CN110600276B - Preparation method of tin oxide nanosheet array supercapacitor positive electrode material - Google Patents
Preparation method of tin oxide nanosheet array supercapacitor positive electrode material Download PDFInfo
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- CN110600276B CN110600276B CN201910995576.9A CN201910995576A CN110600276B CN 110600276 B CN110600276 B CN 110600276B CN 201910995576 A CN201910995576 A CN 201910995576A CN 110600276 B CN110600276 B CN 110600276B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to a preparation method of an alloying enhanced oxygen-deficient tin oxide nanosheet array supercapacitor positive electrode material, and belongs to the technical field of new energy material preparation and application thereof. The anode material is composed of an oxygen-deficient tin oxide nanosheet array structure which grows on a foamed nickel substrate and is partially alloyed by Sn-Ni, and the nanosheets grow in a vertically staggered manner to form a wall shape; as a working electrode, the electrode has larger specific capacitance, good circulation stability and no toxicity or harm to human bodies. According to the method, firstly, stannous chloride dihydrate and trisodium citrate dihydrate are used as raw materials, an anoxic tin oxide wall-shaped nanosheet array structure is obtained by growing on a foamed nickel substrate through a solvothermal method, and then high-temperature thermal reduction and alloying are carried out in a vacuum tube furnace, so that the cathode material is finally obtained. The method has the advantages of high product yield, controllable composition and appearance; the raw materials, equipment and process are simple, the cost is low, the production process is safe, clean and environment-friendly, and the method is favorable for large-scale production.
Description
Technical Field
The invention relates to a preparation method of an alloying enhanced oxygen-deficient tin oxide nanosheet array supercapacitor positive electrode material, and belongs to the technical field of new energy material preparation and application thereof.
Background
In recent years, energy storage materials have been rapidly developed to meet the sustainable and renewable requirements of modern society for energy. Compared to conventional batteries and other types of capacitors, supercapacitors exhibit faster charge and discharge rates, higher power densities, longer cycle lives, as well as wide operating temperature intervals and lower maintenance costs, and thus have attracted extensive attention from materials researchers. Supercapacitors are mainly classified into electric double layer supercapacitors and pseudocapacitive supercapacitors according to the charge storage mechanism. The electric double layer super capacitor is usually made of a carbon-based active material with a high specific surface area, and stores electric energy through reversible ion adsorption-desorption at a contact interface of an electrode and an electrolyte, and has high power density, small specific capacitance and poor rate capability; in contrast, pseudocapacitive supercapacitors generally exhibit a greater specific capacitance and a higher energy density due to the rapid reversible redox reactions that the electrode materials undergo during charging and discharging. However, in order to obtain a high-performance pseudocapacitive supercapacitor, the active material on the electrode should also have the characteristics of large specific surface area, high cycling stability, fast electrochemical oxidation/reduction rate and the like. Among them, many metal oxide nanomaterials are potential high-performance electrode materials.
Among the numerous metal oxides, tin dioxide (SnO)2) As an important n-type semiconductor, the N-type semiconductor is considered to be a very potential energy storage material due to the advantages of low cost, no toxicity, no harm, good thermal stability and the like. However, the tin dioxide has the defects of poor conductivity, serious agglomeration of nano structures, poor multiplying power performance of the capacitor and the like, so that the tin dioxide hinders the practical application of the tin dioxide as a high-performance pseudo-capacitance electrode material. In order to improve SnO2As for the electrochemical performance of the electrode material, many attempts have been made by researchers: (1) at SnO2Constructing a heterostructure with other metal oxide nanostructures, and establishing an internal electric field in the sample; (2) synthesis of SnO by selecting highly conductive carbon-based materials2A nanostructured composite material; (3) SnO enhancement using certain conductive polymers2The electrical conductivity, specific surface area or even the final specific capacitance of the electrode material. To improve the capacitance performance of the material, some scholars propose that SnO can be used2And is compounded with manganese oxide, cobalt oxide, titanium oxide and other materials. In fact, improving the electrochemical performance of energy storage devices can also start from the aspect of material preparation. For example, An electrochemically active material is directly grown on a highly conductive substrate (current collector), which not only can avoid a complex preparation process of a powdery electrode and improve the electron conduction rate in the electrode, but also can improve the specific surface area of a nano material and increase active sites, thereby ensuring that An oxidation-reduction reaction is efficiently and sufficiently performed, and further greatly improving the electrochemical performance of the electrode material (Yifei Guo, et al.
