CN110212165B - Sb2O5Preparation method of/GO/carbon cloth sodium ion battery cathode material - Google Patents
Sb2O5Preparation method of/GO/carbon cloth sodium ion battery cathode material Download PDFInfo
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Abstract
The invention provides Sb2O5The preparation method of the/GO/carbon cloth sodium ion battery anode material comprises the following steps: step 1: soaking the carbon cloth in acetone to remove impurities, washing, carrying out anodic oxidation treatment, washing and drying; step 2: adding graphene oxide and antimony trichloride into absolute ethyl alcohol to obtain an antimony solution, then adding a sodium hydroxide aqueous solution into the antimony solution, adjusting the pH value to 8-12 to obtain a mixed solution, and soaking the carbon cloth pretreated in the step 1 into the mixed solution; and step 3: transferring the mixed solution obtained in the step 2 and the carbon cloth to a reaction vessel for hydrothermal reaction at the temperature of 150-180 ℃, cooling to room temperature after the reaction is finished, taking out the carbon cloth, cleaning and drying to obtain Sb2O5The negative electrode material of the/GO/carbon cloth sodium ion battery. Sb prepared by the invention2O5the/GO/carbon cloth sodium ion battery cathode material shows excellent electrochemical cycle performance, and meanwhile, the preparation method is simple and novel, short in preparation period, high in repeatability and suitable for large-scale production.
Description
Technical Field
The invention belongs to the field of new energy materials, and particularly relates to Sb2O5A preparation method of a/GO/carbon cloth sodium ion battery cathode material.
Background
The sodium element and the lithium element have the same main group and have a plurality of similar physicochemical properties. However, the radius of sodium ions (0.113nm) is much larger than that of lithium ions (0.076nm), so that the problems of low capacity, poor magnification and short cycle life can occur when some negative electrode materials for lithium ion batteries are applied to the sodium ion batteries, and therefore, the exploration of the negative electrode materials for high-performance sodium ion batteries is very necessary. At present, the research on the negative electrode material of the sodium ion battery mainly comprises carbon materials, alloy materials, metal oxides, phosphorus and the like. Among them, metal oxides have a high theoretical specific capacity and are widely concerned. Some metal oxides such as CuO, NiO and Fe2O3The sodium storage process only has one-step conversion reaction, and the reaction mechanism is
Where M is a metal, it is generally not capable of further reaction with Na +. It is clear that if the metal M can continue to undergo alloying reaction, further with Na+The specific capacity will be higher.
Due to Sb and Na+Can generate alloying reaction, so the antimony oxide has received high attention as the cathode material of the sodium ion battery. But the metal oxide is used as a battery material,as the sodium elimination reaction is repeated, a large volume effect is generated. Thus, in the preparation of conventional electrodes, the modification is often carried out by a complex method. At present, Sb is the most studied electrode material of antimony oxide2O3For example, sting Zhou et al prepared Sb by wet chemical method2O3the/RGO has better cycle stability as the cathode material of the sodium ion battery and has the current density of 50mA g-1The first discharge specific capacity is 1769mA hg-1The reversible capacity can be kept at 562mA h g after 100 cycles-1(3D nest-shaped Sb2O3RGOcomposite based high-performance characteristics-ion batteries, nanoscale.2016; 8(39):17131-17135). Sb is prepared by Xiao zhong Zhou and the like by a wet chemical method2O3/CNTs/rGO as the cathode material of the sodium ion battery has better cycle stability and the current density is 200 mA g-1The first specific capacity is 1090mA h g-1The reversible capacity can be maintained at 543.8mA h g after 50 cycles-1(Facile and rapid synthesis ofSb2O3/CNTs/rGO nanocomposite with excellent sodium storageperformances.Materials Letters.2016；213:201-203)。
It can be seen that Sb can be increased by compounding2O3Cycle stability of (B), but currently for the higher valence antimony oxides Sb2O5It is not reported as the electrode material of secondary battery.
