CN110767460B - Preparation method of partially alloyed tin oxide nanorod array supercapacitor positive electrode material - Google Patents
Preparation method of partially alloyed tin oxide nanorod array supercapacitor positive electrode material Download PDFInfo
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000002073 nanorod Substances 0.000 title claims abstract description 70
- 229910001887 tin oxide Inorganic materials 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 97
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 230000002950 deficient Effects 0.000 claims abstract description 20
- 239000010405 anode material Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 229910020938 Sn-Ni Inorganic materials 0.000 claims abstract description 14
- 229910008937 Sn—Ni Inorganic materials 0.000 claims abstract description 14
- SFXJSNATBHJIDS-UHFFFAOYSA-N disodium;dioxido(oxo)tin;trihydrate Chemical compound O.O.O.[Na+].[Na+].[O-][Sn]([O-])=O SFXJSNATBHJIDS-UHFFFAOYSA-N 0.000 claims abstract description 13
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
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- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 3
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- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
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- 239000005416 organic matter Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
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- C01G19/02—Oxides
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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- C23C18/125—Process of deposition of the inorganic material
- C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic material
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- H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
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Abstract
The invention relates to a preparation method of a partially alloyed tin oxide nanorod array supercapacitor positive electrode material, and belongs to the technical field of new energy material preparation and application. The anode material provided by the invention is formed by an oxygen-deficient tin oxide nanorod array structure which grows on a foamed nickel substrate and is partially alloyed by Sn-Ni, can be directly used as a working electrode of a super capacitor, and has the advantages of large specific capacitance, good circulation stability and no toxicity or harm to a human body. The method comprises the steps of firstly, taking sodium stannate trihydrate and sodium hydroxide as raw materials, growing a tin dioxide nanorod array on a current collector foamed nickel substrate by adopting a solvothermal method, and then carrying out high-temperature heat treatment in a vacuum tube furnace in a reducing atmosphere to finally obtain the cathode material. The tin oxide nanorod array structure obtained by the method is high in yield and controllable in 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 a partially alloyed tin oxide nanorod array supercapacitor positive electrode material, and belongs to the technical field of new energy material preparation and application.
Background
In recent years, in order to alleviate the energy shortage and environmental pollution caused by the excessive exploitation and use of fossil energy and meet the increasing energy demand of modern society, various sustainable and renewable energy storage materials are widely researched. Compared with batteries and conventional capacitors, supercapacitors have a faster charge-discharge rate, higher power density, longer cycle life, wider application temperature, and lower maintenance costs, making them of great interest. For a high performance supercapacitor, the electrode material should have a large specific surface area, a high specific capacitance, a long cycle life and a high electrochemical oxidation/reduction rate. The metal oxide is one of typical pseudocapacitance type super capacitor anode materials.
The first reported metal oxide pseudocapacitance type super capacitor anode material with excellent performance in literature is ruthenium oxide (RuO)2) The electrochemical capacitor has the advantages of quick electrochemical response, high specific capacitance and the like. However, the ruthenium oxide electrode has the disadvantages of high cost and high environmental toxicity, and the large-scale application of the ruthenium oxide electrode in industry is greatly limited. Therefore, it is very meaningful to find nontoxic and cheap metal oxides as the electrodes of the high-performance supercapacitors in the future. Among various metal oxides, SnO2Has the advantages of low cost, no toxicity, good thermal stability, strong power transfer capability and the like, and has become a hotspot of research of people. For example, Pusawale et al have deposited nano-SnO by chemical means2The film obtains the optimal specific capacitance of a sample to be 66F/g under the condition that the scanning speed is 10 mV/s; shide et al anodically oxidize a metallic tin substrate in an aqueous electrolyte containing oxalic acid or phosphoric acid to produce a self-organized nanoporous tin oxide film having a maximum specific capacitance of 274F/g at 10mV/s for the resulting film sample. However, the commercialization of the tin oxide-based supercapacitor electrode material is still hindered by the factors of poor conductivity, obvious particle agglomeration, poor rate performance and the like. In order to improve SnO2The electrochemical performance of the electrodes, some attempts have been made by researchers. Shakir et al synthesized tin oxide coated molybdenum oxide nanowires (SnO) by a sol-thermal and wet chemical route2/MoO3) The results show that: SnO synthesized under the condition of 500mA/g2/MoO3The specific capacitance of the composite nanowire can reach 295F/g; wang et al synthesized SnO by a simple in situ preparation method2@ polyaniline nanocomposite, the specific capacitance at 100mV/s is 335.5F/g. However, these composite materials have serious problems such as insufficient exposure of active sites, poor material conductivity, and poor performance stability.
