CN113023706B - Carbon-coated antimony selenide/graphene composite material and preparation method and application thereof - Google Patents

Carbon-coated antimony selenide/graphene composite material and preparation method and application thereof Download PDF

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CN113023706B
CN113023706B CN202110258408.9A CN202110258408A CN113023706B CN 113023706 B CN113023706 B CN 113023706B CN 202110258408 A CN202110258408 A CN 202110258408A CN 113023706 B CN113023706 B CN 113023706B
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antimony selenide
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graphene composite
mixed solution
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黄剑锋
郭玲
雒甜蜜
曹丽云
李嘉胤
许占位
冯永强
王海
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Shaanxi University of Science and Technology
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Abstract

The invention discloses a carbon-coated antimony selenide/graphene composite material and a preparation method and application thereof, wherein the preparation method is characterized in that Sb is subjected to a one-step hydrothermal method 2 Se 3 The composite material with the sandwich structure is obtained, antimony selenide grows on the reduced graphene oxide, and the conductivity of the antimony selenide can be improved by combining the antimony selenide and the reduced graphene oxide; the carbon source coated antimony selenide can relieve the volume expansion of antimony selenide during the embedding and the removal of sodium ions to the maximum extent, and the carbon source coated antimony selenide serving as a sodium ion battery cathode material has excellent capacity, conductivity and cycling stability, and improves the stability of the electrode material so as to ensure that the battery has a long service life in practical application.

Description

Carbon-coated antimony selenide/graphene composite material and preparation method and application thereof
Technical Field
The invention belongs to the field of new energy batteries, and particularly relates to a carbon-coated antimony selenide/graphene composite material as well as a preparation method and application thereof.
Background
In recent years, research on energy storage materials becomes a hot spot explored by researchers, and electrochemical energy storage is distinguished from a plurality of energy storage modes due to the characteristics of high efficiency, safety and the like. Compared with the lithium ion battery which is successfully commercialized, the sodium ion battery has rich raw materials, is convenient to extract, and has very wide application prospect. However, the sodium ion battery has small specific capacity and low cycling efficiency, and the electrode material is easy to be pulverized along with huge volume change in the cycling process, which becomes an important problem affecting the further development of the sodium ion battery.
The metal selenide has higher initial efficiency due to small volume change and large reversibility in the lithium intercalation and deintercalation process. Wherein Sb 2 Se 3 Has a weight ratio of about 670mAhg -1 However, since the carbon material has poor conductivity and is liable to undergo volume expansion during charge and discharge, which leads to unstable cycle, there is a need to find a carbon material having excellent conductivity and to compound the carbon material with the carbon material, and there is also a strong need to find a method for effectively improving the stability of a selenide electrode material.
With Sb 2 Se 3 Although the material has high specific capacity when used as a negative electrode material of a sodium ion battery, if an electrode material which has excellent electrochemical performance and high cycle stability is to be obtained, sb is required to be used 2 Se 3 And compounding with other materials. So that Sb will be attached to the graphene 2 Se 3 Coating with carbon to obtain C/Sb 2 Se 3 The composite material with the/rGO sandwich structure is a high-efficiency and feasible method capable of achieving ideal effects.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a carbon-coated antimony selenide/graphene composite material and a preparation method and application thereof, wherein the preparation method is to mix Sb by a one-step hydrothermal method 2 Se 3 The in-situ oriented anchoring is carried out on the graphene, carbon coating is simultaneously realized, the preparation process is simple, and the prepared composite material is used as a sodium ion battery cathode material and has excellent capacity, conductivity and cycling stability.
In order to achieve the above object, the present invention provides a preparation method of a carbon-coated antimony selenide/graphene composite material, comprising the following steps:
1) Adding 40-80 mg of graphene oxide into 40-80 ml of distilled water, dissolving, adding 0.2701-0.6759 g of antimony potassium tartrate, 0.1-0.3 g of polyvinylpyrrolidone and 0.5-2.5 g of carbon source, and stirring to obtain a mixed solution A;
2) Dispersing 0.1326-0.1907 g of selenium powder in 2-6 ml of hydrazine hydrate and stirring to obtain wine red mixed solution B;
3) Mixing and dispersing the mixed solution B and the mixed solution A to obtain a mixed solution C;
4) And carrying out hydrothermal reaction on the mixed solution C at 160-220 ℃ for 12-24 h, cooling to room temperature after the reaction is finished, washing, separating precipitate, and freeze-drying the separated precipitate to obtain the carbon-coated antimony selenide/graphene composite material.
