CN109872881B - Application of nickel sulfide/carbon nanotube flexible composite film material to super capacitor - Google Patents
Application of nickel sulfide/carbon nanotube flexible composite film material to super capacitor Download PDFInfo
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- CN109872881B CN109872881B CN201711251918.3A CN201711251918A CN109872881B CN 109872881 B CN109872881 B CN 109872881B CN 201711251918 A CN201711251918 A CN 201711251918A CN 109872881 B CN109872881 B CN 109872881B
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Abstract
The invention discloses an application of a nickel sulfide/carbon nano tube flexible composite film material in a super capacitor, which is characterized in that the preparation method of the nickel sulfide/carbon nano tube flexible composite film material comprises the following steps: weighing 3-4 mg of nickel silicate/carbon nanotube film, placing the nickel silicate/carbon nanotube film in a polytetrafluoroethylene reaction kettle, adding absolute ethyl alcohol into the reaction kettle, and completely soaking the silicon oxide/carbon nanotube film with an ethyl alcohol solution; weighing 15-16 mL of 1.0-3.0 mg/mL sodium sulfide solution as a sulfur source, adding a mixture of water and ethanol as a solvent of sodium sulfide in sequence into a polytetrafluoroethylene reaction kettle, reacting at 160 ℃ for 9-24h, naturally cooling at room temperature, washing with deionized water to be neutral, soaking in ethanol, spreading on a polytetrafluoroethylene membrane, and airing at room temperature to obtain a nickel sulfide/carbon nanotube membrane material, wherein the phase in the nickel sulfide/carbon nanotube flexible composite membrane material can be adjusted by adjusting the reaction time and the concentration of reaction materials.
Description
Technical Field
The invention relates to the technical field of carbon-based composite materials, in particular to an application of a nickel sulfide/carbon nanotube flexible composite film material in a super capacitor.
Background
The metal sulfide, particularly nickel sulfide, is favored by researchers due to its characteristics of good conductivity and cycle performance, abundant resources, environmental friendliness and the like, and has caused a new trend of electrode material research in energy storage systems in recent times. The unique structure of the carbon nano tube enables the carbon nano tube to have higher specific surface area, good mechanical property and conductivity, and has huge application potential in the field of super capacitors. However, carbon nanotubes are nonpolar molecules, have poor wettability in aqueous solutions, and tend to be entangled and aggregated with each other due to large van der waals attraction between tube bundles. The surface of a common carbon material presents hydrophobic property, which is not beneficial to the reaction in aqueous solution, so that the reaction only stays on the macroscopic surface of the material, the reaction is not uniform and thorough, and meanwhile, the contact and the infiltration of inorganic electrolyte are not beneficial, thereby greatly limiting the application of the carbon nano tube.
Researchers now treat the surface of electrode materials, such as with concentrated acid or plasma-assisted O2-The carbon material is treated to form surface structure defects and oxygen-containing functional groups on the surface of the carbon material, the surface of the material is in a high-energy state, the chemical activity is high, and the surface wettability of the material is improved. But on one hand, the surface treatment process is complicated and can damage the original macroscopic structure; on the other hand, the existence of some organic functional groups can increase the internal resistance of the electrode, increase the leakage current and reduce the cycle performance of the capacitor. Therefore, the method can change the wettability of the carbon nanotube film without damaging the macroscopic performance of the carbon nanotube film, so that the chemical reaction is not only stopped on the macroscopic surface of the carbon nanotube film, but also a long way is needed for improving the bonding strength and the loading capacity of the active substance and the carbon nanotube.
Disclosure of Invention
The invention aims to provide an application of a nickel sulfide/carbon nanotube flexible composite film material on a super capacitor aiming at the technical defects in the prior art.
