CN113036139B - Se/C/Sb2Se3Double-shell hollow nano rod-shaped sodium ion battery cathode material and preparation method thereof - Google Patents

Se/C/Sb2Se3Double-shell hollow nano rod-shaped sodium ion battery cathode material and preparation method thereof Download PDF

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CN113036139B
CN113036139B CN202110258717.6A CN202110258717A CN113036139B CN 113036139 B CN113036139 B CN 113036139B CN 202110258717 A CN202110258717 A CN 202110258717A CN 113036139 B CN113036139 B CN 113036139B
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cathode material
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CN113036139A (en
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黄剑锋
雒甜蜜
郭玲
曹丽云
李嘉胤
许占位
冯永强
胡郁竹
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Shaanxi University of Science and Technology
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Abstract

The invention discloses Se/C/Sb2Se3A double-shell hollow nano rod-shaped sodium ion battery cathode material and a preparation method thereof are provided, wherein the preparation method comprises the step of clathrating antimony selenide molecules by gamma-cyclodextrin to obtain C/Sb with a core-shell structure2Se3The complex with the core-Shell structure is placed in an alkaline solution for etching treatment, part of selenium in the internal antimony selenide is separated out and grown on the surface of carbon in the reaction process, and finally Se/C/Sb with the York-Shell structure is obtained2Se3Double-shell hollow nanorods. The generation of the hollow structure can effectively buffer the volume expansion phenomenon of sodium ions in the charge-discharge cycle process due to larger radius, so that the cycle stability of the battery cathode material is greatly improved. The target York-Shell double-Shell hollow nanorod structure can be synthesized only by adopting a hydrothermal method, the preparation raw materials are easy to obtain, the process operation is simple, and the feasibility is strong.

Description

Se/C/Sb2Se3Double-shell hollow nano rod-shaped sodium ion battery cathode material and preparation method thereof
Technical Field
The invention belongs to the technical field of electrochemical sodium storage, and particularly relates to Se/C/Sb2Se3A double-shell hollow nano rod-shaped sodium ion battery cathode material and a preparation method thereof.
Background
With the rapid development of the new energy electric automobile industry, the energy storage battery has a wide application prospect. Sodium ion batteries have abundant raw material reserves and low costs, and have been considerably competitive in the secondary battery market. However, the radius of sodium ions is large, and the electrochemical performance of the electrode material is not ideal due to the large volume change phenomenon in the charge-discharge cycle process, so that the large-scale commercialization of the sodium ion battery is prevented. The problem of regulating the microstructure to improve the volume expansion of the sodium-ion battery electrode material is a feasible method. Correlation technique by using a p-MoO3The selenization treatment of the raw material prepares the MoSe with a yolk shell structure2And (3) microspheres. The core-shell structure can effectively buffer the volume expansion of the electrode generated in the charge-discharge cycle process, and the reversible capacity of 433 mA.h/g is released after the electrode is subjected to charge-discharge cycle for 50 times under the current density of 0.2A/g.
The metal oxygen, sulfur and selenide in the anode material of the sodium ion battery researched at present have higher theoretical specific capacity and are easy to regulate and control the appearance. Sb2Se3As a representative selenide, has about 670mAhg-1The conductive material has high capacity, but the conductivity is poor, so that the structural design needs to be carried out while the conductive material is compounded to obtain the sodium ion battery cathode material with excellent electrochemical performance and stable structure.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides Se/C/Sb2Se3The double-shell hollow nano rod-shaped sodium ion battery cathode material and the preparation method thereof are characterized in that a host molecule carbon source and a guest molecule Sb are subjected to inclusion technology2Se3The material prepared by complexing and regulating the morphology of the material has a York-Shell special structure and excellent electrochemical properties.