Preferably, the graphene oxide in the step 1) is added into distilled water and is dissolved completely by ultrasonic oscillation, the power of the ultrasonic oscillation is 80-120W, the temperature of the ultrasonic oscillation is 40-60 ℃, and the time of the ultrasonic oscillation is 8-12 h.
Preferably, the carbon source in step 1) comprises chitosan, citric acid or fructose.
Preferably, the stirring speed in the step 1) is 500-600 r/min, and the stirring time is 20-30 min.
Preferably, the stirring speed in the step 2) is 500-600 r/min, the stirring time is 20-30 min, and the stirring temperature is 40-60 ℃.
Preferably, the dispersion in the step 3) is ultrasonic dispersion, the ultrasonic power is 80W-120W, the ultrasonic temperature is 40-60 ℃, and the ultrasonic time is 8-12 h.
Preferably, the mixed solution C in the step 4) is filled into a polytetrafluoroethylene lining, and then is filled into a hydrothermal kettle and then is put into a homogeneous reactor for hydrothermal reaction.
Preferably, the filling ratio of the polytetrafluoroethylene lining in the step 4) is 50% -70%, the washing is performed by alternately washing with distilled water and ethanol for 4-6 times, and the freeze drying is performed under a vacuum condition.
The invention also provides a carbon-coated antimony selenide/graphene composite material prepared by the preparation method of the carbon-coated antimony selenide/graphene composite material.
The invention also provides an application of the carbon-coated antimony selenide/graphene composite material as a sodium ion battery cathode material.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the antimony selenide material growing on the graphene is wrapped by different carbon sources, and the sandwich structure sodium-ion battery cathode material with excellent capacity, conductivity and cycling stability is obtained by regulating the ratio of two carbon sources, namely the graphene and the carbon source wrapped by the outer layer.
2. According to the invention, antimony selenide grows on reduced graphene oxide, and the combination of the two can improve the conductivity of the antimony selenide; the carbon source is used for wrapping the antimony selenide, so that the volume expansion of the antimony selenide during the embedding and the removal of sodium ions can be relieved to the maximum extent, and the stability of the electrode material is improved to ensure that the battery has a longer service life in practical application.
3. The carbon source selection in the invention is diversified and is not limited to one, so that the possibility of successful preparation of the material is greatly increased. Compared with other preparation methods, the invention can synthesize the target sandwich structure material by only one-step hydrothermal method, and has the advantages of rich preparation raw materials, simple process operation and easy implementation.
Drawings
FIG. 1 shows C/Sb prepared according to the invention 2 Se 3 XRD patterns for/rGO electrode materials;
FIG. 2 shows C/Sb prepared according to the present invention 2 Se 3 SEM images of/rGO electrode materials;
FIG. 3 shows C/Sb prepared according to the present invention 2 Se 3 TEM image of/rGO electrode material;
FIG. 4 shows C/Sb prepared according to the present invention 2 Se 3 Electrochemical performance profile of/rGO 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 obtained by a person of ordinary skill in the art based on the embodiments in the present application without making any creative effort belong to the protection scope of the present application.
The invention provides a preparation method of a carbon-coated antimony selenide/graphene composite material, which comprises the following steps:
1) Adding 40-80 mg of graphene oxide into 40-80 ml of distilled water, carrying out ultrasonic vibration (the power is 80-120W, the ultrasonic temperature is 40-60 ℃, and the ultrasonic time is 8-12 h) until the graphene oxide is completely dissolved, adding 0.2701-0.6759 g of antimony potassium tartrate, 0.1-0.3 g of polyvinylpyrrolidone and 0.5-2.5 g of carbon sources (chitosan, citric acid and fructose) into the solution, stirring the solution for 500-600 r/min and 20-30 min until the graphene oxide is completely dissolved, and carrying out ultrasonic dispersion to obtain a mixed solution A;
2) Dispersing (0.1326-0.1907) g selenium powder in (2-6) ml hydrazine hydrate, stirring (the stirring speed is 500-600 r/min, the stirring time is 20-30 min, and the stirring temperature is 40-60 ℃) to obtain a wine red solution B;
3) Mixing the solution B with the solution A, and performing ultrasonic treatment (the ultrasonic power is 80W-120W, the ultrasonic temperature is 40-60 ℃, and the ultrasonic time is 8-12 h) until the solution B and the solution A are uniformly dispersed to obtain a mixed solution C;
4) Filling the mixed solution C into a polytetrafluoroethylene lining with a filling ratio of 50-70%, filling the mixed solution C into a hydrothermal kettle, putting the hydrothermal kettle into a homogeneous reactor, carrying out hydrothermal reaction for 12-24 h at 160-220 ℃, and cooling to room temperature after the reaction is finished; washing (washing with water and ethanol alternately for 4-6 times), separating the precipitate, and freeze-drying the separated precipitate under a vacuum condition to obtain the carbon-coated antimony selenide/graphene composite material powder.