The technical scheme adopted for realizing the purpose of the invention is as follows:
the application of the nickel sulfide/carbon nano tube flexible composite film material to the super capacitor is characterized in that the preparation method of the nickel sulfide/carbon nano tube flexible composite film material comprises the following steps:
when the sodium sulfide in the step 5 is 1.4-1.6mg/mL and the reaction time is 9-15h, the phase in the nickel sulfide/carbon nano tube membrane material is Ni3S2And Ni3Si2O5(OH)4And is mainly Ni3Si2O5(OH)4；
When the sodium sulfide in the step 5 is 1.4-1.6mg/mL and the reaction time is 20-24h, the phase in the nickel sulfide/carbon nano tube membrane material is Ni3S2And Ni3Si2O5(OH)4And is mainly Ni3S2；
When the sodium sulfide in the step 5 is 1.7-1.9mg/mL and the reaction time is 20-24h, the phase in the nickel sulfide/carbon nano tube membrane material is Ni3S2；
When the sodium sulfide in the step 5 is 2.0-2.2mg/mL and the reaction time is 20-24h, the phase in the nickel sulfide/carbon nano tube membrane material is Ni3S2And NiS;
when the sodium sulfide in the step 5 is 2.3-2.5mg/mL and the reaction time is 20-24h, the phase in the nickel sulfide/carbon nano tube membrane material is Ni3S4。
Preferably, the method for preparing the silicon oxide/carbon nanotube film in step 1 comprises the following steps:
s1, weighing and mixing ethanol, ferrocene and thiophene according to the mass ratio of (95-100): 1.5-2):1 to obtain a mixed solution, wherein the ethanol is used as a carbon source of the reaction, the ferrocene is used as a catalyst, the thiophene is used as an accelerator, then, weighing Tetraethoxysilane (TEOS) with the total mass fraction of 1-8% as a silicon source of the reaction, adding the Tetraethoxysilane (TEOS) into the mixed solution, continuously performing ultrasonic dispersion at the temperature of 40-60 ℃ to obtain a uniform dispersion liquid, and transferring the uniform dispersion liquid to an injector to be used as a precursor solution;
s2, completely sealing the vertical CVD furnace (water seal or oil seal), continuously introducing Ar of 50-200 sccm, completely removing residual air in the furnace, heating the vertical CVD furnace to 1000-1250 ℃, and preserving heat for 2-6 hours;
s3, after finishing, closing Ar, and continuously injecting H of 600-900 sccm into the furnace2Wait for H2Filling the whole vertical CVD furnace chamber, and injecting the precursor solution into the furnace chamber at the injection rate of 4-12 mL/h; and collecting the cylindrical silicon oxide/carbon nano tube film at the bottom of the hearth within about 10-30min after the reaction starts.
Preferably, the mass fraction of the tetraethoxysilane in the step S1 is 4%.
Preferably, when the sodium sulfide in the step 5 is 1.4-1.6mg/mL and the reaction time is 9-15h, the specific capacity of the nickel sulfide/carbon nanotube membrane material is 540-550F/g at a current density of 10A/g.
Preferably, when the sodium sulfide in the step 5 is 1.4-1.6mg/mL and the reaction time is 20-24h, the specific capacity of 1400-1500F/g is obtained under the current density of 10A/g for the nickel sulfide/carbon nanotube membrane material.
Preferably, when the sodium sulfide in the step 5 is 1.7-1.9mg/mL and the reaction time is 20-24h, the specific capacity of the nickel sulfide/carbon nanotube membrane material is 1900-2000F/g at the current density of 10A/g.
Preferably, when the sodium sulfide in the step 5 is 2.0-2.2mg/mL and the reaction time is 20-24h, the specific capacity of the nickel sulfide/carbon nanotube film material is 2500-2600F/g under the current density of 10A/g.
Preferably, when the sodium sulfide in the step 5 is 2.3-2.5mg/mL and the reaction time is 20-24h, the specific capacity of 1600-1700F/g is obtained under the current density of 10A/g for the nickel sulfide/carbon nanotube membrane material.
Compared with the prior art, the invention has the beneficial effects that:
1. the anhydrous ethanol is added in the reaction process and is added firstly, so that the 4% silicon oxide/carbon nano tube can be better infiltrated, the chemical reaction is further caused to stay on the macroscopic surface of the carbon nano tube membrane material and further enter the microscopic carbon nano tubes, and finally, the reaction is more complete, the product is more uniform, the loading capacity of the active substance is higher, and the combination between the active substance and the carbon nano tubes is tighter;
2. by optimizing the reaction conditions, the material manufacturing process is simpler and more convenient, and the material manufacturing time cost is greatly shortened;
3. the different microcosmic appearances of the nickel sulfide, even the microcosmic crystal forms and the adjustability are achieved by adjusting the reaction process;
4. the nickel sulfide/carbon nano tube membrane material prepared by the method has stable preparation process, low preparation cost and larger industrial application potential.
5. The nickel sulfide/carbon nanotube film material prepared by the method is used in the field of super capacitors, and extremely high electrochemical performance is obtained.