In addition, literature studies show that the direct synthesis of electroactive materials on metal current collectors to prepare binderless samples as electrodes is a very potential method, which not only can avoid the complicated preparation process of powder electrodes, but also can make more active materials on the samples contact with electrolyte to participate in redox reaction, thereby greatly improving the electrochemical performance of the electrode materials (Yifei Guo, et al. vertical standing MoP electrode on Mo substrate: integrated binder-free electrode for high purity effect and stable hydrogen evolution. journal of Alloys and Compounds,2019,792: 732-. Moreover, the metal current collector is also beneficial to the conduction of electrons, and the conductivity of the electrode material is enhanced. In addition, the existence of defects in the nanomaterial can significantly improve the conductivity of the nanomaterial (Yang Wang, et al. tunable electrical resistance of oxygen-specific zinc oxide films. surface Engineering, 2017,33(3): 217-225).
Therefore, the invention provides a preparation method of a partially alloyed tin oxide nanorod array supercapacitor positive electrode material. In the technology provided by the invention, sodium stannate trihydrate and sodium hydroxide are used as raw materials, a tin dioxide nanorod array is grown on a foamed nickel substrate by adopting a solvothermal method, and then high-temperature heat treatment is carried out in a vacuum tube furnace in a reducing atmosphere, so that a partial Sn-Ni alloyed oxygen-deficient tin oxide nanorod array structure grown on the foamed nickel substrate is finally obtained. The tin oxide nanorod 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 foam nickel substrate in the form of a nanorod array, the specific surface area of the material is large, the active sites are fully exposed, and 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 (current collector) of the electrode material is metal with excellent conductivity, the active substances are oxygen-deficient tin oxide with strong conductivity and newly-added Sn-Ni alloy with good conductivity, and the oxygen-deficient tin oxide and the newly-added Sn-Ni alloy are organically combined together through high-temperature heat treatment, so that the electrode material has good conductivity and is beneficial to the rapid transfer of charges; the gaps among the nanorods in the electrode material provide buffer space for the volume expansion of electrochemical reaction caused by ion intercalation and deintercalation, 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 tin oxide nanorod array structure has high yield and controllable 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 a partially metallized tin oxide nanorod array supercapacitor positive electrode material. The super capacitor anode material is composed of a partial Sn-Ni alloyed oxygen-deficient tin oxide nanorod array structure which grows on a foamed nickel substrate. The tin oxide nanorod 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 foam nickel substrate in the form of a nanorod array, the specific surface area of the material is large, the active sites are fully exposed, and 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 (current collector) of the electrode material is metal with excellent conductivity, the active substances are oxygen-deficient tin oxide with strong conductivity and newly-added Sn-Ni alloy with good conductivity, and the oxygen-deficient tin oxide and the newly-added Sn-Ni alloy are organically combined together through high-temperature heat treatment, so that the electrode material has good conductivity and is beneficial to the rapid transfer of charges; the gaps among the nanorods in the electrode material provide buffer space for the volume expansion of electrochemical reaction caused by ion intercalation and deintercalation, 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 invention also aims to provide a corresponding preparation method of the partially alloyed tin oxide nanorod array supercapacitor positive electrode material. The tin oxide nanorod array structure obtained by the method has high yield and controllable composition and appearance; 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 above object, the partially alloyed tin oxide nanorod array supercapacitor positive electrode material provided by the invention is characterized in that the tin oxide nanorods are vertically, uniformly and tightly attached to a current collector foam nickel substrate to form an array structure, the main body of the tin oxide nanorods is oxygen-deficient tin oxide, and the tin oxide nanorods contain a small amount of Ni-Sn alloy; the nanorod has a diameter of about 40-120nm and a length of 0.5-3 μm. The super capacitor anode material has the advantages of rich metal cation valence, large specific surface area, full active site exposure, good conductivity, large electrode specific capacitance, good circulation stability, no toxicity or harm to human bodies, and is an excellent super capacitor anode material.