In order to achieve the above object, the present invention provides a Se/C/Sb alloy2Se3The preparation method of the double-shell hollow nano rod-shaped sodium ion battery cathode material is characterized by comprising the following steps of:
1) adding gamma-cyclodextrin with the substance amount of 0.5 mmol-2 mmol into distilled water and stirring to obtain a mixed solution A;
2) adding antimony trichloride into absolute ethyl alcohol or ethylene glycol solvent and stirring to obtain a mixed solution B, wherein the volume ratio of distilled water to the absolute ethyl alcohol or the ethylene glycol in the step 1) is (5:1) - (10: 1);
3) adding selenium powder and sodium borohydride into 5-10 mL of distilled water, and stirring at 40-70 ℃ to obtain a mixed solution C, wherein the mass ratio of antimony trichloride to selenium powder in the step 2) is (1:2) - (1:1), and the mass ratio of selenium powder to sodium borohydride is (1:2) - (1: 1);
4) mixing the mixed solution B with the mixed solution C, dropwise adding the mixed solution A into the mixed solution B, and stirring to obtain a mixed solution D;
5) carrying out hydrothermal reaction on the mixed solution D at 150-210 ℃, cooling to room temperature after the reaction is finished, washing, separating and precipitating, and carrying out freeze drying on the precipitate to obtain C/Sb2Se3A complex powder;
6) taking 0.1-0.8 g of C/Sb2Se3Adding the complex powder into 50-80 mL of 0.5-2 g/L sodium hydroxide aqueous solution and stirring to obtain a mixed solution E;
7) carrying out hydrothermal reaction on the mixed solution E at the temperature of 80-160 ℃, cooling to room temperature after the reaction is finished, washing, separating and drying the precipitate to obtain Se/C/Sb2Se3Double-shell hollow nano rod-shaped sodium ion battery cathode material.
Preferably, in the step 1), the stirring speed is 500-600 r/min, and the stirring time is 30-40 min, so as to obtain a clear and transparent mixed solution A.
Preferably, the stirring speed in the step 2) is 500-600 r/min, and the stirring time is 30-60 min, so as to obtain a clear and transparent mixed solution B.
Preferably, the stirring speed in the step 3) is 500-600 r/min, and the stirring time is 10-30 min, so as to obtain the wine red mixed solution C.
Preferably, the stirring speed in the step 4) is 500-600 r/min, and the stirring time is 10-30 min.
Preferably, in the step 5), the mixed solution D is filled into a polytetrafluoroethylene lining with a filling ratio of 50% -80%, and then the polytetrafluoroethylene lining is filled into a hydrothermal kettle to perform hydrothermal reaction in a homogeneous phase reactor for 12-24 hours.
Preferably, the freeze drying in the step 5) and the step 7) is carried out for 9-16 h under the conditions of-40 to-50 ℃ and the pressure of 20-30 Mpa.
Preferably, the stirring speed in the step 6) is 500-600 r/min, and the stirring time is 30-40 min.
Preferably, in the step 7), the mixed solution E is filled into a polytetrafluoroethylene lining with a filling ratio of 50% -80%, and then the polytetrafluoroethylene lining is filled into a hydrothermal kettle to perform hydrothermal reaction in a homogeneous reactor for 3-12 hours.
The invention also provides Se/C/Sb2Se3The double-shell hollow nano rod-shaped sodium ion battery cathode material adopts the Se/C/Sb2Se3The double-shell hollow nano rod-shaped sodium ion battery cathode material is prepared by a preparation method.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention uses gamma-cyclodextrin to carry out inclusion on antimony selenide molecules to obtain C/Sb with a core-shell structure2Se3The complex, wherein the special cavity structure of the gamma-cyclodextrin and the stable existing state of the gamma-cyclodextrin in an alkaline medium provide a favorable place for alkaline etching, and simultaneously, the complex serving as a carbon source can effectively improve the conductivity of the antimony selenide.
2. The core-Shell structure complex is further innovatively placed in an alkaline solution for etching treatment, part of selenium in the internal antimony selenide is separated out and is longer than the carbon surface in the reaction process, and finally Se/C/Sb with a York-Shell structure is obtained2Se3Double-shell hollow nanorods. The generation of the hollow structure can effectively buffer the radius of the sodium ionsThe volume expansion phenomenon occurring during the charge-discharge cycle is large.
3. The target York-Shell double-Shell hollow nanorod structure can be synthesized only by adopting a hydrothermal method, the preparation raw materials are easy to obtain, the process operation is simple, and the feasibility is strong.
Drawings
FIG. 1 is Se/C/Sb prepared by the invention2Se3XRD pattern of electrode material;
FIG. 2 is Se/C/Sb prepared by the invention2Se3TEM images of the electrode material.
Detailed Description
The present invention will be further explained with reference to the drawings and specific examples in the specification, and it should be understood that the examples described are only a part of the examples of the present application, and not all examples. 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 application.