In combination with the analysis, the invention provides a preparation method of the alloying enhanced oxygen-deficient tin oxide nanosheet array supercapacitor positive electrode material, considering the high specific surface area of the two-dimensional nanostructure, the excellent conductivity and the additional electrochemical reaction process of the metal alloy material, and the higher conductivity and the excellent electrochemical performance of the oxygen-deficient tin oxide. According to the technology provided by the invention, firstly, stannous chloride dihydrate and trisodium citrate dihydrate are used as raw materials, an anoxic tin oxide wall-shaped nanosheet array structure (nanowall) is obtained by growing on a foamed nickel substrate by adopting a solvothermal method, then high-temperature thermal reduction and alloying are carried out in a vacuum tube furnace, and finally the anoxic tin oxide wall-shaped nanosheet array structure growing on the foamed nickel substrate and partially alloyed by Sn-Ni is obtained. The oxygen-deficient tin oxide wall-shaped nanosheet array structure can be directly used as a working electrode (positive electrode) of a supercapacitor. According to the super capacitor anode material prepared by the method, as the active substance grows on the nickel foam substrate in the form of the vertically staggered nano-sheet array structure (nano-wall), the specific surface area of the material is large, the active sites are fully exposed, and the gaps constructed by the regularly arranged nano-walls provide sufficient channels and spaces for the electrochemical reaction between the electrolyte and the active substance, so that the specific capacitance of the electrode is large; in the electrode material, the valence state of metal cations is rich, the electrochemical reaction is complex, and the material capacitance is high; the substrate of the electrode material is metal with excellent conductivity, the active substance is oxygen-deficient tin oxide with stronger conductivity and Sn-Ni alloy with excellent conductivity, and the oxygen-deficient tin oxide and the Sn-Ni alloy are organically combined together through high-temperature thermal reduction treatment, so the electrode material has good conductivity and is beneficial to the rapid transfer of charges; abundant gaps in the nanometer wall provide sufficient buffer space for volume expansion of electrochemical reaction caused by ion embedding and de-embedding, so that the capacitor has good structural stability, and the electrode material has excellent cycling stability due to the existence of Ni alloy. In addition, the electrode material of the super capacitor is a tin oxide-based material, so that the super capacitor is non-toxic and harmless to human bodies; the obtained partial-alloying anoxic tin oxide wall-shaped nanosheet array structure is high in yield and controllable in composition and appearance. In addition, the preparation method of the supercapacitor anode material provided by the invention has the advantages of simple raw materials, equipment and process, strong controllability of process and parameters, high product yield, low cost, safe, clean and environment-friendly production process and contribution to large-scale production.
Disclosure of Invention
The invention aims to provide an alloying enhanced oxygen-deficient tin oxide nanosheet array supercapacitor positive electrode material. The super capacitor anode material is formed by an oxygen-deficient tin oxide nanosheet array structure which grows on a foamed nickel substrate and is partially alloyed by Sn-Ni, and the nanosheets grow in a vertically staggered mode to form a nanometer wall shape. The partially metallized and oxygen-deficient tin oxide wall-shaped nanosheet array structure can be directly used as a working electrode (positive electrode) of a supercapacitor. According to the super capacitor anode material prepared by the method, as the active substance grows on the nickel foam substrate in the form of the nano-sheet array structure (nano-wall) which vertically grows in a staggered manner, the specific surface area of the material is large, the active sites are fully exposed, and the gaps constructed by the regularly arranged nano-walls provide sufficient channels and spaces for the electrochemical reaction between the electrolyte and the active substance, so that the specific capacitance of the electrode is large; in the electrode material, the valence state of metal cations is rich, the electrochemical reaction is complex, and the material capacitance is high; the substrate of the electrode material is metal with excellent conductivity, the active substance is oxygen-deficient tin oxide with stronger conductivity and Sn-Ni alloy with excellent conductivity, and the oxygen-deficient tin oxide and the Sn-Ni alloy are organically combined together through high-temperature thermal reduction treatment, so the electrode material has good conductivity and is beneficial to the rapid transfer of charges; abundant gaps in the nanometer wall provide sufficient buffer space for volume expansion of electrochemical reaction caused by ion embedding and de-embedding, so that the capacitor has good structural stability, and the electrode material has excellent cycling stability due to the existence of Ni alloy. In addition, the electrode material of the super capacitor is a tin oxide-based material, so that the electrode material is non-toxic and harmless to human bodies.