The preparation method of the partially alloyed tin oxide nanorod array supercapacitor positive electrode material is characterized in that firstly sodium stannate trihydrate and sodium hydroxide are used as raw materials, a solvothermal method is adopted to grow a tin dioxide nanorod array on a current collector foamed nickel substrate, then high-temperature heat treatment is carried out in a vacuum tube furnace in a reducing atmosphere, and finally a partially Sn-Ni alloyed oxygen-deficient tin oxide nanorod array structure growing on the foamed nickel substrate is obtained.
The invention provides a preparation method of a partially alloyed tin oxide nanorod array supercapacitor anode material, which comprises the following steps and contents:
(1) deionized water is put into a beaker, sodium stannate trihydrate and sodium hydroxide are dissolved in the deionized water, and colorless clear solution is obtained after magnetic stirring for 30-60 min. Then, the absolute ethyl alcohol is slowly poured into a beaker, and the stirring is continued for 30-60min to obtain milky precursor thick turbid liquid for later use.
(2) And transferring the precursor solution into a high-pressure stainless steel reaction kettle, and vertically fixing the clean foam nickel sheet in the reaction kettle and completely immersing the foam nickel sheet in the precursor solution. Then, the reaction kettle is sealed and is placed in an 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 to room temperature along with the furnace and taking out to obtain the partially alloyed tin oxide nanorod array supercapacitor anode material.
In the preparation method, the dosage ratio of the deionized water, the sodium stannate trihydrate and the sodium hydroxide in the step (1) is (20-60mL): (1-4g): 0.2-1.0 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 1:1-1: 7.
In the preparation method, in the step (1), when the sodium stannate trihydrate and the sodium hydroxide are dissolved in water, the solution is magnetically stirred until the solution is completely clear; after the addition of absolute ethanol, the mixture was stirred by magnetic force until a milky thick turbid solution was obtained.
In the preparation method, the volume of the inner lining of the reaction kettle in the step (2) is 60-150 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 heat preservation temperature of the reaction kettle in the oven in the step (2) is 130-.
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 0.5-8.0 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-.
The invention is characterized in that:
(1) the super capacitor anode material is composed of a partial Sn-Ni alloyed oxygen-deficient tin oxide nanorod array structure which grows on a foamed nickel substrate. The tin oxide nano-rods are vertically, uniformly and tightly attached to a current collector foam nickel substrate to form an array structure, the main body of the tin oxide nano-rods is oxygen-deficient tin oxide, and a small amount of Ni-Sn alloy is contained to form a uniform compound. The complex has rich cation valence and complex electrochemical oxidation-reduction reaction process; the partially alloyed and anoxic compound and the metal current collector are organically combined together, so that the conductive performance is good; the nano-scale structure of the nano-rod is beneficial to improving the performance of the super capacitor by utilizing the small-size effect of the material.
(2) In the process of preparing the partially alloyed tin oxide nanorod array supercapacitor positive electrode material, firstly, sodium stannate trihydrate and sodium hydroxide are used as raw materials, a solvothermal method is adopted to grow a tin dioxide nanorod array on a current collector foamed nickel substrate, then, high-temperature heat treatment is carried out in a vacuum tube furnace in a reducing atmosphere, and finally, a partially Sn-Ni alloyed oxygen-deficient tin oxide nanorod array structure growing on the foamed nickel substrate 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 foam nickel substrate in the form of a nanorod array, the specific surface area of the material is large, the active sites are fully exposed, and 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 (current collector) of the electrode material is metal with excellent conductivity, the active substances are oxygen-deficient tin oxide with strong conductivity and newly-added Sn-Ni alloy with excellent conductivity, and the oxygen-deficient tin oxide and the newly-added Sn-Ni alloy are organically combined together through high-temperature heat treatment without any binder, so that the electrode material has good conductivity and is beneficial to quick transfer of charges; the gaps among the nanorods in the electrode material provide buffer space for the volume expansion of electrochemical reaction caused by ion intercalation and deintercalation, 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 tin oxide nanorod array structure obtained by the method has high yield and controllable composition and appearance; 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. Particularly, the raw materials of the technology are nontoxic, harmless, simple and easy to obtain; in the thermal reduction process of the tin oxide nano rod, the reducing atmosphere generated by the thermal decomposition of the preoxidized polyacrylonitrile or epoxy resin organic matter is adopted instead of the traditional hydrogen thermal reduction, so that the method is clean and environment-friendly, and the safety is greatly improved.
