An integrated underwater adhesive energy recovery material, its preparation method and application

Abstract

This invention discloses an integrated underwater adhesion and energy recovery material, its preparation method, and its application. The integrated underwater adhesion-energy recovery material has a layered structure with inconsistent upper and lower layers. The upper layer is a three-dimensional carbon material framework structure, and the lower layer has vertically oriented channels and surface pores. The three-dimensional carbon material framework structure is a vertically oriented three-dimensional structure formed by carbon material. This invention achieves integrated underwater adhesion and energy recovery functions through a special layered structure design. Furthermore, this material can be used not only as a multifunctional material but also as a standalone underwater adhesion material or energy recovery material, demonstrating strong applicability. This invention can also convert the mechanical energy generated by underwater robots into electrical energy while assisting in underwater robot operations, providing a convenient and green charging method and reducing energy consumption.

Description

Technical Field

[0001] This invention belongs to the field of mechanical energy recovery technology, specifically relating to an integrated underwater adhesive energy recovery material, its preparation method, and its application. Background Technology

[0002] With the continuous development of marine resources and the objective challenges posed by harsh underwater environments and the limited diving depth of humans, underwater robots have become crucial tools for ocean development. Underwater robots require stable and recyclable underwater adhesive materials for crawling, grasping, and other operations. However, achieving underwater adhesive materials with both high adhesion strength and high recyclability remains challenging. Furthermore, underwater robots face the problem of limited battery life, which severely restricts their ability to perform extended missions. In summary, underwater adhesive materials and the power supply for underwater robots are two major issues that urgently need to be addressed in the field of underwater robotics.

[0003] Underwater robots, as energy-consuming devices, require regular charging, and the underwater environment increases the complexity of their electrical systems. Furthermore, the physical movements involved in underwater robot operations, such as crawling and grasping, generate mechanical energy, which is often wasted. In recent years, self-powered energy harvesting technology has become an widely studied alternative method for charging energy-consuming devices. Researchers have developed energy harvesting devices based on four mechanisms: piezoelectricity, ferroelectricity, triboelectricity, and electrochemistry. If the mechanical energy generated by the physical movements of underwater robots can be converted into electrical energy and harvested to charge the robot, it will represent a new breakthrough in the field of underwater robotics. This technology would allow underwater robots to obtain timely power supply when energy reserves are insufficient during missions.

[0004] In summary, the use of adhesive materials and energy recovery materials is a requirement for the multifunctional development of underwater robots, and multifunctional integration can reduce the complexity of robot systems. Therefore, this invention aims to develop an integrated underwater circulating adhesive-energy recovery material. Summary of the Invention

[0005] To address the aforementioned deficiencies or improvement needs of existing technologies, this invention provides an integrated underwater cyclic adhesion and energy recovery material. This invention achieves a layered structure through a special preparation process using a vertically oriented three-dimensional carbon material framework and a polymer solution, resulting in a multifunctional underwater cyclic adhesion and energy recovery material. The layered structure includes vertical channels and surface pores that provide underwater cyclic adhesion properties, while the three-dimensional carbon material framework provides energy recovery properties. When applied to underwater robots, this material can ensure stable operation while recovering the mechanical energy generated during robot operations and converting it into electrical energy, thus reducing energy waste and consumption.

[0006] As one aspect of the present invention, the present invention provides an integrated underwater adhesion-energy recovery material, wherein: the integrated underwater cyclic adhesion-energy recovery material has a layered structure with inconsistent upper and lower layers, the upper layer being a three-dimensional carbon material skeleton structure, and the lower layer having vertically oriented pore channels and surface pore structures; wherein the three-dimensional carbon material skeleton structure is a vertically oriented three-dimensional structure formed by carbon material.

[0007] As a preferred embodiment of the underwater adhesive energy recovery integrated material of the present invention, the ratio of the height of the upper structure to the height of the lower structure is 0.1-10.

[0008] As a preferred embodiment of the underwater adhesive energy recovery integrated material described in this invention: the carbon material includes one or more of carbon nanotubes, graphene, and activated carbon.

[0009] As a preferred embodiment of the underwater adhesion energy recovery integrated material of the present invention: the polymer material includes one or more of gelatin, polyvinyl alcohol, and conductive polymers, wherein the conductive polymers include polyaniline and polypyrrole.