The second purpose of the invention is to provide a corresponding preparation method of the alloying enhanced oxygen-deficient tin oxide nanosheet array supercapacitor positive electrode material. The partially-alloyed and anoxic tin oxide wall-shaped nanosheet array structure obtained by the method has the advantages of high yield, controllable composition and morphology; meanwhile, the method has the advantages of simple raw materials, equipment and process, strong controllability of process parameters, high product yield, low cost, safe, clean and environment-friendly production process and contribution to large-scale production.
In order to achieve the aim, the alloying enhanced oxygen-deficient tin oxide nanosheet array supercapacitor positive electrode material is characterized in that the oxygen-deficient tin oxide nanosheet array structure is regularly and tightly attached to a foamed nickel substrate in a vertically staggered growth mode to form a nanometer wall shape; the main body of the composition is oxygen-deficient tin oxide and contains a small amount of Ni-Sn alloy; the diameter of the nano-sheet is about 40 nm-2 μm, and the thickness is about 20-60 nm. The metal cations of the super capacitor anode material have rich valence, large specific surface area, fully exposed active sites, full contact reaction between active substances and electrolyte, good conductivity, large specific capacitance of electrodes, good circulation stability, no toxicity or harm to human bodies, and is an excellent super capacitor anode material.
The preparation method of the alloying enhanced anoxic tin oxide nanosheet array supercapacitor positive electrode material is characterized in that firstly stannous chloride dihydrate and trisodium citrate dihydrate are used as raw materials, a solvothermal method is adopted to grow on a foamed nickel substrate to obtain an anoxic tin oxide wall-shaped nanosheet array structure, then high-temperature thermal reduction and alloying are carried out in a vacuum tube furnace, and finally the anoxic tin oxide wall-shaped nanosheet array structure growing on the foamed nickel substrate and being partially alloyed by Sn-Ni is obtained.
The invention provides a preparation method of an alloying enhanced oxygen-deficient tin oxide nanosheet array supercapacitor positive electrode material, which comprises the following steps and contents:
(1) firstly, deionized water is filled into a beaker, then stannous chloride dihydrate and trisodium citrate are dissolved in the deionized water, uniform and stable milky suspension is obtained after magnetic stirring is carried out for 20-40min, then absolute ethyl alcohol is slowly added into the beaker, and stirring is continuously carried out for 30-60min, so as to obtain whitish precursor solution for later use.
(2) And transferring the precursor solution into a polytetrafluoroethylene lining of a high-pressure reaction kettle, and vertically fixing a clean foam nickel sheet in the reaction kettle and completely immersing the foam nickel sheet in the precursor solution. And then, after the sealing and assembling of the reaction kettle are finished, placing the reaction kettle in a drying oven for heat preservation treatment. Naturally cooling to room temperature, opening the reaction kettle, taking out the foam nickel sample, washing with deionized water for 3-5 times, and drying.
(3) And placing the obtained foam nickel sample at the bottom of an alumina crucible, surrounding some pre-oxidized polyacrylonitrile or epoxy resin around the foam nickel sample, then placing the crucible in a vacuum tube furnace, heating under the protection of inert atmosphere, and finally cooling along with the furnace to room temperature and taking out the sample to obtain the alloyed reinforced oxygen-deficient tin oxide nanosheet array supercapacitor anode material.
