Preparation method of a biomimetic flagellum-shaped nanowire

Abstract

The application provides a preparation method of a biomimetic flagelliform nanowire and relates to the technical field of nanowire material preparation. The method comprises the following steps: mixing and immersing a trithiocyanic acid solution and copper hydroxide nanowires, and obtaining immersed nanowires after drying; the immersion conditions comprise the following steps: the temperature is 20-45 DEG C, and the time is 0.01-50 min; and the obtained immersed nanowires are calcined at 250-500 DEG C for 2-6 h. The method provided by the application uses a trithiocyanic acid solution to immerse Cu(OH)2 nanowires, and then calcines in a muffle furnace. The method provided by the application is simple in operation, the prepared nanowires are uniform and controllable in morphology, and can be applied to the fields of oil-water separation, battery negative electrode current collectors, adsorption and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of nanowire material preparation, in particular to a preparation method of biomimetic flagelliform nanowires. BACKGROUND

[0002] As a nanoscale material, nanowires have quantum effect, interface effect, small size effect and surface effect, which make them show superior physical and chemical properties different from traditional materials. One-dimensional nanowires, such as copper nanowires and silver nanowires, have been widely concerned in the fields of oil-water separation, photocatalysis, electrocatalysis, battery negative electrode current collector and adsorption.

[0003] Biomimetic materials have the characteristics, principles and interactions of biological systems, which provide new ideas and applications for science and technology. By drawing on the structure of biology, biomimetic materials with micro or nanoscale structures are prepared, which is a hot topic in current scientific research and has important scientific significance and application value. However, there are still great difficulties in preparing multi-dimensional nanowire materials with biomimetic structures. SUMMARY

[0004] In order to solve the above problems, the present application provides a preparation method of biomimetic flagelliform nanowires. The present application successfully prepares nanowires with unique biomimetic flagelliform structure by using a simple preparation method. The biomimetic flagelliform nanowires prepared by simple immersion modification of one-dimensional Cu(OH)2 nanowires and then calcination have uniform morphology, simple operation and important practical value.

[0005] In order to achieve the above purpose, the present application provides the following technical scheme:

[0006] The present application provides a preparation method of biomimetic flagelliform nanowires, comprising the following steps:

[0007] 1) Mix and immerse trithiocyanic acid solution with copper hydroxide nanowires, and obtain immersed nanowires after drying;

[0008] The immersion conditions include: temperature of 20-45℃, time of 0.01-50min;

[0009] 2) Calcine the immersed nanowires obtained in step 1) at 250-500℃ for 2-6h.

[0010] Preferably, the concentration of trithiocyanic acid solution in step 1) is 0.001-0.002mol / L.

[0011] Preferably, the concentration of trithiocyanic acid solution is 0.0012-0.0018mol / L.

[0012] Preferably, the solvent of the step 1) thiocyanic acid solution comprises an ethanol solution, and the volume percentage of ethanol in the ethanol solution is 80-100%.

[0013] Preferably, the volume of the step 1) thiocyanic acid solution to the mass of the copper hydroxide nanowires is 100-220 ml: 1-2.5 g.

[0014] Preferably, the volume of the step 1) thiocyanic acid solution to the mass of the copper hydroxide nanowires is 150-200 ml: 1.4-2 g.

[0015] Preferably, the conditions of the step 1) immersion include that the temperature is 25-40℃, and the time is 10-40 min.

[0016] Preferably, the conditions of the step 2) calcination include that the temperature is 300-400℃, and the time is 3-4 h.

[0017] Preferably, the step 2) calcination further comprises pre-calcination before calcination, and the conditions of the pre-calcination include that the temperature is 100-300℃, and the time is 1 h.

[0018] Preferably, the temperature of the pre-calcination is 150-200℃.

[0019] The present application utilizes the simple acid-base reaction between thiocyanic acid and Cu(OH)2, forms the coating of thiocyanic acid on the Cu(OH)2 nanowires. By utilizing the Kirkendall effect, the different diffusion speeds of Cu and S ions at the calcination temperature, realizes the outward diffusion of Cu ions, and further forms the unique structure of the biomimetic flagelliform nanowires.

[0020] Advantages:

[0021] The present application uses the thiocyanic acid solution to immerse the Cu(OH)2 nanowires, and then calcines in a muffle furnace. The method provided by the present application is simple in operation, and the prepared nanowires are uniform and controllable in morphology, and can be applied in the fields of oil-water separation, battery negative electrode current collector, adsorption, etc. BRIEF DESCRIPTION OF DRAWINGS

[0022] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the drawings needed to be used in the embodiments will be briefly introduced below.