[0010] As another aspect of the present invention, the present invention provides a method for preparing the aforementioned integrated underwater adhesive energy recovery material, which includes the following steps:

[0011] (1) Prepare a vertically oriented three-dimensional carbon material framework and use it as a template material;

[0012] (2) Immerse part of the template material in the polymer solution and expose the other part to the air;

[0013] (3) The template material immersed in the polymer solution is sealed by physical and / or chemical action to finally form an integrated underwater adhesion energy recovery material with a layered structure.

[0014] As a preferred embodiment of the preparation method of the underwater adhesive energy recovery integrated material of the present invention, the viscosity range of the polymer solution is 1 cs-3000 cs.

[0015] As a preferred embodiment of the preparation method of the underwater adhesive energy recovery integrated material of the present invention: the physical action is physical cross-linking and curing, and the chemical action is chemical cross-linking.

[0016] As another aspect of the invention, the invention provides the use of the material in the preparation of materials having underwater cyclic adhesion and / or energy recovery functions.

[0017] The three-dimensional carbon material skeleton structure provides energy recovery, the vertically oriented pore channel and surface pore structure provide underwater circulation adhesion, and the integrated underwater adhesion energy recovery material can be used as a multifunctional material or as an underwater circulation adhesion material or energy recovery material alone; the energy recovery function is to convert mechanical energy into electrical energy.

[0018] The underwater adhesion energy recovery integrated material can be assembled with a current collector, a wire, and a counter electrode to form an underwater circulating adhesion-energy recovery integrated device. When the device realizes the energy recovery function, the electrolyte environment includes seawater, lake water, NaCl aqueous solution, and KOH aqueous solution.

[0019] The beneficial effects of this invention are:

[0020] (1) The underwater circulating adhesion-energy recovery integrated material of the present invention achieves the integration of underwater circulating adhesion and energy recovery functions through a special layered structure design. In addition, this material can be used not only as a multifunctional material, but also as an underwater circulating adhesion material or an energy recovery material, making it highly applicable.

[0021] (2) The underwater circulating adhesion-energy recovery integrated material described in this invention can convert the mechanical energy generated by underwater robots into electrical energy while assisting underwater robot operations. It provides a convenient and green charging method and reduces energy consumption. Attached Figure Description

[0022] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below, wherein:

[0023] Figure 1 This is a schematic diagram of the structure of an underwater circulating adhesion-energy recovery integrated material provided by the present invention.

[0024] Figure 2 This is a schematic diagram of the preparation process in Example 1.

[0025] Figure 3 The adhesion performance of the integrated underwater cyclic adhesion-energy recovery material obtained in Example 1 at different immersion depths is shown.

[0026] Figure 4 The output power of the underwater circulating adhesion-energy recovery integrated material obtained at different immersion depths in Example 1 is shown.

[0027] Figure 5 The cycling performance of the underwater cyclic adhesion-energy recovery integrated material obtained in Example 1 is shown.

[0028] Figure 6The adhesion performance of the underwater circulating adhesion-energy recovery integrated material obtained in Example 1 on different substrates is shown.

[0029] Figure 7 The cycling performance of the underwater cyclic adhesion-energy recovery integrated material obtained in Example 2 is shown.

[0030] Figure 8 The electrical signal output of the underwater circulating adhesion-energy recovery integrated material obtained in Example 2 under different pressures.

[0031] Figure 9 The cyclic adhesion performance of the underwater cyclic adhesion-energy recovery integrated material obtained in Example 3 is shown.

[0032] Figure 10 The electrical signal output of the underwater circulating adhesion-energy recovery integrated material obtained in Example 3 under different pressures.

[0033] Figure 11 The cyclic adhesion performance of the underwater cyclic adhesion-energy recovery integrated material obtained in Example 4 is shown.

[0034] Figure 12 The electrical signal output of the underwater circulating adhesion-energy recovery integrated material obtained in Example 4 under different pressures. Detailed Implementation

[0035] To make the above-mentioned objectives, features and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below with reference to specific examples.