The invention provides Se/C/Sb2Se3The preparation method of the double-shell hollow nano rod-shaped sodium ion battery cathode material specifically comprises the following steps:
1) adding gamma-cyclodextrin with the substance amount of 0.5 mmol-2 mmol into distilled water, stirring at the speed of 500-600 r/min for 30-40 min until the mixture is clear and transparent, and obtaining a mixed solution A;
2) adding antimony trichloride into an absolute ethyl alcohol or ethylene glycol solvent, wherein the volume ratio of the distilled water in the step 1) to the absolute ethyl alcohol or the ethylene glycol is V (water), and V (alcohol) is (5:1) - (10:1), stirring for 500-600 r/min for 30-60 min until the solution is clear and transparent, so as to obtain a mixed solution B;
3) adding selenium powder and sodium borohydride into 5-10 mL of distilled water, wherein the mass ratio of antimony trichloride to selenium powder in the step 2) is n (SbCl)3) N (Se): (1:2) - (1:1), the mass ratio of selenium powder and sodium borohydride is n (Se): n (NaBH)4) Stirring for 500-600 r/min for 10-30 min at 40-70 ℃ to obtain a wine red mixed solution C (1:2) - (1: 1);
4) mixing the mixed solution B with the mixed solution C, and dropwise adding the mixed solution A into the mixed solution B, wherein the stirring speed is 500-600 r/min, and the stirring time is 10-30 min to obtain a mixed solution D;
5) filling the mixed solution D into a polytetrafluoroethylene lining with a filling ratio of 50-80%, then filling the mixed solution D into a hydrothermal kettle, carrying out hydrothermal reaction in a homogeneous reactor at 150-210 ℃ for 12-24 h, and cooling to room temperature after the reaction is finished; washing with water and absolute ethyl alcohol alternately for multiple times, separating precipitates, and freeze-drying the precipitates for 9-16 hours at the temperature of-40 to-50 ℃ and the pressure of 20-30 Mpa to obtain C/Sb2Se3A complex powder; (ii) a
6) Taking 0.1-0.8 g C/Sb2Se3Adding the complex powder into 50-80 mL of 0.5-2 g/L sodium hydroxide aqueous solution, stirring at 500-600 r/min for 30-40 min to obtain a mixed solution E;
7) filling the mixed solution E into a polytetrafluoroethylene lining with a filling ratio of 50-80%, filling the mixed solution E into a hydrothermal kettle, carrying out hydrothermal reaction in a homogeneous reactor at 80-160 ℃ for 3-12 h, and cooling to room temperature after the reaction is finished; washing with water and absolute ethyl alcohol alternately for multiple times, separating precipitates, and freeze-drying the precipitates for 9-16 hours at the temperature of-40 to-50 ℃ and the pressure of 20-30 Mpa to finally obtain Se/C/Sb2Se3Composite powders, i.e. Se/C/Sb having the York-Shell structure2Se3Double-shell hollow nano rod-shaped sodium ion battery cathode material.
The invention also provides Se/C/Sb2Se3The double-Shell hollow nano rod-shaped sodium ion battery cathode material is prepared by the preparation method, and the material is Se/C/Sb with a York-Shell structure2Se3The double-shell hollow nano rod-shaped structure can effectively buffer the volume expansion phenomenon of sodium ions in the charging and discharging cycle process due to larger radius, so that the cycle stability of the sodium ion battery cathode material is greatly improved.
The present invention will be described with reference to specific examples.
