A method for preparing a transparent flexible zinc mesh by a combination of inkjet printing and chemical deposition

Abstract

The present application adopts inkjet printing and non-catalyst chemical nickel plating method to deposit metal nickel on transparent nylon net and silk net, realizes the preparation of low-cost large-scale flexible transparent conductive substrate with controllable morphology, and is suitable for large-scale mass production. The present application is very beneficial to the integration of planar microelectronic devices. Based on the technology, a flexible transparent Zn net electrode is prepared by electroplating Zn on the Ni-P pattern nylon net. The ZECD window with zinc net anode and prussian blue (PB) cathode shows significant electrochromic performance, including fast switching time, high optical contrast and excellent cycle performance. These ZECDs are also very suitable for solar charging intelligent windows, which can further solve the problem of solar intermittency. These findings open up new opportunities for energy storage and conversion transparent devices.

Description

Technical Field

[0001] This invention belongs to the field of transparent electronics technology, specifically relating to a method for preparing transparent flexible zinc mesh using a combination of inkjet printing and chemical deposition. Background Technology

[0002] Zn anode-based electrochromic devices (ZECDs) are among the most promising technologies in transparent electronics, combining energy storage and electrochromic functionality. However, the opaque Zn anode (Zn foil) limits the performance of existing ZECDs, and this problem can only be solved by developing transparent Zn anodes.

[0003] Currently, transparent conductive electrodes mainly include: conductive glass, silver nanowire transparent conductive substrates, copper nanowire transparent conductive substrates, carbon nanotube transparent conductive substrates, and graphene transparent conductive substrates. However, these materials are too expensive to be suitable for large-scale production, and their complex manufacturing processes further increase production costs.

[0004] Currently, Zn-based anodes are typically zinc sheets placed around the color-changing device, making it difficult to fabricate transparent anodes. Because this sheet-like anode material is located at the edge of the device and far from the center, it exhibits a significant potential difference, leading to uneven electric field distribution and affecting the performance of the electrochromic device. Summary of the Invention

[0005] To address the aforementioned shortcomings in existing technologies, the present invention aims to provide a method for preparing transparent flexible zinc mesh using a combination of inkjet printing and chemical deposition, thereby precisely preparing Ni-P electrode patterns through a cost-effective catalytic electroless deposition method.

[0006] The present invention adopts the following technical solution:

[0007] 1. Prepare a nickel sulfate solution and add it to the ink cartridge of the inkjet printer to prepare for inkjet printing; place the flexible screen into the inkjet printer, print the nickel sulfate evenly onto the screen, and then let it air dry at room temperature;

[0008] 2. Place the dried flexible mesh into a sodium borohydride solution to reduce nickel sulfate to elemental nickel;

[0009] 3. Place the above materials into a chemical nickel plating solution to carry out a nickel plating reaction;

[0010] 4. A layer of metallic zinc is deposited on the nickel surface of the nickel-plated flexible mesh using an electrodeposition method.

[0011] Furthermore, the flexible mesh is made of transparent nylon mesh or silk mesh.

[0012] Furthermore, in step 1, the concentration of the nickel sulfate solution is 0.1-0.5 mol / L.

[0013] Furthermore, in step 2, the concentration of the sodium borohydride solution is 0.2-0.5 mol / L.

[0014] Furthermore, in step 3, the electroless nickel plating solution is: 10-15g of nickel sulfate, 15-20g of sodium hypophosphite, and 15-20g of sodium citrate in 100mL of aqueous solution; the nickel plating reaction temperature is 60-80℃, and the time is 1-4 hours.

[0015] Furthermore, in step 4, the zinc-containing solution used in the electrodeposition method consists of 10-15 g of zinc sulfate and 10-20 g of sodium citrate in 100 mL of aqueous solution; the electrodeposition current is 5-10 mA / cm. 2 The time is 1-4 hours.

[0016] The beneficial effects of this invention are:

[0017] This invention employs inkjet printing and catalyst-free electroless nickel plating to deposit metallic nickel on transparent nylon mesh or silk mesh, achieving morphology-controllable and low-cost large-scale preparation of flexible transparent conductive substrates suitable for mass production.

[0018] This invention is highly advantageous for the integration of planar microelectronic devices. Based on this technology, flexible and transparent Zn mesh electrodes are fabricated by electroplating Zn onto Ni-P patterned nylon or silk mesh. ZECD windows with zinc mesh anodes and Prussian blue (PB) cathodes exhibit remarkable electrochromic properties, including fast switching times, high optical contrast, and excellent cycling performance. These ZECDs are also well-suited for solar-charged smart windows, further addressing the intermittent nature of solar energy. These findings open new opportunities for transparent energy storage and conversion devices. Attached Figure Description

[0019] Figure 1 This is a schematic diagram of the inkjet printing process for electroless nickel plating.

[0020] Figure 2 This is the flexible transparent zinc mesh prepared according to the present invention.

[0021] Figure 3 This is a simulation diagram of the electric field distribution of different types of Zn anodes.