Drawings
FIG. 1 is a surface scanning electron micrograph of a partially alloyed tin oxide nanorod array supercapacitor positive electrode material prepared in example 3 of the present invention
FIG. 2 is a scanning electron micrograph of a cross section of a partially alloyed tin oxide nanorod array supercapacitor positive electrode material prepared in example 3 of the present invention
FIG. 3 shows the X-ray diffraction pattern and the analysis result of the partially alloyed tin oxide nanorod array supercapacitor positive electrode material prepared in example 3 of the present invention
FIG. 4 is a cyclic voltammogram of the partially alloyed tin oxide nanorod array supercapacitor positive electrode material prepared in example 3 of the present invention
Detailed Description
The technical solution of the present invention is further illustrated by the following examples.
The invention provides a partially alloyed tin oxide nanorod array supercapacitor positive electrode material which is characterized in that tin oxide nanorods are vertically, uniformly and tightly attached to a current collector foam nickel substrate to form an array structure, the main body of the tin oxide nanorod array positive electrode material is oxygen-deficient tin oxide and contains a small amount of Ni-Sn alloy; the nanorod has a diameter of about 40-120nm and a length of 0.5-3 μm. The super capacitor anode material has the advantages of rich metal cation valence, large specific surface area, full active site exposure, good conductivity, large electrode specific capacitance, good circulation stability, no toxicity or harm to human bodies, and is an excellent super capacitor anode material.
The preparation method of the partially alloyed tin oxide nanorod array supercapacitor positive electrode material is characterized in that firstly sodium stannate trihydrate and sodium hydroxide are used as raw materials, a solvothermal method is adopted to grow a tin dioxide nanorod array on a current collector foamed nickel substrate, then high-temperature heat treatment is carried out in a vacuum tube furnace in a reducing atmosphere, and finally a partially Sn-Ni alloyed oxygen-deficient tin oxide nanorod array structure growing on the foamed nickel substrate is obtained.
The invention provides a preparation method of a partially alloyed tin oxide nanorod array supercapacitor anode material, which comprises the following steps and contents:
(1) 20-60mL of deionized water is placed in a beaker, 1-4g of sodium stannate trihydrate and 0.2-1.0g of sodium hydroxide are dissolved in the deionized water, and colorless clear solution is obtained after magnetic stirring for 30-60 min. Then, slowly pouring the absolute ethyl alcohol into a beaker according to the volume ratio of the absolute ethyl alcohol to the deionized water of 1:1-1:7, and continuously stirring for 30-60min to obtain milky precursor thick turbid liquid for later use.
(2) And transferring the precursor solution into a high-pressure stainless steel reaction kettle, and vertically fixing the clean foam nickel sheet in the reaction kettle and completely immersing the foam nickel sheet in the precursor solution. Then, the reaction kettle is sealed and is placed in an 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 0.5-8.0g 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 partially alloyed tin oxide nanorod array supercapacitor anode material.
(4) In the step (2), the volume of the inner liner of the reaction kettle is 60-150mL, 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 heat preservation temperature of the reaction kettle in the oven is 130-.
(7) The heat treatment temperature in the step (3) is 200-.
The obtained partially alloyed tin oxide nanorod array supercapacitor positive electrode material was a white to gray solid in appearance. Under a scanning electron microscope, a plurality of nano rods can be observed, the diameter is about 40-120nm, and the length is 0.5-3 μm; the nano-rods are in a highly ordered structure when observed from the surface; viewed in cross section, such highly ordered nanorods grow uniformly vertically on a nickel foam substrate. 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 technology can be used for preparing the high-performance partially-alloyed tin oxide nanorod array supercapacitor positive electrode material.