Disclosure of Invention
The invention aims to provide Sb2O5A preparation method of a/GO/carbon cloth sodium ion battery anode material comprises the step of mixing Sb2O5The electrolyte is directly used in a negative electrode of a sodium ion battery and shows good electrochemical performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
sb2O5The preparation method of the/GO/carbon cloth sodium ion battery cathode material comprises the following steps:
step 1: placing the carbon cloth into acetone, soaking, removing impurities, washing and drying, carrying out anodic oxidation treatment on the dried carbon cloth, and drying after washing;
step 2: adding 3-10 mg of graphene oxide and 0.3-1.0 g of antimony trichloride into 20-60 mL of absolute ethanol, and dissolving to obtain an antimony solution; adjusting the pH value of the antimony solution to 8-12 by using a sodium hydroxide aqueous solution to obtain a mixed solution, and soaking the carbon cloth subjected to anodic oxidation in the mixed solution;
and step 3: transferring the mixed solution obtained in the step (2) and the carbon cloth into a reaction container for hydrothermal reaction at the temperature of 150-180 ℃, cooling to room temperature after the reaction is finished, taking out the carbon cloth, cleaning and drying to obtain Sb2O5The negative electrode material of the/GO/carbon cloth sodium ion battery.
Further, the carbon in the step 1 is soaked in acetone for 24-72 hours and then washed by deionized water and absolute ethyl alcohol respectively.
Further, electrolyte used in the anodic oxidation in the step 1 is one of ammonium dihydrogen phosphate, ammonium dihydrogen carbonate, ammonium carbonate and ammonium hydrogen carbonate with the concentration of 15-25 g/L; the anodic oxidation voltage is 5-10V, and the time is 3-10 min.
Further, the mass ratio of the graphene oxide to the antimony trichloride in the step 2 is 0.5-1.7%.
Furthermore, the graphene oxide is single-layer graphene oxide powder, the sheet diameter of the graphene oxide powder is 0.5-5 μm, and the thickness of the graphene oxide powder is 0.8-1.2 nm.
Further, the process of adjusting the pH value of the antimony solution by the sodium hydroxide aqueous solution in the step 2 is to gradually add the sodium hydroxide aqueous solution into the antimony solution and stir the sodium hydroxide aqueous solution to obtain a mixed solution; and (3) soaking the carbon cloth after the anodic oxidation in the mixed solution and stirring for 20-40 min.
Further, magnetic stirring is adopted in the step 2.
Further, in the step 3, the reaction vessel is a polytetrafluoroethylene kettle, the mixed solution and the carbon cloth are transferred into the polytetrafluoroethylene kettle and placed in a homogeneous phase reactor for hydrothermal reaction for 4-48 hours; the cleaning is repeatedly performed by using deionized water and absolute ethyl alcohol respectively.
Further, Sb prepared in step 32O5Sb in/GO/carbon cloth sodium ion battery cathode material2O5Has a particle diameter of 50 to 100nm and Sb2O5The graphene oxide is uniformly distributed on the carbon cloth substrate with the graphene oxide as the buffer layer.
Furthermore, the carbon cloth is hydrophilic carbon cloth with the specification of 4cm x2 cm.
The invention has the beneficial effects that:
the invention provides Sb2O5The preparation method of the/GO/carbon cloth sodium ion battery cathode material innovatively combines Sb with a flexible electrode2O5Growing the Sb on a carbon cloth flexible substrate in situ by compounding GO and Sb2O5the/GO/carbon cloth composite material is directly used in the negative electrode of the sodium ion battery and shows good electrochemical performance; the preparation method combines Sb2O5The high specific capacity property of the electrode material of the battery and the polar oxide can form firm chemical bonding with the graphene oxide with oxygen-rich functional groups, and simultaneously have the characteristic of good dispersibility of the graphene oxide, and Sb is effectively regulated and controlled by regulating and controlling the mass ratio of antimony trichloride and the graphene oxide which are reaction precursors2O5Uniformly growing a composite structure of carbon cloth with GO as a buffer layer; the preparation method used by the invention is simple and novel, has short preparation period and high repeatability, and has important significance for preparing the composite carbon cloth flexible electrode material.
Drawings
FIG. 1 shows Sb prepared in example 32O5The X-ray diffraction spectrum of the/GO/carbon cloth sodium ion battery negative electrode material;
FIG. 2 shows Sb prepared in example 32O5Scanning electron microscope photos of the/GO/carbon cloth sodium ion battery cathode material;
FIG. 3 shows Sb prepared in example 32O5And the electrochemical cycle performance diagram of the/GO/carbon cloth sodium ion battery negative electrode material.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and examples.