Drawings
FIG. 1 is an XRD pattern of a nickel sulfide/carbon nanotube film of example 1;
FIG. 2 is an XRD pattern of the nickel sulfide/carbon nanotube film of example 2;
FIG. 3 is an XRD pattern of the nickel sulfide/carbon nanotube film of example 3;
FIG. 4 is an XRD pattern of the nickel sulfide/carbon nanotube film of example 4;
FIG. 5 is an XRD pattern of the nickel sulfide/carbon nanotube film of example 5;
FIG. 6 is an SEM image of a nickel sulfide/carbon nanotube film of example 1;
FIG. 7 is an SEM image of a nickel sulfide/carbon nanotube film of example 2;
FIG. 8 is an SEM image of a nickel sulfide/carbon nanotube film of example 3;
FIG. 9 is an SEM image of a nickel sulfide/carbon nanotube film of example 4;
FIG. 10 is an SEM image of a nickel sulfide/carbon nanotube film of example 5;
FIG. 11 is a cyclic voltammogram of the nickel sulfide/carbon nanotube film of example 1;
FIG. 12 is a discharge curve of the nickel sulfide/carbon nanotube film of example 1;
FIG. 13 is a cyclic voltammogram of the nickel sulfide/carbon nanotube film of example 2;
FIG. 14 is a discharge curve of the nickel sulfide/carbon nanotube film of example 2;
FIG. 15 is a cyclic voltammogram of the nickel sulfide/carbon nanotube film of example 3;
FIG. 16 is a discharge curve of the nickel sulfide/carbon nanotube film of example 3;
FIG. 17 is a cyclic voltammogram of the nickel sulfide/carbon nanotube film of example 4;
FIG. 18 is a discharge curve of the nickel sulfide/carbon nanotube film of example 4;
FIG. 19 is a cyclic voltammogram of the nickel sulfide/carbon nanotube film of example 5;
FIG. 20 is a discharge curve of the nickel sulfide/carbon nanotube film of example 5;
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
(1) Weighing 15mg of 4% silicon oxide/carbon nanotube film, placing the film in a 100mL blue bottle cap glass bottle, weighing 20mL absolute ethyl alcohol, adding the absolute ethyl alcohol into the bottle, and slightly shaking the bottle body to enable the ethyl alcohol solution to completely soak the silicon oxide/carbon nanotube film.
(2) 60mL of deionized water and 2.4mL of 0.1M nickel nitrate solution are weighed, 2g of urea is weighed and sequentially added into a blue-cap bottle, and the mixture is gently stirred until the urea is completely dissolved.
(3) Placing the blue-covered bottle in an oven to react for 12 hours at 105 ℃, naturally cooling at room temperature, washing with deionized water to be neutral, and drying to obtain a nickel silicate/carbon nanotube film for later use;
(4) 3.5mg of the obtained nickel silicate/carbon nanotube film is weighed and placed in a 20mL polytetrafluoroethylene reaction kettle, 4mL of absolute ethyl alcohol is weighed and added into the reaction kettle, and the silicon oxide/carbon nanotube film is completely soaked by the ethyl alcohol solution.
(5) Weighing 12mL of deionized water, weighing 1.5mg/mL of sodium sulfide as a sulfur source, sequentially adding into a polytetrafluoroethylene reaction kettle, reacting at 160 ℃ for 12h, naturally cooling at room temperature, washing to be neutral by the deionized water, soaking in ethanol, spreading on a polytetrafluoroethylene membrane, and drying at room temperature to obtain the nickel sulfide/carbon nanotube membrane material.
The XRD pattern of the nickel sulfide/carbon nanotube film in example 1 is shown in fig. 1, from which it can be seen that the peak value in the XRD pattern of the material is not very sharp, which indicates that the crystallinity of the material is not very good under this condition, but the main peak position can be distinguished, and by comparing with the standard PDF card, it can be determined that the main phase in the material is Ni3S2And Ni3Si2O5(OH)4And is mainly Ni3Si2O5(OH)4This indicates that under the above conditions, since the second-step sulfidation was incomplete for a short period of time, a large amount of unreacted Ni remained3Si2O5(OH)4. An SEM atlas of the nickel sulfide/carbon nanotube film in example 1 is shown in fig. 6, where it can be seen that curved, elongated and smooth carbon nanotubes are mutually lapped to form a network, thin nickel sulfide nanosheets in the form of "flower clusters" are uniformly distributed in the middle of the carbon nanotube network, some nickel sulfide nanosheets are wrapped on the carbon nanotubes, some nickel sulfide nanosheets are distributed among the carbon nanotubes, some nickel sulfide nanosheets grow on the nodes of the carbon nanotube network, the flower clusters "of nickel sulfide nanosheets are tightly bonded with the carbon nanotubes, and the sheet flower clusters are in an open three-dimensional porous structure. Electrochemical tests are performed on the material in example 1, and fig. 11 is a cyclic voltammetry curve of the nickel sulfide/carbon nanotube film in example 1, wherein the scanning voltage range is 0-0.5V, and the scanning rate is changed to 5-200 mV/s. The CV curve in the graph is obviously different from a standard rectangle, so that the electrode material can be judged to be mainly used for storing charges based on a Faraday reaction mechanism, a pair of oxidation-reduction peaks exist between 0.17 and 0.2V and between 0.35 and 0.4V, and the peak shapes areThe shape has good symmetry, which corresponds to the redox reaction that occurs with nickel ions. Under the scanning speed of 5-200 mV/s, the shape of a CV curve is almost unchanged, even under the high scanning speed of 200mV/s, the material still has an obvious oxidation-reduction peak, the change of the cathode peak current potential is about 0.1V, and the material is proved to have good reversibility and simultaneously indicates that the electrode material has good rate characteristics. FIG. 12 is a chronopotentiometric graph of the nickel