Preparation method of copper sulfide-based flexible supercapacitor electrode

Abstract

The present invention relates to a preparation method of a copper sulfide-based flexible supercapacitor electrode, belonging to the field of new energy device fabrication. It is characterized in that the copper wire of the supercapacitor electrode substrate is used as the copper source, and sodium sulfide is used as the sulfur source, and sheet-structured copper sulfide is obtained through a one-step liquid-phase reaction. The preparation process includes the following steps: First, stir the sodium sulfide solution with a concentration of 0.5 mol / L - 2 mol / L at room temperature for 20 min, and then ultrasonically clean a copper wire with an appropriate length in acetone, concentrated hydrochloric acid, and deionized water for 10 min each; after drying the above copper wire with nitrogen, immerse it in the sodium sulfide solution, transfer it to a sample tube and seal it, and let it stand at room temperature for 24 h - 48 h; finally, wash the copper wire with deionized water and dry it with nitrogen to obtain a copper sulfide-based flexible supercapacitor electrode. The present invention has the advantages of being simple and easy to implement and having a high repetition rate. The copper wire and copper sulfide are firmly combined. The electrode has a long cycle life and good stability, and there is no obvious change in the structure after experiencing multiple charge and discharge cycles.

Description

Technical Field

[0001] The present invention relates to a preparation method of a copper sulfide-based flexible supercapacitor electrode, belonging to the field of new energy device manufacturing. Background Art

[0002] With people's unremitting pursuit of a better life, portable electronic products have brought people a high-quality life experience. For example, smart phones, wireless earphones, smart bracelets, etc. Correspondingly, the research and development of new energy storage devices have become particularly urgent, making the majority of scientific researchers full of strong interest in the research of this field, especially the rapid development and wide use of flexible electronic products in recent years.

[0003] Supercapacitors, as a new type of energy storage device between traditional capacitors and batteries, have the advantages of high power density, long cycle life, fast charge and discharge speed, low price, and environmental friendliness. As the core component of supercapacitors, the electrode active material is the key factor determining the electrochemical performance of energy storage devices.

[0004] Currently, the commonly used active materials mainly include three categories: carbon materials, metal oxides, and conductive polymer materials. With the continuous in-depth research on various electrode active materials, it has been found that transition metal sulfides have high intrinsic conductivity and electrochemical activity, and also have great application potential in supercapacitor electrode active materials. People have carried out various electrochemical performance studies on binary metal sulfides or ternary metal sulfides.

[0005] In this patent, it involves a preparation method of a copper sulfide-based flexible supercapacitor electrode. In this method, copper wire is used as the inner substrate of the electrode and also as the copper source, and sodium sulfide provides sulfide ions. The two react under normal temperature conditions to obtain a large number of flaky structures of copper sulfide attached to the surface of the copper wire. This preparation method has the advantages of being simple and easy to operate, easy to control conditions, environmentally friendly, etc., and at the same time has a low production cost. Summary of the Invention

[0006] 1. A preparation method of a copper sulfide-based flexible supercapacitor electrode, using copper wire as the inner substrate of the electrode and also as the copper source, and sodium sulfide provides sulfide ions. Under normal temperature, copper sulfide with a flaky structure is obtained by reaction. This method has the advantages of being simple and easy to operate, easy to control conditions, environmentally friendly, etc. This method mainly includes the following steps:

[0007] (1) Weigh an appropriate amount of sodium sulfide and add it to a certain amount of deionized water to prepare a sodium sulfide solution with a certain concentration, and stir it evenly for 20 min at normal temperature;

[0008] (2) Transfer the above sodium sulfide solution to a sample tube, and then pass nitrogen into the solution to remove oxygen for 10 min;

[0009] (3) Take a copper wire of a certain length, ultrasonically clean it with acetone solution, concentrated hydrochloric acid and deionized water for 10 minutes in sequence, then take it out and dry it with nitrogen;

[0010] (4) Place the copper wire in a sodium sulfide solution, then seal the sample tube and let it stand for a certain time at room temperature;

[0011] (5) After the reaction is completed, take out the product from the sample tube and wash the product 3 times with deionized water;

[0012] (6) Place the product in a tube furnace, heat-treat it for 1 hour under the protection of a nitrogen atmosphere, then evacuate the tube furnace and let it cool naturally, and a copper sulfide-based flexible supercapacitor electrode is obtained.

[0013] 2. The preparation method of a copper sulfide-based flexible supercapacitor electrode according to claim 1, wherein the concentration of the sodium sulfide solution in step (1) is 0.5 mol / L to 2 mol / L.

[0014] 3. The preparation method of a copper sulfide-based flexible supercapacitor electrode according to claim 1, wherein the standing time in step (4) is 24 h - 72 h. Description of the Drawings

[0015] Figure 1 is a low-magnification scanning electron microscope photograph of a copper sulfide-based flexible supercapacitor electrode. It can be observed from this figure that the copper wire is uniformly covered with flaky sodium sulfide.