The invention also provides a carbon-coated antimony selenide/graphene composite material which has a sandwich structure, wherein antimony selenide grows on reduced graphene oxide, and the combination of the antimony selenide and the reduced graphene oxide can improve the conductivity of the antimony selenide; the carbon source is used for wrapping the antimony selenide, so that the volume expansion of the antimony selenide during the embedding and the removal of sodium ions can be relieved to the maximum extent, the carbon source is applied to the cathode material of the sodium ion battery, the capacity, the conductivity and the cycling stability are excellent, and the stability of the electrode material is improved to ensure that the battery has a longer service life in practical application.
The present invention will be described with reference to specific examples.
Example 1:
1) Adding 60mg of graphene oxide into 60ml of distilled water, oscillating by ultrasonic (80W, 40 ℃,8 h) until the graphene oxide is completely dissolved, adding 0.4731g of antimony potassium tartrate, 0.2g of polyvinylpyrrolidone and 1.5g of chitosan, stirring (500 r/min,20 min) until the graphene oxide is completely dissolved, and then performing ultrasonic 30min to uniformly disperse the mixture to obtain a mixed solution A;
2) Dispersing 0.1658g selenium powder in 4ml hydrazine hydrate, stirring (500 r/min,50 deg.C, 20 min) to obtain wine red solution B;
3) Dropwise adding the solution B into the solution A under the condition of continuous stirring, and uniformly performing ultrasonic dispersion to obtain a mixed solution C;
4) Filling the mixed solution C into a polytetrafluoroethylene lining with the filling degree of 60%, filling the mixed solution C into a hydrothermal kettle, putting the hydrothermal kettle into a homogeneous reactor, carrying out hydrothermal reaction for 24 hours at 180 ℃, and cooling to room temperature after the reaction is finished; and (2) alternately washing the two solutions by using ethanol and distilled water as solvents for 6 times, washing and centrifuging (7500 r/min) to separate precipitates, and freeze-drying the separated precipitates under a vacuum condition (50 ℃ below zero, 20MPa, and 1 2h) to obtain the carbon-coated antimony selenide/graphene composite powder.
For C/Sb prepared in example 1 2 Se 3 XRD analysis is carried out on the/rGO electrode material, the result is shown in figure 1, and the comparison with a standard card 71-0143 can be seen from the figure 1, the prepared sample has obvious characteristic peaks, the characteristic diffraction peaks can be well matched, and the synthesized sample is pure-phase Sb 2 Se 3 。
For C/Sb prepared in example 1 2 Se 3 SEM analysis of the/rGO electrode material, results are shown in FIG. 2, from which it can be seen that Sb is 50nm in diameter 2 Se 3 The surface of the nano rod is coated.
For C/Sb prepared in example 1 2 Se 3 TEM analysis of/rGO electrode material is carried out, the result is shown in FIG. 3, the synthesized composite material has different crystal phases which can be seen from FIG. 3, and the analysis result combined with FIG. 1 and FIG. 2 judges that Sb growing on graphene is Sb 2 Se 3 Is coated with carbon.
For C/Sb prepared in example 1 2 Se 3 The electrochemical test of the/rGO electrode material is carried out, the result is shown in figure 4, and the sample prepared in figure 4 can be seen along with the progress of charging and dischargingAlthough the amount has certain fluctuation, the whole amount tends to 802.3mAh g -1 。
Example 2:
1) Adding 80mg of graphene oxide into 80ml of distilled water, oscillating by ultrasonic waves (80W, 40 ℃,8 h) until the graphene oxide is completely dissolved, adding 0.5407g of antimony potassium tartrate, 0.25g of polyvinylpyrrolidone and 2g of chitosan, stirring (600 r/min,20 min) until the graphene oxide is completely dissolved, and uniformly dispersing by ultrasonic waves for 30min to obtain a mixed solution A;
2) Dispersing 0.1782g selenium powder in 5ml hydrazine hydrate, stirring (600 r/min,60 ℃,20 min) to obtain wine red solution B;
3) Dropwise adding the solution B into the solution A under the condition of continuous stirring, and uniformly dispersing by ultrasonic to obtain a mixed solution C;
4) Filling the mixed solution C into a polytetrafluoroethylene lining, filling the polytetrafluoroethylene lining with the filling degree of 80%, filling the polytetrafluoroethylene lining into a hydrothermal kettle, putting the hydrothermal kettle into a homogeneous reactor, carrying out hydrothermal reaction for 24 hours at 200 ℃, and cooling to room temperature after the reaction is finished; and (2) alternately washing the two solutions by using ethanol and distilled water as solvents for 6 times, washing and centrifuging (7500 r/min) to separate precipitates, and freeze-drying the separated precipitates under a vacuum condition (50 ℃ below zero, 20MPa, and 1 2h) to obtain the carbon-coated antimony selenide/graphene composite powder.