sulfide/carbon nanotube film composite material of example 1 under different current density loads, no obvious IR drop is seen in the graph, which shows that the resistance of the material is relatively small, and a discharge plateau exists between 0.2V and 0.3V, which shows that a pseudo-capacitance reaction exists at the position. The specific capacity of the nickel sulfide/carbon nanotube film composite material obtained at 1A/g current density is 808.2F/g, and when the scanning rate is increased to 2,5, 10, 20 and 50A/g, the specific capacity is 766.3, 664.2,548.1,419.7F/g, and is 94.8%, 82.2%, 67.8% and 51.9% of the initial capacity, which indicates that the nickel sulfide/carbon nanotube film composite material has good rate capability while having large capacity. Combined with the morphology and structure analysis of the flaky Ni3S2The specific surface area of the composite material is greatly increased, sufficient reaction sites are provided for electrode reaction, the four-way eight-reach carbon nanotube network reduces the transmission path of electrons and ions, not only plays a role of a framework, but also provides a transmission highway for electrons, and the conductivity of metal sulfides is increased; meanwhile, the mutually crossed sheet metal sulfides form a three-dimensional honeycomb shape, which is beneficial to the diffusion of electrolyte, and the specific capacity of the nickel sulfide/carbon nanotube film composite material is remarkably improved by combining the reasons, and the nickel sulfide/carbon nanotube film composite material has very good rate property.
Example 2
(1) Weighing 15mg of 4% silicon oxide/carbon nanotube film, placing the film in a 100mL blue bottle cap glass bottle, weighing 20mL absolute ethyl alcohol, adding the absolute ethyl alcohol into the bottle, and slightly shaking the bottle body to enable the ethyl alcohol solution to completely soak the silicon oxide/carbon nanotube film.
(2) 60mL of deionized water and 2.4mL of 0.1M nickel nitrate solution are weighed, 2g of urea is weighed and sequentially added into a blue-cap bottle, and the mixture is gently stirred until the urea is completely dissolved.
(3) Placing the blue-covered bottle in an oven to react for 12 hours at 105 ℃, naturally cooling at room temperature, washing with deionized water to be neutral, and drying to obtain a nickel silicate/carbon nanotube film for later use;
(4) 3.5mg of the obtained nickel silicate/carbon nanotube film is weighed and placed in a 20mL polytetrafluoroethylene reaction kettle, 4mL of absolute ethyl alcohol is weighed and added into the reaction kettle, and the silicon oxide/carbon nanotube film is completely soaked by the ethyl alcohol solution.
(5) Weighing 12mL of deionized water, weighing 1.5mg/mL of sodium sulfide as a sulfur source, adding the sodium sulfide into a polytetrafluoroethylene reaction kettle, reacting at 160 ℃ for 24 hours, naturally cooling at room temperature, washing to be neutral by the deionized water, soaking in ethanol, spreading on a polytetrafluoroethylene membrane, and drying at room temperature to obtain the nickel sulfide/carbon nanotube membrane material.
The XRD pattern of the nickel sulfide/carbon nanotube film in example 2 is shown in fig. 2, from which it can be seen that the peak value of the XRD pattern of the material is sharper than that of example 1, which shows that the crystallization property of the nickel sulfide/carbon nanotube film material can be significantly changed by increasing the hydrothermal reaction time. By comparing with the standard PDF card, the main phase in the material can be judged to be Ni3S2And Ni3Si2O5(OH)4However, Ni is more apparent than FIG. 13S2The corresponding peak is more obvious, which shows that the sulfurization process can be more complete by increasing the hydrothermal reaction time, and Ni in the material3S2The phase ratio is greatly increased, but a small amount of unreacted Ni remains3Si2O5(OH)4. The SEM image of the nickel sulfide/carbon nanotube film in example 2 is shown in fig. 7, which shows that the material microstructure is substantially the same as that of example 1, but compared with the SEM image of example 1, the sheet-like clusters account for a larger amount, the clusters are tightly bonded to themselves, and the bare carbon tubes are reduced. Electrochemical tests are performed on the material in example 2, and fig. 13 is a cyclic voltammetry curve of the nickel sulfide/carbon nanotube film in example 2, wherein the scanning voltage range is 0-0.5V, and the scanning rate is changed to 5-50 mV/s. The CV curve shape in the figure is similar to that of FIG. 11, and it can be determined from the description that the electrode material is mainly based on FaradayThe second reaction mechanism proceeds to store charge. The larger area of the curve wall at the same scan rate in fig. 13 compared to fig. 11 illustrates the superior performance of the material. FIG. 14 is a chronopotentiometric graph of the nickel sulfide/carbon nanotube film composite material of example 3 under different current density loads, no obvious IR drop is seen in the graph, which shows that the resistance of the material is relatively small, and a discharge plateau exists between 0.2V and 0.3V, which shows that a pseudo-capacitance reaction exists at the position. Calculation can show that the specific capacity of 1431.2 obtained by the nickel sulfide/carbon nanotube film composite material at the current density of 10A/g is 1269.8, 1182.5,1100.5 and 1005.2F/g when the scanning rate is increased to 20, 30, 40 and 50A/g, and is 88.6%, 82.5%, 76.8% and 70.2% of the initial capacity, which indicates that the nickel sulfide/carbon nanotube film composite material has good rate characteristics while having large capacity.