[0023] Figure 1 The SEM image of the biomimetic flagelliform nanowires prepared by the present application;

[0024] Figure 2 The SEM image of a single biomimetic flagelliform nanowire;

[0025] Figure 3 The result image of the flagelliform nanowires which cannot be prepared by the comparative example 1. DETAILED DESCRIPTION

[0026] The application provides a preparation method of a biomimetic flagelliform nanowire, which comprises the following steps:

[0027] 1) mixing and immersing a thiocyanic acid solution with copper hydroxide nanowires, and drying to obtain immersed nanowires;

[0028] The immersion conditions comprise that the temperature is 20-45 ℃ and the time is 0.01-50 min.

[0029] 2) calcining the immersed nanowires obtained in the step 1) at 250-500 ℃ for 2-6 h.

[0030] The application mixes and immerses a thiocyanic acid solution with copper hydroxide nanowires, and dries to obtain immersed nanowires; the immersion conditions comprise that the temperature is 20-45 ℃ and the time is 0.01-50 min.

[0031] In the application, the concentration of the thiocyanic acid solution is preferably 0.001-0.002 mol / L, more preferably 0.0012-0.0018 mol / L, and most preferably 0.0013 mol / L. In the application, the solvent of the thiocyanic acid solution preferably comprises an ethanol solution, the volume percentage of ethanol in the ethanol solution is preferably 80-100%, more preferably 85-95%, and most preferably 90%. In the application, the volume of the thiocyanic acid solution to the mass of the copper hydroxide nanowires is preferably 100-220 ml: 1-2.5 g, more preferably 150-200 ml: 1.4-2 g, and most preferably 180 ml: 1.5-1.8 g. In the application, the immersion conditions preferably comprise that the temperature is 25-40 ℃ and the time is 10-40 min. The immersion in the application is preferably carried out under the conditions of water bath and stirring. After the immersion, the retained substances are preferably filtered and dried to obtain the immersed nanowires, and the application does not have special limitations on the conditions of the filtering and drying, and the person skilled in the art can perform the operations according to the conventional operations.

[0032] The application calcines the obtained immersed nanowires at 250-500 ℃ for 2-6 h. In the application, the calcination conditions preferably comprise that the temperature is 300-400 ℃ and the time is 3-4 h. The application preferably further comprises pre-calcination before the calcination, and the pre-calcination conditions comprise that the temperature is 100-300 ℃ and the time is 1 h. In the application, the pre-calcination temperature is more preferably 150-200 ℃.

[0033] In order to further illustrate the application, the application is described in detail in combination with the examples below, but they should not be understood as limitations on the protection scope of the application.

[0034] Example 1

[0035] An ethanol solution of 100 mL volume and 0.001 mol / L concentration was prepared using ethanol with a volume fraction of 80%, and the solution was stirred in a 40°C water bath to keep the temperature constant. Then, 1 g of Cu(OH)2nanowires was immersed in the solution for 50 min, and then filtered to remove the excess solvent from the Cu(OH)2nanowires.

[0036] The Cu(OH)2nanowires were dried, and then calcined in a muffle furnace at 100°C for 1 h and then at 400°C for 4 h to prepare the flagellum-shaped nanowires.

[0037] Example 2

[0038] An ethanol solution of 200 mL volume and 0.0012 mol / L concentration was prepared using ethanol with a volume fraction of 85%, and the solution was stirred in a 35°C water bath to keep the temperature constant. Then, 1.5 g of Cu(OH)2nanowires was immersed in the solution for 40 min, and then filtered to remove the excess solvent from the Cu(OH)2nanowires.

[0039] The Cu(OH)2nanowires were dried, and then calcined in a muffle furnace at 300°C for 4 h to prepare the flagellum-shaped nanowires.

[0040] Example 3

[0041] An ethanol solution of 180 mL volume and 0.0018 mol / L concentration was prepared using ethanol with a volume fraction of 90%, and the solution was stirred in a 45°C water bath to keep the temperature constant. Then, 2 g of Cu(OH)2nanowires was immersed in the solution for 20 min, and then filtered to remove the excess solvent from the Cu(OH)2nanowires.

[0042] The Cu(OH)2nanowires were dried, and then calcined in a muffle furnace at 150°C for 1 h and then at 400°C for 2 h to prepare the flagellum-shaped nanowires.

[0043] Example 4

[0044] An ethanol solution of 150 mL volume and 0.002 mol / L concentration was prepared using ethanol with a volume fraction of 95%, and the solution was stirred in a 30°C water bath to keep the temperature constant. Then, 2.5 g of Cu(OH)2nanowires was immersed in the solution for 1 min, and then filtered to remove the excess solvent from the Cu(OH)2nanowires.

[0045] The Cu(OH)2nanowires after impregnation were dried, and then calcined in a muffle furnace at 200°C for 1 h, and then heated to 500°C for 3 h to prepare the flagelliform nanowires.