[0016] Figure 2 is a high-magnification scanning electron microscope photograph of a copper sulfide-based flexible supercapacitor electrode. It can be observed from this figure that the thickness of the sodium sulfide flakes is relatively consistent, and the thickness distribution range is between 400 - 700 nm.

[0017] Figure 3 is a high-resolution X-ray photoelectron spectroscopy spectrum of copper element of a copper sulfide-based flexible supercapacitor electrode.

[0018] Figure 4 is a high-resolution X-ray photoelectron spectroscopy spectrum of sulfur element of a copper sulfide-based flexible supercapacitor electrode. Detailed Embodiments Detailed Embodiment One:

[0020] (1) Weigh 6.127 g of sodium sulfide and add it to 50 mL of deionized water to prepare a solution, and stir it at room temperature for 20 minutes;

[0021] (2) Transfer 10 mL of the above solution to a sample tube and purge the solution with nitrogen to remove oxygen for 10 minutes;

[0022] (3) Take a copper wire of a certain length, ultrasonically clean it with acetone solution, concentrated hydrochloric acid and deionized water for 10 min in sequence, and then dry it with nitrogen gas;

[0023] (4) Place the copper wire in a sodium sulfide solution, then seal the sample tube and let it stand at room temperature for 24 h;

[0024] (5) After the reaction is completed, take out the product from the sample tube and wash the product 3 times with deionized water;

[0025] (6) Place the product in a tube furnace, heat-treat it for 1 h under the protection of a nitrogen atmosphere, then evacuate the tube furnace and let it cool naturally to obtain a one-dimensional copper sulfide-based flexible supercapacitor electrode. Specific Embodiment 2:

[0027] (1) Weigh 12.254 g of sodium sulfide and add it to 50 mL of deionized water to prepare a solution, and stir it at room temperature for 20 min;

[0028] (2) Transfer 10 mL of the above solution to a sample tube and purge the solution with nitrogen to remove oxygen for 10 min;

[0029] (3) Take a copper wire of a certain length, ultrasonically clean it with acetone solution, concentrated hydrochloric acid and deionized water for 10 min in sequence, and then dry it with nitrogen gas;

[0030] (4) Place the copper wire in a sodium sulfide solution, then seal the sample tube and let it stand at room temperature for 24 h;

[0031] (5) After the reaction is completed, take out the product from the sample tube and wash the product 3 times with deionized water;

[0032] (6) Place the product in a tube furnace, heat-treat it for 1 h under the protection of a nitrogen atmosphere, then evacuate the tube furnace and let it cool naturally to obtain a one-dimensional copper sulfide-based flexible supercapacitor electrode. Specific Embodiment 3:

[0034] (1) Weigh 24.508 g of sodium sulfide and add it to 50 mL of deionized water to prepare a solution, and stir it at room temperature for 20 min;

[0035] (2) Transfer 10 mL of the above solution to a sample tube and purge the solution with nitrogen to remove oxygen for 10 min;

[0036] (3) Take a copper wire of a certain length, ultrasonically clean it with acetone solution, concentrated hydrochloric acid and deionized water for 10 min in sequence, and then dry it with nitrogen gas;

[0037] (4) Place the copper wire in a sodium sulfide solution, then seal the sample tube and let it stand at room temperature for 24 h;

[0038] (5) After the reaction is completed, take out the product from the sample tube and wash the product three times with deionized water;

[0039] (6) Place the product in a tube furnace and heat-treat it for 1 h under the protection of a nitrogen atmosphere. Then evacuate the tube furnace and let it cool naturally to obtain the one-dimensional copper sulfide-based flexible supercapacitor electrode. Specific Embodiment Four:

[0041] (1) Weigh 6.127 g of sodium sulfide and add it to 50 mL of deionized water to prepare a solution, and stir it at room temperature for 20 min;

[0042] (2) Transfer 10 mL of the above solution to a sample tube and purge the solution with nitrogen for 10 min to remove oxygen;

[0043] (3) Take a certain length of copper wire, ultrasonically clean it with acetone solution, concentrated hydrochloric acid and deionized water for 10 min in sequence, and then dry it with nitrogen;

[0044] (4) Place the copper wire in the sodium sulfide solution, then seal the sample tube and let it stand at room temperature for 48 h;

[0045] (5) After the reaction is completed, take out the product from the sample tube and wash the product three times with deionized water;

[0046] (6) Place the product in a tube furnace and heat-treat it for 1 h under the protection of a nitrogen atmosphere. Then evacuate the tube furnace and let it cool naturally to obtain the one-dimensional copper sulfide-based flexible supercapacitor electrode. Specific Embodiment Five:

[0048] (1) Weigh 12.254 g of sodium sulfide and add it to 50 mL of deionized water to prepare a solution, and stir it at room temperature for 20 min;

[0049] (2) Transfer 10 mL of the above solution to a sample tube and purge the solution with nitrogen for 10 min to remove oxygen;