Example 3
(1) Weighing 15mg of 4% silicon oxide/carbon nanotube film, placing the film in a 100mL blue bottle cap glass bottle, weighing 20mL absolute ethyl alcohol, adding the absolute ethyl alcohol into the bottle, and slightly shaking the bottle body to enable the ethyl alcohol solution to completely soak the silicon oxide/carbon nanotube film.
(2) Measuring 60mL of deionized water and 1.0-2.5 mL of nickel nitrate solution with the concentration of 0.1M, weighing 2g of urea, sequentially adding the urea into a blue-cap bottle, and slightly stirring until the urea is completely dissolved.
(3) Placing the blue-covered bottle in an oven to react for 12 hours at 105 ℃, naturally cooling at room temperature, washing with deionized water to be neutral, and drying to obtain a nickel silicate/carbon nanotube film for later use;
(4) 3.5mg of the obtained nickel silicate/carbon nanotube film is weighed and placed in a 20mL polytetrafluoroethylene reaction kettle, 4mL of absolute ethyl alcohol is weighed and added into the reaction kettle, and the silicon oxide/carbon nanotube film is completely soaked by the ethyl alcohol solution.
(5) Weighing 12mL of deionized water, weighing 1.8mg/mL of sodium sulfide as a sulfur source, sequentially adding into a polytetrafluoroethylene reaction kettle, reacting at 160 ℃ for 24 hours, naturally cooling at room temperature, washing to be neutral by the deionized water, soaking in ethanol, spreading on a polytetrafluoroethylene membrane, and drying at room temperature to obtain the nickel sulfide/carbon nanotube membrane material.
Nickel sulfide in example 3The XRD pattern of the/carbon nanotube film is shown in figure 3, and the peak value in the XRD pattern of the material is more sharp relative to figures 1 and 2, which shows that the crystallization property of the nickel sulfide/carbon nanotube film material can be obviously changed by increasing the hydrothermal reaction time. By comparing with standard PDF card, the main phase in the material can be judged to be basically and completely converted into Ni3S2Almost no residual Ni3Si2O5(OH)4This indicates that the sulfidation process can be made more complete by increasing the hydrothermal reaction time. The SEM image of the nickel sulfide/carbon nanotube film in example 3 is shown in fig. 8, which shows that the material microstructure is substantially the same as that of example 1, but the loading of the flaky nickel sulfide is larger and the exposed carbon tubes are less compared with the SEM image of example 1. Electrochemical tests are performed on the material in example 3, and fig. 15 shows cyclic voltammetry curves of the nickel sulfide/carbon nanotube film in example 3, wherein the scanning voltage range is 0-0.5V, and the scanning rate is changed to 5-100 mV/s. The CV curve shape in the figure is similar to that of fig. 11, and it can be understood from this that the electrode material stores electric charge mainly based on the faraday reaction mechanism. The larger area of the curve wall at the same scan rate in fig. 15 compared to fig. 11 illustrates the superior performance of the material. FIG. 16 is a chronopotentiometric graph of the nickel sulfide/carbon nanotube film composite material of example 3 under different current density loads, no obvious IR drop is seen in the graph, which shows that the resistance of the material is relatively small, and a discharge plateau exists between 0.2V and 0.3V, which shows that a pseudo-capacitance reaction exists at the position. Calculation can show that the nickel sulfide/carbon nanotube film composite material obtains a specific capacity of 1994.7F/g at a current density of 10A/g, and when the scanning rate is increased to 20, 30, 40 and 50A/g, the specific capacities are 1734.0, 1500.0,1356.3 and 1351.1F/g, which are 86.9%, 75.2%, 67.8% and 67.7% of the initial capacity respectively, which indicates that the nickel sulfide/carbon nanotube film composite material has good rate capability while having large capacity.
