and vulcanization processes.
FIG. 6 shows Bi as a final product obtained in example 1 2 S 3 /NiS 2 XRD pattern of @ C, it can be seen that all diffraction peaks are in combination with NiS 2 And Bi 2 S 3 The PDF card is well matched, and proves that Bi 2 S 3 /NiS 2 Successful synthesis of @ C.
FIG. 7 shows Bi as a final product obtained in example 1 2 S 3 /NiS 2 EDS diagram of @ C, diagram (a) being Bi 2 S 3 /NiS 2 The HAADF-STEM chart of @ C (b-e) is an element plane scanning chart of nickel element, bismuth element, sulfur element and carbon element in sequence, and the chart (f) is an element plane scanning superposition chart of carbon and sulfur element, and it can be seen that the red carbon is mainly used as the edge, thus proving the success of coating.
FIG. 8 shows Bi as a final product obtained in example 1 2 S 3 /NiS 2 @ C at 1A g -1 The charge and discharge curves of the 1 st, 100 th, 200 th and 300 th circles under the current density of (1), it can be seen that the first discharge capacity is 818mAh g -1 The charge capacity is 642mAh g -1 (ii) a The charging and discharging curves of the 100 th circle, the 200 th circle and the 300 th circle are basically consistent, and the Bi is proved 2 S 3 /NiS 2 @ C has excellent cycling stability at high current densities.
FIG. 9 shows Bi as a final product obtained in example 1 2 S 3 /NiS 2 @ C at 1A g -1 The current density of (2) is shown in the figure, and it can be seen that the capacity is still maintained to 529mAh g after 500 cycles of charge and discharge -1 It is shown that the anode material prepared in example 1 has excellent cycle life and higher cycle capacity.
Comparative example 1 the negative electrode material was used at a current density of 0.2C/0.2C (0.2C ═ 125mAh g -1 ) Under the condition, the capacity is 512mAh g after 500 times of circulation -1 (CN111048752A), capacity of 282mAh g after 300 cycles of the negative electrode material described in comparative example 2 under the same conditions -1 . Those skilled in the art know that the higher the current density, the lower the cycling capacity of the same material. Therefore, compared with the prior art, the cathode material has higher cycle capacity under high current density.
Intermediate products and end products Bi obtained in examples 2 to 9 2 S 3 /NiS 2 The SEM, XRD, TEM, EDS results and electrochemical performance of @ C are similar, and thus the detailed description is not repeated.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. Bi 2 S 3 /NiS 2 The preparation method of the @ C negative electrode material is characterized by comprising the following steps of:
s1, calcining a metal organic framework with nickel as a metal ion and trimesic acid as an organic ligand to obtain NiO;
s2, mixing NiO, trihydroxymethyl aminomethane, dopamine hydrochloride and a solvent, drying to obtain NiO @ Ppy, and then calcining to obtain NiO @ C; the molar ratio of NiO, trihydroxymethyl aminomethane and dopamine hydrochloride is (1-2): (1-3): (0.3 to 1);
s3, uniformly mixing NiO @ C, a bismuth source and an organic solvent, carrying out hydrothermal reaction, and cleaning and drying after the reaction is finished to obtain an intermediate product; the mass ratio of the NiO @ C to the bismuth source is (70-200): (200-500);
s4, calcining the intermediate product and sulfur in an inert atmosphere to obtain Bi 2 S 3 /NiS 2 @ C; the mass ratio of the intermediate product to sulfur is (1-3): (5-10).
2. The Bi of claim 1 2 S 3 /NiS 2 The preparation method of the @ C negative electrode material is characterized in that in the step S1, trimesic acid, a nickel source and an organic solvent are uniformly mixed, then react for 6-12 hours at 160-190 ℃, and then are calcined to obtain NiO.
3. The Bi according to claim 1 or 2 2 S 3 /NiS 2 The preparation method of the @ C negative electrode material is characterized in that in the step S1, the calcination is carried out for 2-4 hours at the temperature of 300-450 ℃.
4. The Bi of claim 1 2 S 3 /NiS 2 The preparation method of the @ C negative electrode material is characterized in that in the step S2, the calcination is carried out for 1-4 hours at 400-600 ℃.
5. The Bi of claim 1 2 S 3 /NiS 2 The preparation method of the @ C negative electrode material is characterized in that in the step S3, the hydrothermal reaction temperature is 150-180 ℃ and the time is 6-12 hours.
6. The Bi according to claim 1 2 S 3 /NiS 2 The preparation method of the @ C negative electrode material is characterized in that in step S3, the bismuth source is selected from one or more of bismuth nitrate, bismuth acetate and bismuth chloride.
7. The Bi of claim 1 2 S 3 /NiS 2 The preparation method of the @ C negative electrode material is characterized in that in the step S3, the cleaning is performed for 2-4 times by using N-N dimethylformamide and 2-4 times by using absolute ethyl alcohol.
8. The Bi of claim 1 2 S 3 /NiS 2 The preparation method of the @ C negative electrode material is characterized in thatIn step S4, the calcination is carried out at 300-600 ℃ for 1-4 h.
9. The Bi according to any one of claims 1 to 8 2 S 3 /NiS 2 Preparation method of @ C negative electrode material and prepared Bi 2 S 3 /NiS 2 @ C negative electrode material.
10. A sodium ion battery comprising the negative electrode material according to claim 9.
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