Example 3:
1) Adding 40mg of graphene oxide into 40ml of distilled water, oscillating by ultrasonic (80W, 40 ℃,8 h) until the graphene oxide is completely dissolved, adding 0.2701g of antimony potassium tartrate, 0.1g of polyvinylpyrrolidone and 0.5g of chitosan, stirring (500 r/min,20 min) until the graphene oxide is completely dissolved, and then performing ultrasonic 30min to uniformly disperse the graphene oxide to obtain a mixed solution A;
2) Dispersing 0.1326g of selenium powder in 2ml of hydrazine hydrate, and stirring (600 r/min,60 ℃,20 min) to obtain wine red solution B;
3) Dropwise adding the solution B into the solution A under the condition of continuous stirring, and uniformly performing ultrasonic dispersion to obtain a mixed solution C;
4) Filling the mixed solution C into a polytetrafluoroethylene lining, wherein the filling degree is 40%, filling the mixed solution C 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; and (2) alternately washing the two solutions by using ethanol and distilled water as solvents for 6 times, washing and centrifuging (7500 r/min) to separate precipitates, and freeze-drying the separated precipitates under a vacuum condition (50 ℃ below zero, 20MPa, and 1 2h) to obtain the carbon-coated antimony selenide/graphene composite powder.
Example 4:
1) Adding 60mg of graphene oxide into 60ml of distilled water, oscillating by ultrasonic waves (100W, 50 ℃,10 hours) until the graphene oxide is completely dissolved, adding 0.4731g of antimony potassium tartrate, 0.2g of polyvinylpyrrolidone and 1.5g of citric acid, stirring (550 r/min,30 minutes) until the graphene oxide is completely dissolved, and then performing ultrasonic waves for 30 minutes to uniformly disperse to obtain a mixed solution A;
2) Dispersing 0.1658g selenium powder in 4ml hydrazine hydrate, stirring (600 r/min,60 deg.C, 20 min) to obtain wine red solution B;
3) Dropwise adding the solution B into the solution A under the condition of continuous stirring, and uniformly performing ultrasonic dispersion to obtain a mixed solution C;
4) Filling the mixed solution C into a polytetrafluoroethylene lining with the filling degree of 60%, filling the mixed solution C into a hydrothermal kettle, putting the hydrothermal kettle into a homogeneous reactor, carrying out hydrothermal reaction for 12 hours at 180 ℃, and cooling to room temperature after the reaction is finished; and (2) alternately washing the two solutions by using ethanol and distilled water as solvents for 6 times, washing and centrifuging (7500 r/min) to separate precipitates, and freeze-drying the separated precipitates under a vacuum condition (50 ℃ below zero, 20MPa, and 1 2h) to obtain the carbon-coated antimony selenide/graphene composite powder.
Example 5:
1) Adding 70mg of graphene oxide into 70ml of distilled water, oscillating by ultrasound (120W, 60 ℃,12 h) until the graphene oxide is completely dissolved, adding 0.5407g of antimony potassium tartrate, 0.2g of polyvinylpyrrolidone and 2.0g of fructose, stirring (600 r/min,30 min) until the graphene oxide is completely dissolved, and performing ultrasound for 30min to uniformly disperse to obtain a mixed solution A;
2) Dispersing 0.1782g selenium powder in 5ml hydrazine hydrate, stirring (600 r/min,50 ℃,30 min) to obtain wine red solution B;
3) Dropwise adding the solution B into the solution A under the condition of continuous stirring, and uniformly dispersing by ultrasonic to obtain a mixed solution C;
4) Filling the mixed solution C into a polytetrafluoroethylene lining, wherein the filling degree is 70%, then filling the mixed solution C into a hydrothermal kettle, putting the hydrothermal kettle into a homogeneous reactor, carrying out hydrothermal reaction for 12 hours at 220 ℃, and cooling to room temperature after the reaction is finished; and (2) alternately washing the two solutions by using ethanol and distilled water as solvents for 6 times, washing and centrifuging (7500 r/min) to separate precipitates, and freeze-drying the separated precipitates under a vacuum condition (50 ℃ below zero, 20MPa, and 1 2h) to obtain the carbon-coated antimony selenide/graphene composite powder.