Example 4
(1) Weighing 15mg of 4% silicon oxide/carbon nanotube film, placing the film in a 100mL blue bottle cap glass bottle, weighing 20mL absolute ethyl alcohol, adding the absolute ethyl alcohol into the bottle, and slightly shaking the bottle body to enable the ethyl alcohol solution to completely soak the silicon oxide/carbon nanotube film.
(2) 60mL of deionized water and 2.4mL of 0.1M nickel nitrate solution are weighed, 2g of urea is weighed and sequentially added into a blue-cap bottle, and the mixture is gently stirred until the urea is completely dissolved.
(3) Placing the blue-covered bottle in an oven to react for 12 hours at 105 ℃, naturally cooling at room temperature, washing with deionized water to be neutral, and drying to obtain a nickel silicate/carbon nanotube film for later use;
(4) 3.5mg of the obtained nickel silicate/carbon nanotube film is weighed and placed in a 20mL polytetrafluoroethylene reaction kettle, 4mL of absolute ethyl alcohol is weighed and added into the reaction kettle, and the silicon oxide/carbon nanotube film is completely soaked by the ethyl alcohol solution.
(5) Weighing 12mL of deionized water, weighing 2.1mg/mL of sodium sulfide as a sulfur source, sequentially adding into a polytetrafluoroethylene reaction kettle, reacting at 160 ℃ for 24 hours, naturally cooling at room temperature, washing to be neutral by the deionized water, soaking in ethanol, spreading on a polytetrafluoroethylene membrane, and drying at room temperature to obtain the nickel sulfide/carbon nanotube membrane material.
The XRD pattern of the nickel sulfide/carbon nanotube film in example 4 is shown in fig. 4, from which it can be seen that the peaks in the XRD pattern of this material are sharper than those in fig. 1, 2 and 3, which shows that the crystallization properties of the nickel sulfide/carbon nanotube film material can be significantly changed by increasing the hydrothermal reaction time. By comparing with standard PDF card, the main phase in the material can be judged to be basically and completely converted into Ni3S2And NiS, no Ni remaining at all3Si2O5(OH)4This shows that the sulfidation process can be more complete by increasing the hydrothermal reaction time, and the species of the final product can be changed by increasing the sulfidation concentration. The SEM image of the nickel sulfide/carbon nanotube film of example 4 is shown in fig. 9, which shows that the material has substantially the same microstructure as the material of example 1, but compared with the SEM image of example 1, it can be seen that the loading of the flaky nickel sulfide is larger, the exposed carbon tubes are smaller, and the lamella is curved and "soft" and more tightly bonded to the carbon tubes. Electrochemical testing was performed on the material of example 4, and FIG. 17 is a nickel sulfide/carbon nanotube film of example 2The sweep voltage range of the cyclic voltammetry curve is 0-0.5V, and the sweep rate is changed to 5-100 mV/s. The CV curve shape in the figure is similar to that of fig. 11, and it can be understood from this that the electrode material stores electric charge mainly based on the faraday reaction mechanism. Compared with fig. 11, the area enclosed by the curves in fig. 17 is larger at the same scanning speed, which shows that the material has more excellent super-electric performance. FIG. 18 is a chronopotentiometric graph of the nickel sulfide/carbon nanotube film composite material of example 2 under different current density loads, no obvious IR drop is seen in the graph, which shows that the resistance of the material is relatively small, and a discharge plateau exists between 0.2V and 0.3V, which shows that a pseudo-capacitance reaction exists at the position. Calculation can show that the nickel sulfide/carbon nanotube film composite material obtains a specific capacity of 2540.5F/g at a current density of 10A/g, when the scanning rate is increased to 20, 30, 40 and 50A/g, the specific capacities are 2318.9, 2213.5, 2108.1.3 and 2027.0F/g respectively, and are 91.2%, 87.1%, 82.9% and 79.8% of the initial capacity, which indicates that the nickel sulfide/carbon nanotube film composite material has good rate performance while having extremely large capacity.
Example 5
(1) Weighing 15mg of 4% silicon oxide/carbon nanotube film, placing the film in a 100mL blue bottle cap glass bottle, weighing 20mL absolute ethyl alcohol, adding the absolute ethyl alcohol into the bottle, and slightly shaking the bottle body to enable the ethyl alcohol solution to completely soak the silicon oxide/carbon nanotube film.
(2) 60mL of deionized water and 2.4mL of 0.1M nickel nitrate solution are weighed, 2g of urea is weighed and sequentially added into a blue-cap bottle, and the mixture is gently stirred until the urea is completely dissolved.