[0022] Figure 4 These are images showcasing an electrochromic device made from the zinc mesh of this invention (different angles of the same device).

[0023] Figure 5 This is a graph showing the electrochromic performance of the device prepared in this invention (the anode of the electrochromic device is a transparent zinc mesh prepared in Example 1 of this invention, and the cathode is Prussian blue (Prussian blue is deposited on conductive glass ITO by electrodeposition)). Implementation

[0024] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. The components of the embodiments of the present invention described and shown in the accompanying drawings can generally be arranged and designed in various different configurations. Therefore, the following detailed description of the embodiments of the present invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention. Example

[0025] (1) Prepare a 0.5 mol nickel sulfate solution and add it to the ink cartridge of the inkjet printer to prepare for inkjet printing; put the transparent nylon mesh into the inkjet printer, print the nickel sulfate evenly onto the transparent nylon mesh, and then let it air dry at room temperature;

[0026] (2) Place the dried nylon mesh into a sodium borohydride solution (0.5 mol) to reduce nickel sulfate to elemental nickel;

[0027] (3) Place the above materials into a chemical nickel plating solution (100 mL of aqueous solution contains 10 g of nickel sulfate, 15 g of sodium hypophosphite and 15 g of sodium citrate) for nickel plating reaction at a temperature of 60°C for 2 hours.

[0028] (4) A layer of metallic zinc is deposited on the nickel surface of the nickel-plated nylon mesh by electrodeposition; the zinc plating solution (100 mL aqueous solution also contains 10 g of zinc sulfate and 10 g of sodium citrate) is used, and the deposition current is 5 mA / cm. 2 The time is 2 hours. Example

[0029] (1) Prepare a 0.5 mol nickel sulfate solution and add it to the ink cartridge of the inkjet printer to prepare for inkjet printing; put the transparent nylon mesh into the inkjet printer, print the nickel sulfate evenly onto the transparent nylon mesh, and then let it air dry at room temperature;

[0030] (2) Place the dried nylon mesh into a sodium borohydride solution (0.5 mol) to reduce nickel sulfate to elemental nickel;

[0031] (3) Place the above materials into a chemical nickel plating solution (100 mL of aqueous solution contains 15 g of nickel sulfate, 20 g of sodium hypophosphite and 20 g of sodium citrate) for nickel plating reaction at a temperature of 60°C for 4 hours.

[0032] (4) A layer of metallic zinc is deposited on the nickel surface of the nickel-plated nylon mesh by electrodeposition; the zinc plating solution (100 mL aqueous solution also contains 15 g of zinc sulfate and 20 g of sodium citrate), the deposition current is 10 mA / cm2, and the time is 2 hours. Example

[0033] (1) Prepare a 0.1 mol nickel sulfate solution and add it to the ink cartridge of the inkjet printer to prepare for inkjet printing; put the transparent nylon mesh into the inkjet printer, print the nickel sulfate evenly onto the transparent nylon mesh, and then let it air dry at room temperature;

[0034] (2) Place the dried nylon mesh into a sodium borohydride solution (0.2 mol) to reduce nickel sulfate to elemental nickel;

[0035] (3) Place the above materials into a chemical nickel plating solution (100 mL of aqueous solution contains 15 g of nickel sulfate, 15 g of sodium hypophosphite and 15 g of sodium citrate) for nickel plating reaction at a temperature of 80°C for 1 hour.

[0036] (4) A layer of metallic zinc is deposited on the nickel surface of the nickel-plated nylon mesh by electrodeposition; the zinc plating solution (100 mL aqueous solution also contains 15 g of zinc sulfate and 15 g of sodium citrate) is used, and the deposition current is 5 mA / cm. 2 The time is 2 hours. Example

[0037] (1) Prepare a 0.5 mol nickel sulfate solution and add it to the ink cartridge of the inkjet printer to prepare for inkjet printing; put the silk screen into the inkjet printer, print the nickel sulfate evenly onto the silk screen, and then let it dry at room temperature;

[0038] (2) Place the dried silk netting into a sodium borohydride solution (0.5 mol) to reduce nickel sulfate to elemental nickel;

[0039] (3) Place the above materials into a chemical nickel plating solution (100 mL of aqueous solution contains 10 g of nickel sulfate, 15 g of sodium hypophosphite and 15 g of sodium citrate) for nickel plating reaction at a temperature of 60°C for 2 hours.

[0040] (4) A layer of metallic zinc is deposited on the nickel-plated silk mesh by electrodeposition; the zinc plating solution (100 mL aqueous solution also contains 10 g of zinc sulfate and 10 g of sodium citrate) is used, and the deposition current is 5 mA / cm. 2 The time is 2 hours.

[0041]

[0042] Table 1

[0043] Electrochromic performance test:

[0044] Switching time test: The switching time was measured by in-situ UV-Vis spectroscopy. The prepared electrochromic device was placed in the spectrometer, and then colored and faded it using an electrochemical workstation. The coloring and fading times were 15 seconds each. The spectrometer recorded the transmittance changes during the process. The test results are shown in Table 1.