Example 1:
sb2O5sodium/GO/carbon clothThe preparation method of the negative electrode material of the ion battery comprises the following steps:
step 1: putting a carbon cloth with the length of 4cm and the width of 2cm into 50mL of acetone, soaking for 72h to remove impurities, washing with deionized water and absolute ethyl alcohol respectively until the carbon cloth is clean, and drying in an oven at 60 ℃; the dried carbon cloth is used as an anode, the graphite plate is used as a cathode, 20g/L ammonium dihydrogen phosphate aqueous solution is used as electrolyte to carry out anodic oxidation on the carbon cloth, and electrolysis is carried out for 3min under the electrolysis voltage of 5V; washing the carbon cloth after anodic oxidation with deionized water and absolute ethyl alcohol until the carbon cloth is clean, and drying the carbon cloth in an oven at 60 ℃ for later use;
step 2: adding 3mg of graphene oxide and 0.34g of antimony trichloride into 20mL of absolute ethyl alcohol and dissolving to obtain an antimony solution; dropwise adding 0.6g/mL sodium hydroxide aqueous solution into the antimony solution, and adjusting the pH value of the antimony solution to 8 by magnetic stirring to obtain a mixed solution; placing the carbon cloth after anodic oxidation into the mixed solution for soaking and magnetically stirring for 30 min; wherein the graphene oxide is single-layer graphene oxide powder, the sheet diameter of the graphene oxide powder is 0.5 mu m, and the thickness of the graphene oxide powder is 0.8 nm;
and step 3: transferring the mixed solution obtained in the step (2) and the carbon cloth into a polytetrafluoroethylene kettle, placing the polytetrafluoroethylene kettle into a homogeneous reactor, carrying out hydrothermal reaction for 6 hours at 180 ℃, cooling to room temperature after the reaction is finished, and taking out the carbon cloth; repeatedly cleaning the carbon cloth with deionized water and absolute ethyl alcohol until the carbon cloth is clean, and drying to obtain Sb2O5a/GO/carbon cloth sodium ion battery cathode material;
analysis of Sb by means of Japanese science D/max2000 PCX-ray diffractometer2O5the/GO/carbon cloth sample is found to be Sb with the PDF number of 11-06902O5The structures are consistent. The sample was observed with a field emission scanning electron microscope (FEI, USA S-4800 type), and the prepared Sb was observed2O5The particles are uniformly grown on the carbon cloth coated with the graphene oxide, Sb2O5Has a particle diameter of 50 nm. With Sb prepared2O5the/GO/carbon cloth is a sodium ion battery cathode material, is assembled into a CR2032 type battery, is subjected to cycle performance test by using a blue test system, and shows higher electrochemical capacity and stability.
Example 2:
sb2O5The preparation method of the/GO/carbon cloth sodium ion battery cathode material comprises the following steps:
step 1: putting a carbon cloth with the length of 4cm and the width of 2cm into 50mL of acetone, soaking for 72h to remove impurities, repeatedly washing with deionized water and absolute ethyl alcohol respectively until the carbon cloth is clean, and drying in a 60 ℃ drying oven after washing; the dried carbon cloth is used as an anode, the graphite plate is used as a cathode, 20g/L ammonium dihydrogen phosphate aqueous solution is used as electrolyte to carry out anodic oxidation on the carbon cloth, and electrolysis is carried out for 5min under the electrolysis voltage of 5V; repeatedly washing the carbon cloth subjected to anodic oxidation by using deionized water and absolute ethyl alcohol until the carbon cloth is clean, and drying the carbon cloth in an oven at 60 ℃ for later use;
step 2: adding 6mg of graphene oxide and 0.57g of antimony trichloride into 30mL of absolute ethyl alcohol and dissolving to obtain an antimony solution; dropwise adding 0.6g/mL sodium hydroxide aqueous solution into the antimony solution, and adjusting the pH value of the antimony solution to 9 by magnetic stirring to obtain a mixed solution; placing the carbon cloth after anodic oxidation into the mixed solution for soaking and magnetically stirring for 30 min; wherein the graphene oxide is single-layer graphene oxide powder, the sheet diameter of the graphene oxide powder is 0.8 mu m, and the thickness of the graphene oxide powder is 1.2 nm;