(3) Placing the blue-covered bottle in an oven to react for 12 hours at 105 ℃, naturally cooling at room temperature, washing with deionized water to be neutral, and drying to obtain a nickel silicate/carbon nanotube film for later use;
(4) 3.5mg of the obtained nickel silicate/carbon nanotube film is weighed and placed in a 20mL polytetrafluoroethylene reaction kettle, 4mL of absolute ethyl alcohol is weighed and added into the reaction kettle, and the silicon oxide/carbon nanotube film is completely soaked by the ethyl alcohol solution.
(5) Weighing 12mL of deionized water, weighing 2.4mg/mL of sodium sulfide as a sulfur source, adding the sulfur source into a polytetrafluoroethylene reaction kettle, reacting at 160 ℃ for 24 hours, naturally cooling at room temperature, washing to be neutral by the deionized water, soaking in ethanol, spreading on a polytetrafluoroethylene membrane, and airing at room temperature to obtain the nickel sulfide/carbon nanotube membrane material.
The XRD pattern of the nickel sulfide/carbon nanotube film in example 5 is shown in FIG. 5, and by comparing with the standard PDF card, it can be judged that the main phase in the material is almost completely converted into Ni3S4Different from the substances generated in FIGS. 1 to 4, the method can be used to increase the hydrothermal reaction time to make the sulfurization process more complete, and increase the sulfurization concentration to change the type of the final product. The SEM image of the nickel sulfide/carbon nanotube film in example 5 is shown in fig. 10, which shows that the material microstructure is substantially different from that of examples 1 to 4, but it can be seen that nickel sulfide is filled in the carbon nanotube film voids, and the flaky nickel sulfide is significantly reduced and granular crystals appear, compared with the SEM images of examples 1 to 4. The above indicates that the microstructure of the final product can be changed by increasing the sulfidation concentration. Electrochemical tests are performed on the material in example 5, and fig. 19 shows cyclic voltammetry curves of the nickel sulfide/carbon nanotube film in example 2, wherein the scanning voltage range is 0-0.5V, and the scanning rate is changed to 5-100 mV/s. The CV curve shape in the figure is similar to that of fig. 11, and it can be understood from this that the electrode material stores electric charge mainly based on the faraday reaction mechanism. The larger area of the curve wall at the same scan rate in fig. 19 compared to fig. 11 illustrates the superior performance of the material. FIG. 20 is a chronopotentiometric graph of the nickel sulfide/carbon nanotube film composite material of example 2 under different current density loads, no obvious IR drop is seen in the graph, which shows that the resistance of the material is relatively small, and a discharge plateau exists between 0.2V and 0.3V, which shows that a pseudo-capacitance reaction exists at the position. Calculation can show that the nickel sulfide/carbon nanotube film composite material obtains a specific capacity of 1656.9F/g at a current density of 10A/g, when the scanning rate is increased to 20, 30, 40 and 50A/g, the specific capacities are 1626.3, 1507.8,1410.5 and 1315.7F/g respectively, and are 98.1%, 90.9%, 85.1% and 79.4% of the initial capacity, which indicates that the nickel sulfide/carbon nanotube film composite material has good rate capability while having extremely large capacity.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. The application of the nickel sulfide/carbon nano tube flexible composite film material to the super capacitor is characterized in that the preparation method of the nickel sulfide/carbon nano tube flexible composite film material comprises the following steps:
step 1, weighing a silicon oxide/carbon nanotube film and placing the silicon oxide/carbon nanotube film in absolute ethyl alcohol to enable the absolute ethyl alcohol solution to completely infiltrate the silicon oxide/carbon nanotube film;
step 2, adding a nickel nitrate solution, urea and deionized water into the system prepared in the step 1, and uniformly mixing until the urea is completely dissolved;
step 3, placing the system obtained in the step 2 in an oven to react for 6-18h at the temperature of 90-120 ℃, naturally cooling at room temperature, washing with deionized water to be neutral, and drying to obtain a nickel silicate/carbon nanotube film for later use;
step 4, weighing 3-4 mg of the nickel silicate/carbon nanotube film obtained in the step 3, placing the nickel silicate/carbon nanotube film in a polytetrafluoroethylene reaction kettle, adding absolute ethyl alcohol into the reaction kettle, and enabling an ethanol solution to completely infiltrate the nickel silicate/carbon nanotube film;