Example 6:
1) Adding 50mg of graphene oxide into 50ml of distilled water, oscillating by ultrasonic waves (80W, 50 ℃,10 h) until the graphene oxide is completely dissolved, adding 0.6759g of antimony potassium tartrate, 0.3g of polyvinylpyrrolidone and 2.5g of fructose, stirring (550 r/min,25 min) until the graphene oxide is completely dissolved, and uniformly dispersing by ultrasonic waves for 26min to obtain a mixed solution A;
2) Dispersing 0.1907g of selenium powder in 5ml of hydrazine hydrate, and stirring (540 r/min,55 ℃,26 min) to obtain a wine red solution B;
3) Dropwise adding the solution B into the solution A under the condition of continuous stirring, and uniformly performing ultrasonic dispersion to obtain a mixed solution C;
4) Filling the mixed solution C into a polytetrafluoroethylene lining, wherein the filling degree is 50%, filling the mixed solution C into a hydrothermal kettle, putting the hydrothermal kettle into a homogeneous reactor, carrying out hydrothermal reaction for 20 hours at 170 ℃, and cooling to room temperature after the reaction is finished; and (2) alternately washing 6 times by using two solutions of ethanol and distilled water as solvents, washing and centrifuging (7500 r/min) to separate precipitates, and freeze-drying the separated precipitates under a vacuum condition (-50 ℃,20Mpa and 12h) to obtain the carbon-coated antimony selenide/graphene 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 should 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. A preparation method of a carbon-coated antimony selenide/graphene composite material is characterized by comprising the following steps:
1) Adding 40-80 mg of graphene oxide into 40-80 ml of distilled water, dissolving, adding 0.2701-0.6759 g of antimony potassium tartrate, 0.1-0.3 g of polyvinylpyrrolidone and 0.5-2.5 g of carbon source, and stirring to obtain a mixed solution A;
2) Dispersing 0.1326-0.1907 g of selenium powder in 2-6 ml of hydrazine hydrate and stirring to obtain wine red mixed solution B;
3) Mixing and dispersing the mixed solution B and the mixed solution A to obtain a mixed solution C;
4) And carrying out hydrothermal reaction on the mixed solution C at 160-220 ℃ for 12-24 h, cooling to room temperature after the reaction is finished, washing, separating the precipitate, and freeze-drying the separated precipitate to obtain the carbon-coated antimony selenide/graphene composite material.
2. The preparation method of the carbon-coated antimony selenide/graphene composite material as claimed in claim 1, wherein the graphene oxide in the step 1) is added into distilled water and is dissolved completely by ultrasonic oscillation, the power of the ultrasonic oscillation is 80W-120W, the temperature of the ultrasonic oscillation is 40-60 ℃, and the time of the ultrasonic oscillation is 8-12 h.
3. The method for preparing the carbon-coated antimony selenide/graphene composite material according to claim 1, wherein the carbon source in the step 1) comprises chitosan, citric acid or fructose.
4. The preparation method of the carbon-coated antimony selenide/graphene composite material according to claim 1, wherein the stirring speed in the step 1) is 500-600 r/min, and the stirring time is 20-30 min.
5. The preparation method of the carbon-coated antimony selenide/graphene composite material as claimed in claim 1, wherein the stirring speed in the step 2) is 500-600 r/min, the stirring time is 20-30 min, and the stirring temperature is 40-60 ℃.
6. The preparation method of the carbon-coated antimony selenide/graphene composite material according to claim 1, wherein the dispersion in the step 3) is ultrasonic dispersion, the ultrasonic power is 80W-120W, the ultrasonic temperature is 40-60 ℃, and the ultrasonic time is 8-12 h.
7. The method for preparing the carbon-coated antimony selenide/graphene composite material as claimed in claim 1, wherein the mixed solution C in the step 4) is filled into a polytetrafluoroethylene lining, and then is filled into a hydrothermal kettle and then is put into a homogeneous reactor for hydrothermal reaction.
8. The method for preparing the carbon-coated antimony selenide/graphene composite material as claimed in claim 7, wherein the filling ratio of the polytetrafluoroethylene lining in the step 4) is 50% -70%, washing is performed by alternately washing with distilled water and ethanol for 4-6 times, and freeze-drying is performed under a vacuum condition.
9. A carbon-coated antimony selenide/graphene composite material, which is characterized by being prepared by the preparation method of the carbon-coated antimony selenide/graphene composite material as claimed in any one of claims 1 to 8.
10. The use of the carbon-coated antimony selenide/graphene composite material of claim 9 as a cathode material of a sodium-ion battery.
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