and step 3: transferring the mixed solution obtained in the step 2 and the carbon cloth into a polytetrafluoroethylene kettle, placing the polytetrafluoroethylene kettle into a homogeneous reactor, carrying out hydrothermal reaction for 12 hours at 180 ℃, cooling to room temperature after the reaction is finished, and taking out the carbon cloth; repeatedly cleaning the carbon cloth with deionized water and absolute ethyl alcohol until the carbon cloth is clean, and drying to obtain Sb2O5a/GO/carbon cloth sodium ion battery cathode material;
analysis of Sb by means of Japanese science D/max2000 PCX-ray diffractometer2O5the/GO/carbon cloth sample is found to be Sb with the PDF number of 11-06902O5The structures are consistent. The sample was observed with a field emission scanning electron microscope (FEI, USA S-4800 type), and the prepared Sb was observed2O5The particles are uniformly grown on the carbon cloth coated with the graphene oxide, Sb2O5Has a particle diameter of 75 nm. With Sb prepared2O5the/GO/carbon cloth is a sodium ion battery cathode material, is assembled into a CR2032 type battery, and is subjected to cycle performance test by using a blue test systemAnd the electrochemical capacity and stability are high.
Example 3:
sb2O5The preparation method of the/GO/carbon cloth sodium ion battery cathode material comprises the following steps:
step 1: putting a carbon cloth with the length of 4cm and the width of 2cm into 50mL of acetone, soaking for 72h to remove impurities, repeatedly washing with deionized water and absolute ethyl alcohol respectively until the carbon cloth is clean, and drying in an oven at 60 ℃ after washing; the dried carbon cloth is used as an anode, the graphite plate is used as a cathode, 20g/L ammonium dihydrogen phosphate aqueous solution is used as electrolyte to carry out anodic oxidation on the carbon cloth, and electrolysis is carried out for 5min under the electrolysis voltage of 5V; repeatedly washing the carbon cloth subjected to anodic oxidation by using deionized water and absolute ethyl alcohol until the carbon cloth is clean, and drying the carbon cloth in an oven at 60 ℃ for later use;
step 2: adding 10mg of graphene oxide and 0.57g of antimony trichloride into 30mL of absolute ethyl alcohol and dissolving to obtain an antimony solution; dropwise adding 0.6g/mL sodium hydroxide aqueous solution into the antimony solution, and adjusting the pH value of the antimony solution to 11 by magnetic stirring to obtain a mixed solution; placing the carbon cloth after anodic oxidation into the mixed solution for soaking and magnetically stirring for 30 min; wherein the graphene oxide is single-layer graphene oxide powder, the sheet diameter of the graphene oxide powder is 1.5 mu m, and the thickness of the graphene oxide powder is 0.9 nm;
and step 3: transferring the mixed solution obtained in the step (2) and the carbon cloth into a polytetrafluoroethylene kettle, placing the polytetrafluoroethylene kettle into a homogeneous reactor, carrying out hydrothermal reaction for 24 hours at 180 ℃, cooling to room temperature after the reaction is finished, and taking out the carbon cloth; repeatedly cleaning the carbon cloth with deionized water and absolute ethyl alcohol until the carbon cloth is clean, and drying to obtain Sb2O5a/GO/carbon cloth sodium ion battery cathode material;
analysis of Sb by means of Japanese science D/max2000 PCX-ray diffractometer2O5the/GO/carbon cloth sample, as shown in FIG. 1, was found to be in contact with Sb having PDF number of 11-06902O5The structures are consistent. As shown in FIG. 2, when the sample was observed with a field emission scanning electron microscope of type S-4800 manufactured by FEI, USA, it was found that Sb was produced2O5The particles are uniformly grown on the carbon cloth coated with the graphene oxide, Sb2O5Has a particle diameter of 90 nm. As shown in FIG. 3, to producePrepared Sb2O5the/GO/carbon cloth is a sodium ion battery cathode material, is assembled into a CR2032 type battery, is subjected to cycle performance test by using a blue test system, and shows higher electrochemical capacity and stability.