Example 1:
1) adding 1g of gamma-cyclodextrin into 50ml of distilled water, and stirring at 500r/min for 35min until the mixture is clear and transparent to obtain a mixed solution A;
2) 0.2281g of antimony trichloride is added into 5ml of absolute ethyl alcohol, and the mixture is stirred for 30min at a speed of 500r/min until the mixture is clear and transparent, so that a mixed solution B is obtained;
3) 0.1579g of selenium powder and 0.0757g of sodium borohydride are added into 5ml of distilled water, and the mixture is stirred for 30min at the temperature of 40 ℃ and at the speed of 550r/min to obtain wine red mixed solution C;
4) mixing the mixed solution B with the mixed solution C, dropwise adding the mixed solution A into the mixed solution B, and stirring at 500r/min for 20min to obtain a mixed solution D;
5) filling the mixed solution D into a polytetrafluoroethylene lining with a filling ratio of 60%, filling the mixed solution D into a hydrothermal kettle, putting the hydrothermal kettle into a homogeneous reactor, carrying out hydrothermal reaction for 18h at 200 ℃, and cooling to room temperature after the reaction is finished; alternately washing with water and anhydrous ethanol for 6 times, separating precipitate, and freeze drying the precipitate to obtain C/Sb2Se3A complex powder;
6) taking 0.1g of the above C/Sb2Se3Adding the complex powder into 70mL of 1g/L sodium hydroxide aqueous solution, and stirring at 500r/min for 30min to obtain a mixed solution E;
7) filling the mixed solution E into a polytetrafluoroethylene lining with the filling ratio of 70%, filling the mixed solution E into a hydrothermal kettle, putting the hydrothermal kettle into a homogeneous reactor, carrying out hydrothermal reaction for 6 hours at 100 ℃, and cooling to room temperature after the reaction is finished; alternately washing with water and anhydrous ethanol for 6 times, separating precipitate, and freeze drying the precipitate to obtain Se/C/Sb2Se3Composite powders, i.e. Se/C/Sb2Se3Double-shell hollow nano rod-shaped sodium ion battery cathode material.
Se/C/Sb prepared in example 12Se3XRD analysis of the electrode material showed that Sb is in the form of a solid solution, as shown in FIG. 12Se3The standard cards are compared, so that the characteristic diffraction peaks of the two samples can be well matched, and the positions of other peaks are consistent with those of the standard cards; compared with a standard card of Se, the characteristic diffraction peaks of the two samples can be well matched, and the positions of other peaks are consistent with the standard card. It can be concluded therefrom that the synthesized sample contains Se and Sb2Se3Two phases.
Se/C/Sb prepared in example 12Se3The TEM analysis of the electrode material shows that the synthesized sample is obviously in a double-shell hollow nanorod shape, and the middle-layer carbon cavity contains Sb, as shown in FIG. 22Se3The outer layer of the nano-rod is coated by selenium.
Example 2:
1) adding 1.5g of gamma-cyclodextrin into 50ml of distilled water, stirring at 550r/min for 40min until the mixture is clear and transparent, and obtaining a mixed solution A;
2) adding 0.4562g of antimony trichloride into 10ml of ethylene glycol, stirring at 550r/min for 40min until the mixture is clear and transparent, and obtaining a mixed solution B;
3) 0.1579g of selenium powder and 0.0851g of sodium borohydride are added into 5ml of distilled water, and the mixture is stirred for 25min at the temperature of 50 ℃ and at the speed of 550r/min to obtain wine red mixed solution C;
4) mixing the mixed solution B with the mixed solution C, dropwise adding the mixed solution A into the mixed solution B, and stirring at 550r/min for 20min to obtain a mixed solution D;
5) filling the mixed solution D into a polytetrafluoroethylene lining with a filling ratio of 65%, filling the mixed solution D into a hydrothermal kettle, putting the hydrothermal kettle into a homogeneous reactor, carrying out hydrothermal reaction for 22 hours at 180 ℃, and cooling to room temperature after the reaction is finished; alternately washing with water and anhydrous ethanol for 6 times, separating precipitate, and freeze drying the precipitate to obtain C/Sb2Se3A complex powder;
6) taking 0.5g of the above C/Sb2Se3Adding the complex powder into 70mL of 1.5g/L sodium hydroxide aqueous solution, and stirring at 550r/min for 30min to obtain a mixed solution E;
7) filling the mixed solution E into a polytetrafluoroethylene lining with the filling ratio of 70%, filling the mixed solution E into a hydrothermal kettle, putting the hydrothermal kettle into a homogeneous reactor, carrying out hydrothermal reaction for 3 hours at 150 ℃, and cooling to room temperature after the reaction is finished; alternately washing with water and anhydrous ethanol for 6 times, separating precipitate, and freeze drying the precipitate to obtain Se/C/Sb2Se3And (3) composite powder.