Example (b): 40mL of deionized water was placed in a beaker and 2g of sodium stannate trihydrate and 0.44g of sodium hydroxide were dissolved therein and magnetically stirred for 30min to give a colorless clear solution. Then, 40mL of absolute ethyl alcohol is slowly poured into a beaker, and stirring is continued for 30min to obtain milky-white precursor thick turbid liquid. Then, the obtained precursor solution was transferred to a 100mL high-pressure stainless steel reaction kettle, and a clean nickel foam sheet 1cm × 1.5cm in size was vertically fixed in the reaction kettle and completely immersed in the precursor solution. Then, the reaction kettle is sealed and is placed in an oven for heat preservation at 190 ℃ for 24 h. And naturally cooling to room temperature, opening the reaction kettle, taking out the foamed nickel sample, washing with deionized water for 5 times, and drying in an oven at 100 ℃ for 10 hours. Then, placing the obtained nickel foam sample at the bottom of an alumina crucible, surrounding 4.0g of pre-oxidized polyacrylonitrile fiber around the nickel foam sample, then placing the crucible in a vacuum tube furnace, preserving the heat for 30-240min at 200-700 ℃ 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 partially alloyed tin oxide nanorod array supercapacitor anode material.
The typical surface scanning electron microscope photo of the obtained sample is shown in figure 1, the cross-section scanning electron microscope photo is shown in figure 2, and the highly ordered nanorod array structure can be observed; this material is composed mainly of oxygen-deficient tin oxide and contains a small amount of Ni — Sn alloy (see fig. 3); when this sample was used directly as the supercapacitor positive electrode, its cyclic voltammogram exhibited a strong redox peak (see fig. 4), indicating that the sample had excellent capacitive properties (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 can be continuously enhanced along with the increase of cycle times and reaches more than ten times of the initial capacity.
TABLE 1
Claims (3)
1. The preparation method of the partially metallized tin oxide nanorod array supercapacitor positive electrode material is characterized in that the tin oxide nanorods are vertically, uniformly and tightly attached to a current collector foam nickel substrate to form an array structure, the main body of the tin oxide nanorod array positive electrode material is oxygen-deficient tin oxide and contains a small amount of Ni-Sn alloy; the diameter of the nano rod is 40-120nm, and the length is 0.5-3 μm; the preparation method comprises the steps of firstly, taking sodium stannate trihydrate and sodium hydroxide as raw materials, growing a tin dioxide nanorod array on a current collector foamed nickel substrate by adopting a solvothermal method, and then carrying out high-temperature heat treatment in a vacuum tube furnace in a reducing atmosphere to finally obtain a partial Sn-Ni alloyed oxygen-deficient tin dioxide nanorod array structure growing on the foamed nickel substrate; the method comprises the following steps:
(1) adding deionized water into a beaker, dissolving sodium stannate trihydrate and sodium hydroxide in the deionized water, and magnetically stirring for 30-60min to obtain a colorless clear solution; then, slowly pouring absolute ethyl alcohol into the beaker, and continuously stirring for 30-60min to obtain milky precursor thick turbid liquid for later use;
(2) transferring the precursor solution into a high-pressure stainless steel 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, sealing the reaction kettle, and placing the reaction kettle in an oven for heat preservation; 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 epoxy resin or preoxidized polyacrylonitrile 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 to obtain the partially alloyed tin oxide nanorod array supercapacitor anode material.
2. The method according to claim 1, wherein the amount of deionized water, sodium stannate trihydrate and sodium hydroxide used in step (1) is in the ratio of (20-60mL) to (1-4g) to (0.2-1.0g), and the volume ratio of anhydrous ethanol to deionized water in the solvent is 1:1-1: 7; the filling amount of the reaction liquid in the high-pressure reaction kettle in the step (2) is 50-80%; the heat preservation temperature of the reaction kettle in the drying oven in the step (2) is 130-.
3. The method according to claim 1, wherein the thermal reducing atmosphere in the step (3) is provided by thermal decomposition of one of epoxy resin or pre-oxidized polyacrylonitrile; the state of the epoxy resin or the preoxidized polyacrylonitrile is fiber or powder, and the mass is 0.5-8.0 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 200-700 ℃, the heat treatment time is 30-240min, and the temperature rise rate of the tube furnace is 10-25 ℃/min.
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