Example 4:
sb2O5The preparation method of the/GO/carbon cloth sodium ion battery cathode material comprises the following steps:
step 1: putting a carbon cloth with the length of 4cm and the width of 2cm into 50mL of acetone, soaking for 72h to remove impurities, repeatedly washing with deionized water and absolute ethyl alcohol respectively until the carbon cloth is clean, and drying in an oven at 60 ℃ after washing; the dried carbon cloth is used as an anode, the graphite plate is used as a cathode, 20g/L ammonium dihydrogen phosphate aqueous solution is used as electrolyte to carry out anodic oxidation on the carbon cloth, and electrolysis is carried out for 10min under the electrolysis voltage of 5V; repeatedly washing the carbon cloth subjected to anodic oxidation by using deionized water and absolute ethyl alcohol until the carbon cloth is clean, and drying the carbon cloth in an oven at 60 ℃ for later use;
step 2: adding 3mg of graphene oxide and 1g of antimony trichloride into 40mL of absolute ethyl alcohol and dissolving to obtain an antimony solution; dropwise adding 0.6g/mL sodium hydroxide aqueous solution into the antimony solution, and adjusting the pH value of the antimony solution to 10 by magnetic stirring to obtain a mixed solution; placing the carbon cloth after anodic oxidation into the mixed solution for soaking and magnetically stirring for 30 min; wherein the graphene oxide is single-layer graphene oxide powder, the sheet diameter of the graphene oxide powder is 2.5 mu m, and the thickness of the graphene oxide powder is 1 nm;
and step 3: transferring the mixed solution obtained in the step 2) and the carbon cloth into a polytetrafluoroethylene kettle, placing the polytetrafluoroethylene kettle into a homogeneous reactor, carrying out hydrothermal reaction for 24 hours at 180 ℃, cooling to room temperature after the reaction is finished, and taking out the carbon cloth; repeatedly cleaning the carbon cloth with deionized water and absolute ethyl alcohol until the carbon cloth is clean, and drying to obtain Sb2O5a/GO/carbon cloth sodium ion battery cathode material;
analysis of Sb by means of Japanese science D/max2000 PCX-ray diffractometer2O5the/GO/carbon cloth sample is found to be Sb with the PDF number of 11-06902O5The structures are consistent. The sample was observed with a field emission scanning electron microscope (FEI, USA S-4800 type), and the prepared Sb was observed2O5Uniform particle generationGrowing on carbon cloth coated with graphene oxide, Sb2O5Has a particle diameter of 70 nm. With Sb prepared2O5the/GO/carbon cloth is a sodium ion battery cathode material, is assembled into a CR2032 type battery, is subjected to cycle performance test by using a blue test system, and shows higher electrochemical capacity and stability.
Example 5:
sb2O5The preparation method of the/GO/carbon cloth sodium ion battery cathode material comprises the following steps:
step 1: putting a carbon cloth with the length of 4cm and the width of 2cm into 50mL of acetone, soaking for 72h to remove impurities, repeatedly washing with deionized water and absolute ethyl alcohol respectively until the carbon cloth is clean, and drying in an oven at 60 ℃ after washing; the dried carbon cloth is used as an anode, the graphite plate is used as a cathode, 20g/L ammonium dihydrogen phosphate aqueous solution is used as electrolyte to carry out anodic oxidation on the carbon cloth, and electrolysis is carried out for 5min under the electrolysis voltage of 10V; repeatedly washing the carbon cloth subjected to anodic oxidation by using deionized water and absolute ethyl alcohol until the carbon cloth is clean, and drying the carbon cloth in an oven at 60 ℃ for later use;
step 2: adding 6mg of graphene oxide and 0.8g of antimony trichloride into 20mL of absolute ethyl alcohol and dissolving to obtain an antimony solution; dropwise adding 0.6g/mL sodium hydroxide aqueous solution into the antimony solution, and adjusting the pH value of the antimony solution to 12 by magnetic stirring to obtain a mixed solution; placing the carbon cloth after anodic oxidation into the mixed solution for soaking and magnetically stirring for 30 min; wherein the graphene oxide is single-layer graphene oxide powder, the sheet diameter of the graphene oxide powder is 3.5 mu m, and the thickness of the graphene oxide powder is 1.1 nm;
and step 3: transferring the mixed solution obtained in the step 2) and the carbon cloth into a polytetrafluoroethylene kettle, placing the polytetrafluoroethylene kettle into a homogeneous reactor, carrying out hydrothermal reaction for 4 hours at 180 ℃, cooling to room temperature after the reaction is finished, and taking out the carbon cloth; repeatedly cleaning the carbon cloth with deionized water and absolute ethyl alcohol until the carbon cloth is clean, and drying to obtain Sb2O5The negative electrode material of the/GO/carbon cloth sodium ion battery.