Example 3:
1) adding 2g of beta-cyclodextrin into 60ml of distilled water, and stirring for 30min at a speed of 600r/min until the solution is clear and transparent to obtain a mixed solution A;
2) adding 0.4562g of antimony trichloride into 10ml of absolute ethanol, stirring at 550r/min for 40min until the solution is clear and transparent, and obtaining a mixed solution B;
3) 0.2368g of selenium powder and 0.1513g of sodium borohydride are added into 10ml of distilled water, and the mixture is stirred for 20min at the temperature of 60 ℃ and the speed of 600r/min to obtain wine red mixed solution C;
4) mixing the mixed solution B with the mixed solution C, dropwise adding the mixed solution A into the mixed solution B, and stirring at 600r/min for 15min to obtain a mixed solution D;
5) filling the mixed solution D into a polytetrafluoroethylene lining with the filling ratio of 80%, filling the mixed solution D into a hydrothermal kettle, putting the hydrothermal kettle into a homogeneous reactor, carrying out hydrothermal reaction for 24 hours at 160 ℃, and cooling to room temperature after the reaction is finished; alternately washing with water and anhydrous ethanol for 6 times, separating precipitate, and freeze drying the precipitate to obtain C/Sb2Se3A complex powder;
6) taking 0.8g of the above C/Sb2Se3Adding the complex powder into 50mL of 2g/L sodium hydroxide aqueous solution, and stirring at 600r/min for 40min to obtain a mixed solution E;
7) filling the mixed solution E into a polytetrafluoroethylene lining with the filling ratio of 50%, filling the mixed solution E into a hydrothermal kettle, putting the hydrothermal kettle into a homogeneous reactor, carrying out hydrothermal reaction for 12 hours at the temperature of 80 ℃, and cooling to room temperature after the reaction is finished; alternately washing with water and anhydrous ethanol for 6 times, separating precipitate, and freeze drying the precipitate to obtain Se/C/Sb2Se3And (3) composite powder.
Example 4:
1) adding gamma-cyclodextrin with the substance amount of 0.5mmol into distilled water, stirring at 500r/min for 30min until the mixture is clear and transparent to obtain a mixed solution A;
2) adding antimony trichloride into absolute ethyl alcohol, wherein the volume ratio of the distilled water and the absolute ethyl alcohol in the step 1) is V (water), and V (absolute ethyl alcohol) is 5:1, stirring for 500r/min for 30min until the solution is clear and transparent, so as to obtain a mixed solution B;
3) adding selenium powder and sodium borohydride into 5mL of distilled water, wherein the mass ratio of the antimony trichloride to the selenium powder in the step 2) is n (SbCl)3) N (Se) 1:2, the mass ratio of selenium powder to sodium borohydride is n (Se) n (NaBH)4) Stirring at 500r/min for 1:1Stirring at 40 deg.C for 10min to obtain wine red mixed solution C;
4) mixing the mixed solution B with the mixed solution C, and dropwise adding the mixed solution A into the mixed solution B, wherein the stirring speed is 500r/min, and the stirring time is 10min to obtain a mixed solution D;
5) filling the mixed solution D into a polytetrafluoroethylene lining with the filling ratio of 50%, then filling the mixed solution D into a hydrothermal kettle in a homogeneous reactor, carrying out hydrothermal reaction for 12 hours at 150 ℃, and cooling to room temperature after the reaction is finished; washing with water and anhydrous ethanol alternately for multiple times, separating precipitate, and freeze drying at-40 deg.C under 20Mpa for 9 hr to obtain C/Sb2Se3A complex powder; (ii) a
6) Take 0.1g C/Sb2Se3Adding the complex powder into 50mL of 0.5g/L sodium hydroxide aqueous solution, stirring at 500r/min for 30min to obtain a mixed solution E;
7) filling the mixed solution E into a polytetrafluoroethylene lining with the filling ratio of 50%, then filling the mixed solution E into a hydrothermal kettle in a homogeneous reactor, carrying out hydrothermal reaction for 3 hours at the temperature of 80 ℃, and cooling to room temperature after the reaction is finished; washing with water and anhydrous ethanol alternately for multiple times, separating precipitate, freeze drying at-45 deg.C under 25Mpa for 9 hr to obtain Se/C/Sb2Se3And (3) composite powder.