[0046] Example 5

[0047] An ethanol solution of ethanethiothio cyanate with a volume fraction of 98% was used as the solvent, and the solution was prepared in a volume of 200 mL and a concentration of 0.001 mol / L, and was stirred in a water bath at 25°C to keep the temperature of the solution constant. Then, 1.8 g of Cu(OH)2nanowires were put into the solution for impregnation for 10 min, and then were separated by filtration to remove the excess solvent of the Cu(OH)2nanowires.

[0048] The Cu(OH)2nanowires after impregnation were dried, and then calcined in a muffle furnace at 250°C for 6 h to prepare the flagelliform nanowires.

[0049] Example 6

[0050] An ethanol solution of ethanethiothio cyanate with a volume fraction of 100% (i.e. pure ethanol) was used as the solvent, and the solution was prepared in a volume of 220 mL and a concentration of 0.0013 mol / L, and was stirred in a water bath at 20°C to keep the temperature of the solution constant. Then, 1.4 g of Cu(OH)2nanowires were put into the solution for impregnation for 30 min, and then were separated by filtration to remove the excess solvent of the Cu(OH)2nanowires.

[0051] The Cu(OH)2nanowires after impregnation were dried, and then calcined in a muffle furnace at 300°C for 1 h, and then heated to 400°C for 2 h to prepare the flagelliform nanowires.

[0052] Comparative Example 1

[0053] The preparation method was the same as that in Example 1, except that the concentration of the ethanol solution of ethanethiothio cyanate was 0.0025 mol / L, and the calcination was performed in a muffle furnace at 250°C for 7 h, as shown in Figure 3 .

[0054] Comparative Example 2

[0055] The preparation method was the same as that in Example 3, except that an ethanol solution with a volume fraction of 75% was used as the solvent, and the solution was stirred in a water bath at 50°C, and the flagelliform nanowires could not be prepared.

[0056] Comparative Example 3

[0057] The preparation method was the same as that in Example 6, except that the ethanol solution of ethanethiothio cyanate was prepared in a volume of 400 mL and a concentration of 0.0022 mol / L, and the flagelliform nanowires could not be prepared.

[0058] Cu(OH)₂ nanowires were first prepared on 0.5 mm thick copper foam. Then, using the preparation methods described in Examples 1-6 and Comparative Examples 1-3, the Cu(OH)₂ nanowires were transformed into biomimetic flagella-like nanowires. The final material was cut into 12 mm diameter discs as the working electrode and a 15.6 mm diameter lithium sheet as the counter electrode. An ether-based electrolyte (1 M LiTFSI dissolved in DOL / DME (1:1 vol.%), containing 2 wt% LiNO₃) was used. A Celgard 2400 separator was used, and the cells were assembled into 2032 coin cells.

[0059] At 3mA / cm 2 Current density, deposition 1mAh / cm 2 The lithium capacity density was applied to the prepared working electrode, followed by electrochemical stripping at the same current density. After the voltage was increased to 1V, the cycle was switched to the next cycle. The coulombic efficiency (%) of a single cycle = (lithium stripping capacity / lithium deposition capacity) × 100%.

[0060] Table 1. Coulombic efficiency (%) of each battery after 200 cycles

[0061] Example Coulombic efficiency at the 200th cycle (%) Example 1 94.9 Example 2 96.1 Example 3 95.2 Example 4 92.4 Example 5 93.7 Example 6 95.5 Comparative Example 1 70.6 Comparative Example 2 61.3 Comparative Example 3 65.2

[0062] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. People can obtain other embodiments based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A method for preparing a biomimetic flagellated nanowire, characterized by, The method comprises the following steps: 1) mixing and immersing a thiocyanic acid solution with copper hydroxide nanowires, and drying to obtain immersed nanowires; The immersion conditions include a temperature of 20-45℃ and a time of 0.01-50 min; 2) calcining the immersed nanowires obtained in step 1) at 250-500℃ for 2-6 h; The concentration of the thiocyanic acid solution in step 1) is 0.001-0.002 mol / L; The solvent of the thiocyanic acid solution in step 1) includes an ethanol solution, and the volume percentage of ethanol in the ethanol solution is 80-100%; The volume ratio of the thiocyanic acid solution to the mass of copper hydroxide nanowires in step 1) is 100-220 ml:1-2.5 g; The pre-calcination before step 2) includes a temperature of 100-300℃ and a time of 1 h.

2. The method of claim 1, wherein, The concentration of the thiocyanic acid solution is 0.0012-0.0018 mol / L.

3. The method of claim 1, wherein, The volume ratio of the thiocyanic acid solution to the mass of copper hydroxide nanowires is 150-200 ml:1.4-2 g.

4. The method of claim 1, wherein, The immersion conditions in step 1) include a temperature of 25-40℃ and a time of 10-40 min.

5. The method of claim 1, wherein, The calcination conditions in step 2) include a temperature of 300-400℃ and a time of 3-4 h.

6. The method of claim 1, wherein, The pre-calcination temperature is 150-200℃.

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