In the preparation method, the dosage ratio of the deionized water, the stannous chloride dihydrate and the trisodium citrate in the step (1) is (40-80mL): (1.5-2.3g): (2.5-3.5 g).
In the preparation method, the volume ratio of the absolute ethyl alcohol to the deionized water in the solvent in the step (1) is 3:1-1: 5.
In the preparation method, in the step (1), when the stannous chloride dihydrate and the trisodium citrate are dissolved in water, the mixture is magnetically stirred until uniform and stable milky white suspension is formed; after the addition of absolute ethanol, the precursor solution became slightly cloudy under continuous magnetic stirring.
In the preparation method, the volume of the inner lining of the reaction kettle in the step (2) is 100-200 mL.
In the preparation method, the filling amount of the reaction liquid in the high-pressure reaction kettle in the step (2) is 50-80%.
In the above preparation method, the cleaning method of the foamed nickel sheet in the step (2) is: taking a piece of foam nickel, sequentially placing the foam nickel in acetone and absolute ethyl alcohol solution, respectively carrying out ultrasonic cleaning for 15-20min, and then drying.
In the preparation method, the foamed nickel sheet in the step (2) is vertically fixed in the reaction kettle.
In the preparation method, the temperature of the reaction kettle in the oven in the step (2) is 150-250 ℃, and the heat preservation time is 6-24 h.
In the above production method, the thermal reduction atmosphere in the step (3) is provided by thermal decomposition of one of pre-oxidized polyacrylonitrile or epoxy resin; the preoxidized polyacrylonitrile or epoxy resin is fiber or powder, and has a mass of 0.5-4.0 g.
In the above preparation method, the inert atmosphere in the step (3) is provided by high purity nitrogen or argon, and the purity is more than 99.99 vol.%.
In the preparation method, the heat treatment temperature in the step (3) is 200-600 ℃, the heat treatment time is 30-180min, and the temperature rise rate of the tubular furnace is 5-15 ℃/min.
The invention is characterized in that:
(1) the super capacitor anode material is composed of an oxygen-deficient tin oxide nanosheet array structure which grows on a foamed nickel substrate and is partially alloyed by Sn-Ni. Wherein, the oxygen-deficient tin oxide nanosheet array structure is regularly and tightly attached to the foamed nickel substrate in a vertically staggered growth manner to construct a nano wall shape; the main component of the composite is oxygen-deficient tin oxide and contains a small amount of Ni-Sn alloy to form a uniform composite.
(2) In the process of preparing the alloying enhanced anoxic tin oxide nanosheet array supercapacitor positive electrode material, firstly, stannous chloride dihydrate and trisodium citrate dihydrate are used as raw materials, an anoxic tin oxide wall-shaped nanosheet array structure is obtained by growing on a foamed nickel substrate through a solvothermal method, then, high-temperature thermal reduction and alloying are carried out in a vacuum tube furnace, and finally, the anoxic tin oxide wall-shaped nanosheet array structure growing on the foamed nickel substrate and partially alloyed by Sn-Ni is obtained.
The invention has the advantages that:
(1) the tin oxide nanorod array structure can be directly used as a positive electrode material of a super capacitor. According to the super capacitor anode material prepared by the method, as the active substance grows on the nickel foam substrate in the form of the nano-sheet array structure (nano-wall) which vertically grows in a staggered manner, the specific surface area of the material is large, the active sites are fully exposed, and the gaps constructed by the regularly arranged nano-walls provide sufficient channels and spaces for the electrochemical reaction between the electrolyte and the active substance, so that the specific capacitance of the electrode is large; in the electrode material, the valence state of metal cations is rich, the electrochemical reaction is complex, and the material capacitance is high; the substrate of the electrode material is metal with excellent conductivity, the active substance is oxygen-deficient tin oxide with stronger conductivity and Sn-Ni alloy with excellent conductivity, and the oxygen-deficient tin oxide and the Sn-Ni alloy are organically combined together through high-temperature thermal reduction treatment, so the electrode material has good conductivity and is beneficial to the rapid transfer of charges; abundant gaps in the nanometer wall provide sufficient buffer space for volume expansion of electrochemical reaction caused by ion embedding and de-embedding, so that the capacitor has good structural stability, and the electrode material has excellent cycling stability due to the existence of Ni alloy. In addition, the electrode material of the super capacitor is a tin oxide-based material, so that the electrode material is non-toxic and harmless to human bodies.