Example 5:
1) adding gamma-cyclodextrin with the substance amount of 2mmol into distilled water, stirring at 600r/min for 40min until the mixture is clear and transparent to obtain a mixed solution A;
2) adding antimony trichloride into an ethylene glycol solvent, wherein the volume ratio of the distilled water and the ethylene glycol in the step 1) is V (water), V (ethylene glycol) is 10:1, stirring for 600r/min, and stirring for 60min until the mixture is clear and transparent to obtain a mixed solution B;
3) adding selenium powder and sodium borohydride into 10mL of distilled water, wherein the mass ratio of the antimony trichloride to the selenium powder in the step 2) is n (SbCl)3) N (Se) 1:1, wherein the mass ratio of the selenium powder to the sodium borohydride is n (Se) n (NaBH)4) Stirring at a ratio of 1:2 for 600r/min for 30min at a temperature of 70 ℃ to obtain a wine red mixed solution C;
4) mixing the mixed solution B with the mixed solution C, and dropwise adding the mixed solution A into the mixed solution B, wherein the stirring speed is 600r/min, and the stirring time is 30min to obtain a mixed solution D;
5) filling the mixed solution D into a polytetrafluoroethylene lining with the filling ratio of 80%, then filling the mixed solution D into a hydrothermal kettle in a homogeneous reactor, carrying out hydrothermal reaction for 24 hours at 210 ℃, and cooling to room temperature after the reaction is finished; washing with water and anhydrous ethanol alternately for multiple times, separating precipitate, and freeze drying at-50 deg.C under 30Mpa for 16 hr to obtain C/Sb2Se3A complex powder; (ii) a
6) Take 0.8g C/Sb2Se3Adding the complex powder into 80mL of 2g/L sodium hydroxide aqueous solution, stirring at 600r/min for 40min to obtain a mixed solution E;
7) filling the mixed solution E into a polytetrafluoroethylene lining with the filling ratio of 80%, then filling the mixed solution E into a hydrothermal kettle in a homogeneous reactor, carrying out hydrothermal reaction for 12 hours at 160 ℃, and cooling to room temperature after the reaction is finished; washing with water and anhydrous ethanol alternately for several times, separating precipitate, freeze drying at-50 deg.C under 30Mpa for 16 hr to obtain Se/C/Sb2Se3And (3) composite powder.
Example 6:
1) adding gamma-cyclodextrin with the substance amount of 1mmol into distilled water, stirring at 550r/min for 35min until the mixture is clear and transparent to obtain a mixed solution A;
2) adding antimony trichloride into absolute ethyl alcohol, wherein the volume ratio of the distilled water and the absolute ethyl alcohol in the step 1) is V (water), and the volume ratio of the distilled water and the absolute ethyl alcohol is 7:1, stirring for 540r/min for 45min until the solution is clear and transparent, so as to obtain a mixed solution B;
3) adding selenium powder and sodium borohydride into 8mL of distilled water, wherein the mass ratio of the antimony trichloride to the selenium powder in the step 2) is n (SbCl)3) N (Se) 1:1.5, the mass ratio of selenium powder to sodium borohydride is n (Se) n (NaBH)4) Stirring at a ratio of 1:1.7 for 560r/min for 18min at 55 ℃ to obtain a wine red mixed solution C;
4) mixing the mixed solution B with the mixed solution C, and dropwise adding the mixed solution A into the mixed solution B, wherein the stirring speed is 570r/min, and the stirring time is 15min to obtain a mixed solution D;
5) filling the mixed solution D into a polytetrafluoroethylene lining with a filling ratio of 65%, filling the mixed solution D into a hydrothermal kettle in a homogeneous reactor, carrying out hydrothermal reaction for 18h at 180 ℃, and cooling to room temperature after the reaction is finished; washing with water and anhydrous ethanol alternately for multiple times, separating precipitate, and freeze drying at-46 deg.C under 24Mpa for 10 hr to obtain C/Sb2Se3A complex powder; (ii) a
6) Take 0.4g C/Sb2Se3Adding the complex powder into 65mL of 1.7g/L sodium hydroxide aqueous solution, stirring at 530r/min for 36min to obtain a mixed solution E;
7) filling the mixed solution E into a polytetrafluoroethylene lining with the filling ratio of 74%, filling the mixed solution E into a hydrothermal kettle in a homogeneous reactor, carrying out hydrothermal reaction for 8 hours at the temperature of 120 ℃, and cooling to room temperature after the reaction is finished; washing with water and anhydrous ethanol alternately for several times, separating precipitate, freeze drying at-40 deg.C under 20Mpa for 16 hr to obtain Se/C/Sb2Se3And (3) composite powder.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; 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 or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. Se/C/Sb2Se3The preparation method of the double-shell hollow nano rod-shaped sodium ion battery cathode material is characterized by comprising the following steps of:
1) adding gamma-cyclodextrin with the substance amount of 0.5 mmol-2 mmol into distilled water and stirring to obtain a mixed solution A;
2) adding antimony trichloride into absolute ethyl alcohol or ethylene glycol solvent and stirring to obtain a mixed solution B, wherein the volume ratio of distilled water to the absolute ethyl alcohol or the ethylene glycol in the step 1) is (5:1) - (10: 1);
3) adding selenium powder and sodium borohydride into 5-10 mL of distilled water, and stirring at 40-70 ℃ to obtain a mixed solution C, wherein the mass ratio of antimony trichloride to selenium powder in the step 2) is (1:2) - (1:1), and the mass ratio of selenium powder to sodium borohydride is (1:2) - (1: 1);
4) mixing the mixed solution B with the mixed solution C, dropwise adding the mixed solution A into the mixed solution B, and stirring to obtain a mixed solution D;
5) carrying out hydrothermal reaction on the mixed solution D at 150-210 ℃, cooling to room temperature after the reaction is finished, washing, separating and precipitating, and carrying out freeze drying on the precipitate to obtain C/Sb2Se3A complex powder;
6) taking 0.1-0.8 g of C/Sb2Se3Adding the complex powder into 50-80 mL of 0.5-2 g/L sodium hydroxide aqueous solution and stirring to obtain a mixed solution E;
7) carrying out hydrothermal reaction on the mixed solution E at the temperature of 80-160 ℃, cooling to room temperature after the reaction is finished, washing, separating and drying the precipitate to obtain Se/C/Sb2Se3Double-shell hollow nano rod-shaped sodium ion battery cathode material.
2. Se/C/Sb according to claim 12Se3The preparation method of the double-shell hollow nano rod-shaped sodium ion battery cathode material is characterized in that in the step 1), the stirring speed is 500-600 r/min, and the stirring time is 30-40 min, so that a clear and transparent mixed solution A is obtained.
3. Se/C/Sb according to claim 12Se3The preparation method of the double-shell hollow nano rod-shaped sodium ion battery cathode material is characterized in that in the step 2), the stirring speed is 500-600 r/min, and the stirring time is 30-60 min, so that a clear and transparent mixed solution B is obtained.
4. According toA Se/C/Sb alloy as set forth in claim 12Se3The preparation method of the double-shell hollow nano rod-shaped sodium ion battery cathode material is characterized in that in the step 3), the stirring speed is 500-600 r/min, and the stirring time is 10-30 min, so that a wine red mixed solution C is obtained.
5. Se/C/Sb according to claim 12Se3The preparation method of the double-shell hollow nano rod-shaped sodium ion battery cathode material is characterized in that in the step 4), the stirring speed is 500-600 r/min, and the stirring time is 10-30 min.
6. Se/C/Sb according to claim 12Se3The preparation method of the double-shell hollow nano rod-shaped sodium ion battery cathode material is characterized in that in the step 5), the mixed solution D is filled into a polytetrafluoroethylene lining with the filling ratio of 50% -80%, and then the polytetrafluoroethylene lining is filled into a hydrothermal kettle to perform hydrothermal reaction in a homogeneous phase reactor for 12-24 hours.
7. Se/C/Sb according to claim 12Se3The preparation method of the double-shell hollow nano rod-shaped sodium ion battery cathode material is characterized in that the freeze drying in the step 5) and the step 7) is carried out for 9-16 h under the conditions of-40 to-50 ℃ and the pressure of 20-30 Mpa.
8. Se/C/Sb according to claim 12Se3The preparation method of the double-shell hollow nano rod-shaped sodium ion battery cathode material is characterized in that in the step 6), the stirring speed is 500-600 r/min, and the stirring time is 30-40 min.
9. Se/C/Sb according to claim 12Se3The preparation method of the double-shell hollow nano rod-shaped sodium ion battery cathode material is characterized in that in the step 7), the mixed solution E is filled into a polytetrafluoroethylene lining with the filling ratio of 50% -80%, and then polytetrafluoroethylene is addedThe lining is placed into a hydrothermal kettle to perform hydrothermal reaction in a homogeneous phase reactor for 3-12 h.
10. Se/C/Sb2Se3The double-shell hollow nano rod-shaped sodium ion battery cathode material is characterized in that the Se/C/Sb material as claimed in any one of claims 1 to 9 is adopted2Se3The double-shell hollow nano rod-shaped sodium ion battery cathode material is prepared by a preparation method.
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