Analysis of Sb by means of Japanese science D/max2000 PCX-ray diffractometer2O5the/GO/carbon cloth sample is found to be Sb with the PDF number of 11-06902O5The structures are consistent. The sample was scanned by field emission scanning using FEI S-4800The observation by an electron microscope shows that the prepared Sb2O5The particles are uniformly grown on the carbon cloth coated with the graphene oxide, Sb2O5Has a particle diameter of 80 nm. With Sb prepared2O5the/GO/carbon cloth is a sodium ion battery cathode material, is assembled into a CR2032 type battery, is subjected to cycle performance test by using a blue test system, and shows higher electrochemical capacity and stability.
Example 6:
sb2O5The preparation method of the/GO/carbon cloth sodium ion battery cathode material comprises the following steps:
step 1: putting a carbon cloth with the length of 4cm and the width of 2cm into 50mL of acetone, soaking for 24h to remove impurities, repeatedly washing with deionized water and absolute ethyl alcohol respectively until the carbon cloth is clean, and drying in an oven at 90 ℃; the dried carbon cloth is used as an anode, the graphite plate is used as a cathode, 15g/L ammonium dihydrogen phosphate aqueous solution is used as electrolyte to carry out anodic oxidation on the carbon cloth, and electrolysis is carried out for 5min under the electrolysis voltage of 5V; repeatedly washing the carbon cloth subjected to anodic oxidation by using deionized water and absolute ethyl alcohol until the carbon cloth is clean, and drying the carbon cloth in an oven at 90 ℃ for later use;
step 2: adding 8mg of graphene oxide and 0.5g of antimony trichloride into 50mL of absolute ethyl alcohol and dissolving to obtain an antimony solution; dropwise adding 0.6g/mL sodium hydroxide aqueous solution into the antimony solution, and adjusting the pH value of the antimony solution to 8 by magnetic stirring to obtain a mixed solution; placing the carbon cloth after anodic oxidation into the mixed solution for soaking and magnetically stirring for 20 min; wherein the graphene oxide is single-layer graphene oxide powder, the sheet diameter of the graphene oxide powder is 5 μm, and the thickness of the graphene oxide powder is 1.2 nm;
and step 3: transferring the mixed solution obtained in the step 2) and the carbon cloth into a polytetrafluoroethylene kettle, placing the polytetrafluoroethylene kettle into a homogeneous reactor, carrying out hydrothermal reaction for 24 hours at 150 ℃, cooling to room temperature after the reaction is finished, and taking out the carbon cloth; repeatedly cleaning the carbon cloth with deionized water and absolute ethyl alcohol until the carbon cloth is clean, and drying to obtain Sb2O5The negative electrode material of the/GO/carbon cloth sodium ion battery.
Analysis of Sb by means of Japanese science D/max2000 PCX-ray diffractometer2O5the/GO/carbon cloth sample is found to be Sb with the PDF number of 11-06902O5The structures are consistent. The sample was observed with a field emission scanning electron microscope (FEI, USA S-4800 type), and the prepared Sb was observed2O5The particles are uniformly grown on the carbon cloth coated with the graphene oxide, Sb2O5Has a particle diameter of 60 nm. With Sb prepared2O5the/GO/carbon cloth is a sodium ion battery cathode material, is assembled into a CR2032 type battery, is subjected to cycle performance test by using a blue test system, and shows higher electrochemical capacity and stability.