step 5, weighing 15-16 mL of 1.0-3.0 mg/mL sodium sulfide solution as a sulfur source, adding a mixture of water and ethanol as a sodium sulfide solvent into a polytetrafluoroethylene reaction kettle, reacting at 160 ℃ for 9-24h, naturally cooling at room temperature, washing with deionized water to be neutral, soaking in ethanol, spreading on a polytetrafluoroethylene membrane, and airing at room temperature to obtain a nickel sulfide/carbon nanotube membrane material;
when the sodium sulfide in the step 5 is 1.4-1.6mg/mL and the reaction time is 9-15h, the phase in the nickel sulfide/carbon nano tube membrane material is Ni3S2And Ni3Si2O5(OH)4And is mainly Ni3Si2O5(OH)4；
When the sodium sulfide in the step 5 is 1.4-1.6mg/mL, when the reaction time is 20-24h, the phase in the nickel sulfide/carbon nano tube membrane material is Ni3S2And Ni3Si2O5(OH)4And is mainly Ni3S2；
When the sodium sulfide in the step 5 is 1.7-1.9mg/mL and the reaction time is 20-24h, the phase in the nickel sulfide/carbon nano tube membrane material is Ni3S2；
When the sodium sulfide in the step 5 is 2.0-2.2mg/mL and the reaction time is 20-24h, the phase in the nickel sulfide/carbon nano tube membrane material is Ni3S2And NiS;
when the sodium sulfide in the step 5 is 2.3-2.5mg/mL and the reaction time is 20-24h, the phase in the nickel sulfide/carbon nano tube membrane material is Ni3S4；
The preparation method of the silicon oxide/carbon nanotube film in the step 1 comprises the following steps:
s1, weighing and mixing ethanol, ferrocene and thiophene according to the mass ratio of (95-100): 1.5-2):1 to obtain a mixed solution, wherein the ethanol is used as a carbon source of the reaction, the ferrocene is used as a catalyst, the thiophene is used as an accelerator, then, weighing Tetraethoxysilane (TEOS) with the total mass fraction of 1-8% as a silicon source of the reaction, adding the Tetraethoxysilane (TEOS) into the mixed solution, continuously performing ultrasonic dispersion at the temperature of 40-60 ℃ to obtain a uniform dispersion liquid, and transferring the uniform dispersion liquid to an injector to be used as a precursor solution;
s2, completely sealing the vertical CVD furnace, continuously introducing Ar of 50-200 sccm, completely removing residual air in the furnace, heating the vertical CVD furnace to 1000-1250 ℃, and preserving heat for 2-6 hours;
s3, after finishing, closing Ar, and continuously injecting H of 600-900 sccm into the furnace2Wait for H2Filling the whole vertical CVD furnace chamber, and injecting the precursor solution into the furnace chamber at the injection rate of 4-12 mL/h; and collecting the cylindrical silicon oxide/carbon nano tube film at the bottom of the hearth 10-30min after the reaction starts.
2. The application of the nickel sulfide/carbon nanotube flexible composite film material on the supercapacitor, according to claim 1, wherein the mass fraction of the tetraethoxysilane in the step S1 is 4%.
3. The application of the nickel sulfide/carbon nanotube flexible composite film material in the supercapacitor as claimed in claim 1, wherein when the sodium sulfide in the step 5 is 1.4-1.6mg/mL and the reaction time is 9-15h, the nickel sulfide/carbon nanotube film material has a specific capacity of 540-550F/g at a current density of 10A/g.
4. The application of the nickel sulfide/carbon nanotube flexible composite film material in the supercapacitor as claimed in claim 1, wherein when the sodium sulfide in the step 5 is 1.4-1.6mg/mL and the reaction time is 20-24h, the nickel sulfide/carbon nanotube film material has a specific capacity of 1400-1500F/g at a current density of 10A/g.
5. The application of the nickel sulfide/carbon nanotube flexible composite film material in the supercapacitor as claimed in claim 1, wherein when the sodium sulfide in the step 5 is 1.7-1.9mg/mL and the reaction time is 20-24h, the nickel sulfide/carbon nanotube film material has a specific capacity of 1900-2000F/g at a current density of 10A/g.
6. The application of the nickel sulfide/carbon nanotube flexible composite film material in the supercapacitor as claimed in claim 1, wherein when the sodium sulfide in the step 5 is 2.0-2.2mg/mL and the reaction time is 20-24h, the nickel sulfide/carbon nanotube film material has a specific capacity of 2500-2600F/g at a current density of 10A/g.
7. The application of the nickel sulfide/carbon nanotube flexible composite film material in the supercapacitor as claimed in claim 1, wherein when the sodium sulfide in the step 5 is 2.3-2.5mg/mL and the reaction time is 20-24h, the specific capacity of 1600-1700F/g is obtained for the nickel sulfide/carbon nanotube film material at a current density of 10A/g.
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| CN105789624A (en) * | 2016-04-20 | 2016-07-20 | 浙江大学 | Array type trinickel disulfide-based composite electrode as well as preparation method and application thereof |
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