[0050] (3) Take a certain length of copper wire, ultrasonically clean it with acetone solution, concentrated hydrochloric acid and deionized water for 10 min in sequence, and then dry it with nitrogen;

[0051] (4) Place the copper wire in the sodium sulfide solution, then seal the sample tube and let it stand at room temperature for 48 h;

[0052] (5) After the reaction is completed, take out the product from the sample tube and wash the product three times with deionized water;

[0053] (6) Place the product in a tube furnace and heat-treat it for 1 h under the protection of a nitrogen atmosphere. Then, evacuate the tube furnace and let it cool naturally to obtain the one-dimensional copper sulfide-based flexible supercapacitor electrode. Specific Embodiment Six:

[0055] (1) Weigh 24.508 g of sodium sulfide and add it to 50 mL of deionized water to prepare a solution. Stir the solution at room temperature for 20 min.

[0056] (2) Transfer 10 mL of the above solution to a sample tube and purge the solution with nitrogen to remove oxygen for 10 min.

[0057] (3) Take a copper wire of a certain length and ultrasonically clean it with acetone solution, concentrated hydrochloric acid, and deionized water for 10 min in sequence. Then, dry it with nitrogen.

[0058] (4) Place the copper wire in the sodium sulfide solution, then seal the sample tube and let it stand at room temperature for 48 h.

[0059] (5) After the reaction is completed, take out the product from the sample tube and wash the product three times with deionized water.

[0060] (6) Place the product in a tube furnace and heat-treat it for 1 h under the protection of a nitrogen atmosphere. Then, evacuate the tube furnace and let it cool naturally to obtain the one-dimensional copper sulfide-based flexible supercapacitor electrode. Specific Embodiment Seven:

[0062] (1) Weigh 6.127 g of sodium sulfide and add it to 50 mL of deionized water to prepare a solution. Stir the solution at room temperature for 20 min.

[0063] (2) Transfer 10 mL of the above solution to a sample tube and purge the solution with nitrogen to remove oxygen for 10 min.

[0064] (3) Take a copper wire of a certain length and ultrasonically clean it with acetone solution, concentrated hydrochloric acid, and deionized water for 10 min in sequence. Then, dry it with nitrogen.

[0065] (4) Place the copper wire in the sodium sulfide solution, then seal the sample tube and let it stand at room temperature for 72 h.

[0066] (5) After the reaction is completed, take out the product from the sample tube and wash the product three times with deionized water.

[0067] (6) Place the product in a tube furnace and heat-treat it for 1 h under the protection of a nitrogen atmosphere. Then, evacuate the tube furnace and let it cool naturally to obtain the one-dimensional copper sulfide-based flexible supercapacitor electrode. Specific Embodiment Eight:

[0069] (1) Weigh 12.254 g of sodium sulfide and add it to 50 mL of deionized water to prepare a solution, and stir it at room temperature for 20 min;

[0070] (2) Transfer 10 mL of the above solution to a sample tube, and pass nitrogen into the solution to remove oxygen for 10 min;

[0071] (3) Take a copper wire of a certain length, ultrasonically clean it with acetone solution, concentrated hydrochloric acid and deionized water for 10 min in sequence, and then dry it with nitrogen;

[0072] (4) Place the copper wire in the sodium sulfide solution, then seal the sample tube and let it stand at room temperature for 72 h;

[0073] (5) After the reaction is completed, take out the product from the sample tube and wash the product 3 times with deionized water;

[0074] (6) Place the product in a tubular furnace, heat-treat it for 1 h under the protection of a nitrogen atmosphere, then evacuate the tubular furnace and let it cool naturally to obtain a one-dimensional copper sulfide-based flexible supercapacitor electrode.

Claims

1. A preparation method of a copper sulfide-based flexible supercapacitor electrode, using a copper wire as the inner substrate of the electrode and as a copper source, and sodium sulfide providing sulfide ions. Under normal temperature conditions, sheet-structured copper sulfide is obtained through a liquid-phase reaction, with a relatively consistent thickness and a distribution range between 400 - 700 nm. This method mainly includes the following steps: (1) Weigh an appropriate amount of sodium sulfide and add it to a certain amount of deionized water to prepare a sodium sulfide solution with a concentration of 0.5 mol / L - 2 mol / L, and stir it evenly at room temperature for 20 min; (2) Transfer the above sodium sulfide solution to a sample tube, and then introduce nitrogen into the solution to remove oxygen for 10 min; (3) Take a certain length of copper wire, ultrasonically clean it with acetone solution, concentrated hydrochloric acid, and deionized water for 10 min each in turn, then take it out and dry it with nitrogen; (4) Place the copper wire in the sodium sulfide solution, then seal the sample tube, and let it stand at room temperature for 24 h - 72 h; (5) After the reaction is completed, take out the product from the sample tube and wash the product 3 times with deionized water; (6) Place the product in a tube furnace, heat-treat it for 1 h under the protection of a nitrogen atmosphere, then evacuate the tube furnace and let it cool naturally to obtain a copper sulfide-based flexible supercapacitor electrode.

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