Example 7:
sb2O5The preparation method of the/GO/carbon cloth sodium ion battery cathode material comprises the following steps:
step 1: and (3) putting a carbon cloth with the length of 4cm and the width of 2cm into 50mL of acetone, soaking for 48h to remove impurities, repeatedly washing with deionized water and absolute ethyl alcohol respectively until the carbon cloth is clean, and drying in an oven at 120 ℃ after washing. The dried carbon cloth is used as an anode, the graphite plate is used as a cathode, 20g/L ammonium dihydrogen phosphate aqueous solution is used as electrolyte to carry out anodic oxidation on the carbon cloth, and electrolysis is carried out for 8min under the electrolysis voltage of 5V; repeatedly washing the carbon cloth subjected to anodic oxidation by using deionized water and absolute ethyl alcohol until the carbon cloth is clean, and drying the carbon cloth in an oven at 120 ℃ for later use;
step 2: adding 5mg of graphene oxide and 0.7g of antimony trichloride into 60mL of absolute ethyl alcohol and dissolving to obtain an antimony solution; dropwise adding 0.6g/mL sodium hydroxide aqueous solution into the antimony solution, and adjusting the pH value of the antimony solution to 9 by magnetic stirring to obtain a mixed solution; placing the carbon cloth after anodic oxidation into the mixed solution for soaking and magnetically stirring for 40 min; wherein the graphene oxide is single-layer graphene oxide powder, the sheet diameter of the graphene oxide powder is 0.9 μm, and the thickness of the graphene oxide powder is 1.2 nm;
and step 3: transferring the mixed solution obtained in the step 2) and the carbon cloth into a polytetrafluoroethylene kettle, placing the polytetrafluoroethylene kettle into a homogeneous reactor, carrying out hydrothermal reaction for 36 hours at 150 ℃, cooling to room temperature after the reaction is finished, and taking out the carbon cloth; repeatedly cleaning the carbon cloth with deionized water and absolute ethyl alcohol until the carbon cloth is clean, and drying to obtain Sb2O5The negative electrode material of the/GO/carbon cloth sodium ion battery.
Using Japanese science D/max2000 PCX-rayDiffractometer analysis of Sb2O5the/GO/carbon cloth sample is found to be Sb with the PDF number of 11-06902O5The structures are consistent. The sample was observed with a field emission scanning electron microscope (FEI, USA S-4800 type), and the prepared Sb was observed2O5The particles are uniformly grown on the carbon cloth coated with the graphene oxide, Sb2O5Has a particle diameter of 100 nm. With Sb prepared2O5the/GO/carbon cloth is a sodium ion battery cathode material, is assembled into a CR2032 type battery, is subjected to cycle performance test by using a blue test system, and shows higher electrochemical capacity and stability.
In a word, the invention innovatively combines Sb on the basis of combining a flexible electrode2O5Growing the Sb on a carbon cloth flexible substrate in situ by compounding GO and Sb2O5the/GO/carbon cloth composite material is directly used in the negative electrode of the sodium ion battery and shows good electrochemical performance. The method combines Sb2O5The high specific capacity property of the electrode material of the battery and the polar oxide can form firm chemical bonding with the graphene oxide with oxygen-rich functional groups, and simultaneously have the characteristic of good dispersibility of the graphene oxide, and Sb is effectively regulated and controlled by regulating and controlling the mass ratio of antimony trichloride and the graphene oxide which are reaction precursors2O5Uniformly growing on a composite structure of carbon cloth with GO as a buffer layer. The preparation method used by the invention is simple and novel, has short preparation period and high repeatability, and has important significance for preparing the composite carbon cloth flexible electrode material.
Claims (10)
1. Sb2O5The preparation method of the/GO/carbon cloth sodium ion battery cathode material is characterized by comprising the following steps:
step 1: placing the carbon cloth into acetone, soaking, removing impurities, washing and drying, carrying out anodic oxidation treatment on the dried carbon cloth, and drying after washing;
step 2: adding 3-10 mg of graphene oxide and 0.3-1.0 g of antimony trichloride into 20-60 mL of absolute ethanol, and dissolving to obtain an antimony solution; adjusting the pH value of the antimony solution to 8-12 by using a sodium hydroxide aqueous solution to obtain a mixed solution, and soaking the carbon cloth subjected to anodic oxidation in the mixed solution;
and step 3: transferring the mixed solution obtained in the step (2) and the carbon cloth into a reaction container for hydrothermal reaction at the temperature of 150-180 ℃, cooling to room temperature after the reaction is finished, taking out the carbon cloth, cleaning and drying to obtain Sb2O5The negative electrode material of the/GO/carbon cloth sodium ion battery.