(2) The partially-alloyed and anoxic tin oxide wall-shaped nanosheet array structure obtained by the method has the advantages of high yield, controllable composition and morphology; meanwhile, the method has the advantages of simple raw materials, equipment and process, strong controllability of process parameters, high product yield, low cost, safe, clean and environment-friendly production process and contribution to large-scale production.
(3) The raw materials of the technology of the invention are nontoxic, harmless, simple and easily available.
(4) In the thermal reduction process of the anoxic tin oxide wall-shaped nanosheets, the traditional pure hydrogen thermal reduction is replaced by the reducing atmosphere generated by the thermal decomposition of the preoxidized polyacrylonitrile or epoxy resin organic matter, so that the safety is greatly improved while the environmental protection of the process is ensured.
Drawings
FIG. 1 is a scanning electron micrograph of the cathode material of the alloyed enhanced oxygen-deficient tin oxide nanosheet array supercapacitor made in example 5 of the present invention
FIG. 2 shows the X-ray diffraction pattern and the analysis result of the cathode material of the alloyed enhanced anoxic tin oxide nanosheet array supercapacitor made in example 5 of the present invention
FIG. 3 is a cyclic voltammetry curve of the alloyed enhanced anoxic type tin oxide nanosheet array supercapacitor positive electrode material prepared in example 5 of the present invention
Detailed Description
The technical solution of the present invention is further illustrated by the following examples.
The invention provides an alloying enhanced oxygen-deficient tin oxide nanosheet array supercapacitor positive electrode material which is characterized in that an oxygen-deficient tin oxide nanosheet array structure is regularly and tightly attached to a foamed nickel substrate in a vertically staggered growth mode to form a nanometer wall shape; the main body of the composition is oxygen-deficient tin oxide and contains a small amount of Ni-Sn alloy; the diameter of the nano-sheet is about 40 nm-2 μm, and the thickness is about 20-60 nm. The metal cations of the super capacitor anode material have rich valence, large specific surface area, fully exposed active sites, full contact reaction between active substances and electrolyte, good conductivity, large specific capacitance of electrodes, good circulation stability, no toxicity or harm to human bodies, and is an excellent super capacitor anode material.
The preparation method of the alloying enhanced anoxic tin oxide nanosheet array supercapacitor positive electrode material is characterized in that firstly stannous chloride dihydrate and trisodium citrate dihydrate are used as raw materials, a solvothermal method is adopted to grow on a foamed nickel substrate to obtain an anoxic tin oxide wall-shaped nanosheet array structure, then high-temperature thermal reduction and alloying are carried out in a vacuum tube furnace, and finally the anoxic tin oxide wall-shaped nanosheet array structure growing on the foamed nickel substrate and being partially alloyed by Sn-Ni is obtained.
The invention provides a preparation method of an alloying enhanced oxygen-deficient tin oxide nanosheet array supercapacitor positive electrode material, which comprises the following steps and contents:
(1) firstly, 40-80mL of deionized water is filled into a beaker, then 1.5-2.3g of stannous chloride dihydrate and 2.5-3.5g of trisodium citrate are dissolved in the deionized water, uniform and stable milky suspension is obtained after magnetic stirring for 20-40min, then the anhydrous ethanol is slowly added into the beaker according to the volume ratio of the anhydrous ethanol to the deionized water of 3:1-1:5, and stirring is continued for 30-60min, so as to obtain a slightly white precursor solution for later use.