[0045] High optical contrast ratio test: Contrast ratio was measured by in-situ UV-Vis spectroscopy. The prepared electrochromic device was placed in a spectrometer, and then colored and faded using an electrochemical workstation. The coloring and fading times were 10-30 seconds, and the spectrometer recorded the transmittance changes during the process. The control sample was blank conductive glass. The test results are shown in Table 1.

[0046] Cyclic performance testing: Cyclic performance was tested in situ using UV-Vis spectroscopy. The prepared electrochromic device was placed in a spectrometer, and then colored and faded using an electrochemical workstation. The coloring and fading times were 20 seconds each, and the test time was 10,000 seconds. The spectrometer recorded the transmittance changes during the process. The test results are shown in Table 1.

[0047] Tests showed that the ZECD window with zinc mesh anode and Prussian blue (PB) cathode exhibited remarkable electrochromic performance, including fast switching time, high optical contrast and excellent cycling performance.

[0048] Figure 5 These are performance graphs of the electrochromic device prepared in this invention applied to color-changing windows. The test data mainly focuses on the performance of color-changing windows in practical applications. Figure d shows the visible light transmittance during device testing; red represents the fading device, and black represents the visible light absorption spectrum of the coloring device. Figure d indicates the device's ability to transmit and block visible light, reflecting the window's light-blocking capability. Figure e shows the visible light transmittance during the device's transition from transparent to coloring, indicating the color-changing time and the window's speed. Figure f shows the cyclic performance test, where the device is continuously colored and faded to test cyclic stability. Figure f reflects the window's performance after long-term use and repeated color changes. Figure g shows the time the device can maintain its coloring and fading states (red represents the fading device, black represents the coloring device), testing the device's stability. Because electrochromic devices may gradually recolor after fading, this demonstrates the window's ability to maintain its original state after coloring or fading. The device in this invention maintained its original state with minimal change after 2000 seconds. The illustration shows the use of a solar cell as a power source; the device can be integrated with a solar cell. Figure 5 It can be seen that the electrochromic device with transparent flexible zinc mesh as the anode prepared based on the present invention has significant electrochromic properties.

[0049] Figure 3These are simulation diagrams of the electric field distribution of different types of Zn anodes. Figure 3 This shows the electric field distribution of a conventional sheet zinc plate and our prepared transparent Zn electrode after an electric field is applied during testing. Figure 3 In figure b, the upper figure shows the distribution of the electric field in the device after applying voltage to the transparent Zn mesh of the present invention, which is uniform. The lower figure shows the distribution of the electric field in the device after applying voltage to a conventional sheet zinc plate. Because the ordinary zinc plate is located at the edge of the device, the electric field distribution is not uniform after applying voltage. Figure 3 c represents the electric field distribution after applying voltage to the ITO.

[0050] The above content is only for illustrating the technical concept of the present invention and should not be construed as limiting the scope of protection of the present invention. Any modifications made to the technical solution based on the technical concept proposed in this invention shall fall within the scope of protection of the claims of this invention.

Claims

1. A method for preparing transparent flexible zinc mesh by combining inkjet printing and chemical deposition, characterized in that: The specific steps of this method are as follows: (1) Prepare a nickel sulfate solution and add it to the ink cartridge of the inkjet printer to prepare for inkjet printing; put the flexible screen into the inkjet printer, print the nickel sulfate evenly onto the screen, and then let it air dry at room temperature; (2) Place the dried flexible mesh into a sodium borohydride solution to reduce nickel sulfate to elemental nickel; (3) Place the above materials into a chemical nickel plating solution to carry out a nickel plating reaction; (4) A layer of metallic zinc is deposited on the nickel surface of the nickel-plated flexible mesh by electrodeposition.

2. The method for preparing transparent flexible zinc mesh by combining inkjet printing and chemical deposition as described in claim 1, characterized in that: The flexible mesh is made of transparent nylon or silk.

3. The method for preparing transparent flexible zinc mesh by combining inkjet printing and chemical deposition as described in claim 1, characterized in that: In step 1, the concentration of the nickel sulfate solution is 0.1-0.5 mol / L.

4. The method for preparing transparent flexible zinc mesh by combining inkjet printing and chemical deposition as described in claim 1, characterized in that: In step 2, the concentration of sodium borohydride solution is 0.2-0.5 mol / L.

5. The method for preparing transparent flexible zinc mesh by combining inkjet printing and chemical deposition as described in claim 1, characterized in that: In step 3, the electroless nickel plating solution is: 10-15g of nickel sulfate, 15-20g of sodium hypophosphite, and 15-20g of sodium citrate in 100mL of aqueous solution; the nickel plating reaction temperature is 60-80℃, and the time is 1-4 hours.

6. The method for preparing transparent flexible zinc mesh by combining inkjet printing and chemical deposition as described in claim 1, characterized in that: In step 4, the zinc-containing solution used in the electrodeposition method consists of 10-15 g of zinc sulfate and 10-20 g of sodium citrate in 100 mL of aqueous solution; the electrodeposition current is 5-10 mA / cm. 2 The time is 1-4 hours.

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