2. Sb according to claim 12O5The preparation method of the/GO/carbon cloth sodium ion battery cathode material is characterized in that the carbon cloth in the step 1 is soaked in acetone for 24-72 hours and then washed by deionized water and absolute ethyl alcohol respectively.
3. Sb according to claim 1 or 22O5The preparation method of the/GO/carbon cloth sodium ion battery cathode material is characterized in that in the step 1, the electrolyte used for anode oxidation is one of ammonium dihydrogen phosphate, ammonium dihydrogen carbonate, ammonium carbonate and ammonium hydrogen carbonate, wherein the concentration of the electrolyte is 15-25 g/L; the anodic oxidation voltage is 5-10V, and the time is 3-10 min.
4. Sb according to claim 12O5The preparation method of the/GO/carbon cloth sodium ion battery cathode material is characterized in that the mass ratio of the graphene oxide to the antimony trichloride in the step 2 is 0.5-1.7%.
5. Sb according to claim 42O5The preparation method of the/GO/carbon cloth sodium ion battery cathode material is characterized in that the graphene oxide is single-layer graphene oxide powder, the sheet diameter of the graphene oxide powder is 0.5-5 mu m, and the thickness of the graphene oxide powder is 0.8-1.2 nm.
6. Sb according to claim 12O5The preparation method of the/GO/carbon cloth sodium ion battery cathode material is characterized in that the process of adjusting the pH value of the antimony solution by the sodium hydroxide aqueous solution in the step 2 is the sodium hydroxideGradually adding the sodium water solution into the antimony solution and stirring to obtain a mixed solution; and (3) soaking the carbon cloth after the anodic oxidation in the mixed solution and stirring for 20-40 min.
7. Sb according to claim 62O5The preparation method of the/GO/carbon cloth sodium ion battery cathode material is characterized in that magnetic stirring is adopted in the step 2.
8. Sb according to claim 12O5The preparation method of the/GO/carbon cloth sodium ion battery cathode material is characterized in that in the step 3, a reaction container is a polytetrafluoroethylene kettle, and the mixed solution and the carbon cloth are transferred into the polytetrafluoroethylene kettle and placed in a homogeneous phase reactor for hydrothermal reaction for 4-48 hours; the cleaning is repeatedly performed by using deionized water and absolute ethyl alcohol respectively.
9. Sb according to claim 12O5The preparation method of the/GO/carbon cloth sodium ion battery cathode material is characterized in that the Sb prepared in the step 3 is Sb2O5Sb in/GO/carbon cloth sodium ion battery cathode material2O5Has a particle diameter of 50 to 100nm and Sb2O5The graphene oxide is uniformly distributed on the carbon cloth substrate with the graphene oxide as the buffer layer.
10. Sb according to claim 12O5The preparation method of the/GO/carbon cloth sodium ion battery cathode material is characterized in that the carbon cloth is hydrophilic carbon cloth, and the specification is 4 cm-2 cm.
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| CN110615475B (en) * | 2019-09-24 | 2021-12-17 | 陕西科技大学 | Preparation of antimony pentoxide/silicon dioxide/carbon cloth flexible material and application of antimony pentoxide/silicon dioxide/carbon cloth flexible material as sodium-ion battery cathode |
| CN111446443B (en) * | 2020-04-03 | 2021-05-18 | 陕西科技大学 | Preparation method and application of carbon cloth in-situ constructed double-oxide self-supporting battery electrode material |
| CN112038607B (en) * | 2020-09-09 | 2021-08-27 | 陕西科技大学 | Carbon cloth loaded flower-shaped Sb2O4@ polyhedral Sb2O5Composite self-supporting electrode material and preparation method thereof |
| CN112038623A (en) * | 2020-09-09 | 2020-12-04 | 陕西科技大学 | Sb based on controllable construction of carbon cloth substrate2O4Self-supporting electrode material for sodium ion battery cathode and preparation method thereof |
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