(2) And transferring the precursor solution into a polytetrafluoroethylene lining of a high-pressure reaction kettle, and vertically fixing a clean foam nickel sheet in the reaction kettle and completely immersing the foam nickel sheet in the precursor solution. And then, after the sealing and assembling of the reaction kettle are finished, placing the reaction kettle in a drying oven for heat preservation treatment. Naturally cooling to room temperature, opening the reaction kettle, taking out the foam nickel sample, washing with deionized water for 3-5 times, and drying.
(3) And placing the obtained nickel foam sample at the bottom of an alumina crucible, surrounding 0.5-4.0g of pre-oxidized polyacrylonitrile or epoxy resin around the nickel foam sample, then placing the crucible in a vacuum tube furnace, heating under the protection of over 99.99 vol.% of high-purity nitrogen or argon inert atmosphere, and finally cooling to room temperature along with the furnace and taking out to obtain the alloying enhanced oxygen-deficient tin oxide nanosheet array supercapacitor anode material.
(4) In the step (2), the volume of the inner liner of the reaction kettle is 100-200mL, and the filling amount of the reaction liquid in the high-pressure reaction kettle is 50-80%.
(5) The cleaning method of the foam nickel sheet in the step (2) comprises the following steps: taking a piece of foam nickel, sequentially placing the foam nickel in acetone and absolute ethyl alcohol solution, respectively carrying out ultrasonic cleaning for 15-20min, and then drying.
(6) In the step (2), the temperature of the reaction kettle in the oven is 150-250 ℃, and the heat preservation time is 6-24 h.
(7) In the step (3), the heat treatment temperature is 200-600 ℃, the heat treatment time is 30-180min, and the temperature rise rate of the tubular furnace is 5-15 ℃/min.
The obtained alloyed enhanced oxygen-deficient tin oxide nanosheet array supercapacitor positive electrode material is a white to gray solid in appearance. Under a scanning electron microscope, many nanosheets can be observed; the diameter of the nano-sheet is about 40 nm-2 μm, and the thickness is about 20-60 nm; the nano sheets are regularly and tightly attached to the foam nickel substrate in a vertically staggered growth mode to construct a nano wall shape. X-ray diffraction analysis shows that the material mainly comprises oxygen-deficient tin oxide and contains a small amount of Ni-Sn alloy. The cyclic-voltammetry test shows that the sample has obvious redox peaks, and the electrochemical performance of the sample is excellent.
In a word, the alloying enhanced oxygen-deficient tin oxide nanosheet array supercapacitor positive electrode material can be prepared by the technology.
Example (b): firstly, 40mL of deionized water is filled into a beaker, then 2.073g of stannous chloride dihydrate and 2.971g of trisodium citrate are dissolved in the deionized water, uniform and stable milky suspension is obtained after magnetic stirring is carried out for 30min, then 40mL of absolute ethyl alcohol is slowly added into the beaker, and stirring is carried out for 30min continuously, so as to obtain a slightly white precursor solution. The precursor solution was then transferred to the teflon liner of a 100mL autoclave and a piece of clean nickel foam of 3.5cm x 3.5cm size was vertically fixed in the autoclave and completely immersed in the precursor solution. And then, after the sealing assembly of the reaction kettle is finished, placing the reaction kettle in an oven and preserving heat for 12 hours at 180 ℃. And naturally cooling to room temperature, opening the reaction kettle, taking out the foamed nickel sample, washing with deionized water for 5 times, and placing in an oven to preserve heat for 4 hours at 100 ℃ for drying. And then, placing the obtained nickel foam sample at the bottom of an alumina crucible, surrounding 3.0g of pre-oxidized polyacrylonitrile fiber around the nickel foam sample, then placing the crucible in a vacuum tube furnace, preserving the heat for 30-180min at 200-600 ℃ under the protection of over 99.99 vol.% of high-purity argon inert atmosphere, and finally cooling the crucible along with the furnace to room temperature and taking out the cooled crucible to obtain the alloyed reinforced oxygen-deficient tin oxide nanosheet array supercapacitor anode material.
A typical scanning electron micrograph of the obtained sample is shown in fig. 1, from which it can be observed that the nano sheets are regularly and closely attached to the substrate in a vertically staggered growth manner to construct a nano wall; the material mainly comprises oxygen-deficient tin oxide and contains a small amount of Ni-Sn alloy (see figure 2); when the sample is directly used as the positive electrode of the supercapacitor, the sample has obvious oxidation-reduction peaks (see fig. 3), and the electrochemical performance of the sample is excellent (see table 1). Different from the traditional electrode material, the electrode material prepared by the invention has super-strong electrochemical cycle performance, and the specific capacity of the electrode material even exceeds the initial capacity of the electrode material along with the increase of cycle times.
TABLE 1
Claims (3)
1. A preparation method of an alloying enhanced oxygen-deficient tin oxide nanosheet array supercapacitor positive electrode material is characterized in that the oxygen-deficient tin oxide nanosheet array structure is regularly and tightly attached to a foamed nickel substrate in a vertically staggered growth mode to form a nanometer wall shape; the main body of the composition is oxygen-deficient tin oxide and contains a small amount of Ni-Sn alloy; firstly, using stannous chloride dihydrate and trisodium citrate dihydrate as raw materials, growing on a foamed nickel substrate by adopting a solvothermal method to obtain an anoxic tin oxide wall-shaped nanosheet array structure, and then carrying out high-temperature thermal reduction and alloying in a vacuum tube furnace to finally obtain a part of Sn-Ni alloyed anoxic tin oxide wall-shaped nanosheet array structure growing on the foamed nickel substrate; the method comprises the following steps:
(1) firstly, adding deionized water into a beaker, then dissolving stannous chloride dihydrate and trisodium citrate into the deionized water, magnetically stirring for 20-40min to obtain uniform and stable milky suspension, slowly adding absolute ethyl alcohol into the beaker, and continuously stirring for 30-60min to obtain a whitish precursor solution for later use;
(2) transferring the precursor solution into a polytetrafluoroethylene lining of a high-pressure reaction kettle, vertically fixing a clean foam nickel sheet in the reaction kettle, and completely immersing the foam nickel sheet in the precursor solution; then, after the sealing assembly of the reaction kettle is finished, placing the reaction kettle in a drying oven for heat preservation treatment; naturally cooling to room temperature, opening the reaction kettle, taking out the foam nickel sample, washing with deionized water for 3-5 times, and drying;
(3) and placing the obtained foam nickel sample at the bottom of an alumina crucible, surrounding 0.5-4.0g of pre-oxidized polyacrylonitrile or epoxy resin around the foam nickel sample, then placing the crucible in a vacuum tube furnace, heating under the protection of inert atmosphere, cooling to room temperature along with the furnace, and taking out to obtain the alloyed reinforced oxygen-deficient tin oxide nanosheet array supercapacitor anode material.
2. The method according to claim 1, wherein the deionized water, stannous chloride dihydrate and trisodium citrate are used in the amount ratio of (40-80mL) to (1.5-2.3g) to (2.5-3.5g) in step (1); in the step (1), the volume ratio of absolute ethyl alcohol to deionized water in the solvent is 3:1-1: 5; in the step (2), the volume of the inner liner of the reaction kettle is 100-200mL, and the filling amount of the reaction liquid in the reaction kettle is 50-80%; in the step (2), the temperature of the reaction kettle in the oven is 150-250 ℃, and the heat preservation time is 6-24 h.
3. The method according to claim 1, wherein the thermal reducing atmosphere in the step (3) is provided by thermal decomposition of one of pre-oxidized polyacrylonitrile or epoxy resin; the preoxidized polyacrylonitrile or epoxy resin is fiber or powder, and the mass is 0.5-4.0 g; the inert atmosphere is provided by high-purity nitrogen or argon, and the purity is over 99.99 vol.%; the heat treatment temperature is 200-600 ℃, the heat treatment time is 30-180min, and the temperature rise rate of the tubular furnace is 5-15 ℃/min.
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