[0036] Please see Figure 1 The present invention provides an integrated underwater circulating adhesion-energy recovery material, wherein the material has a layered structure, the upper layer being a three-dimensional carbon material framework structure, and the lower layer having vertically oriented pore channels and surface pore structures. The upper carbon material structure provides energy recovery functionality through the electrochemical double-layer effect in an electrolyte environment. The vertically oriented pore channels and surface pore structures of the lower structure provide underwater circulating adhesion performance. The preparation method for achieving the above structure includes the following steps:

[0037] Step 1: Prepare the template material. To simultaneously achieve underwater cyclic adhesion and energy recovery functions, a vertically oriented three-dimensional carbon material framework needs to be prepared as the template material. Step 2: Immerse a portion of the template material in a polymer (monomer) solution, while exposing the other portion to air. Step 3: Seal the template material immersed in the polymer (monomer) solution through physical and / or chemical processes. This ultimately forms an integrated underwater cyclic adhesion-energy recovery material with a layered structure. It should be noted that during the preparation of this integrated underwater cyclic adhesion-energy recovery material, the structural parameters of the three-dimensional carbon material framework and the immersion height of the template material in the solution are controllable. The following examples further illustrate this invention in detail.

[0038] Example 1:

[0039] Example 1 of this invention provides an integrated underwater circulating adhesion-energy recovery material and its preparation method. A carbon nanotube array is prepared as the template material, and an aqueous solution of aniline is selected as the monomer liquid. The preparation process is as follows: Figure 2 As shown, the detailed preparation steps are as follows:

[0040] (1) Carbon nanotube arrays were prepared as a three-dimensional carbon material framework by water-assisted chemical vapor deposition. The specific steps were as follows: ① First, a buffer layer and a catalyst layer were deposited on a single-sided polished silicon wafer using magnetron sputtering. The buffer layer was composed of aluminum and was sputtered by radio frequency reactive sputtering. High-purity argon gas was introduced at 15 sccm during the sputtering process, the sputtering power was 200 W, and the sputtering time was 60 s. The catalyst layer was composed of iron and was sputtered by DC sputtering. High-purity argon gas was introduced at 12 sccm during the sputtering process, the sputtering power was 20 W, and the sputtering time was 45 s. ② The silicon wafers that had undergone radio frequency sputtering and DC sputtering were placed in a three-inch tube furnace, and carbon nanotube forests were grown by water-assisted chemical vapor deposition. The total gas flow rate during the growth process was 1000 sccm, with hydrogen content ranging from 5% to 20%, ethylene content from 15%, and argon carrying water vapor comprising 25% of the total gas, while the argon content ranged from 40% to 55%. The growth temperature was 780℃, and the growth time ranged from 300 to 900 s. The resulting carbon nanotube forests ranged in height from 400 to 1000 μm and in density from 5 to 35 mg / cm³. 3 The carbon nanotube forest density was selected to be 20 mg / cm³. 3 A carbon nanotube forest with a height of 900 μm was prepared and tested as follows.

[0041] (2) Weigh 0.1g of ammonium persulfate, place it in container A, add 1mL of deionized water to fully dissolve the ammonium persulfate, and cool to 4℃ for later use.

[0042] (3) Place 2 mL of deionized water in container B. Use a pipette to add 920 μL of a 50% phytic acid aqueous solution to container B and mix thoroughly. Then add 350 μL of aniline and stir the mixture with a magnetic stirrer until it becomes colorless and transparent. Cool the mixture to 4°C in a low-temperature environment for later use.

[0043] (4) The density obtained in step (1) is 20 mg / cm³ 3 A portion of a carbon nanotube forest with a height of 900 μm was immersed in the solution obtained in step (3) to a depth of 300 μm for about 2 hours and then placed in an environment at 4°C for later use.

[0044] (5) Add the solution obtained in step (2) to the solution in step (4), mix well, and place in a low temperature environment of 4℃ to carry out a chemical cross-linking reaction for ≥8 hours.

[0045] (6) Take out the sample obtained in step (5) and rinse the surface with deionized water to remove excess reaction products.

[0046] Similarly, samples with carbon nanotube forest immersion depths of 400 μm, 500 μm, 600 μm, and 700 μm were prepared using the above steps. These samples were then assembled into energy recovery devices, and their underwater cycling adhesion performance was tested using a static mechanical testing instrument, while their energy recovery function was tested using an electrochemical workstation. Theoretically, under the same parameters of the carbon nanotube forest and the polymer liquid, the immersion depth of the carbon nanotube forest in the polymer liquid is independent of the formation of its surface pore structure. Therefore, for samples with immersion depths of 300 μm, 400 μm, 500 μm, 600 μm, and 700 μm, their underwater adhesion strengths under a 5 N pre-pressure are not significantly different, at 24.3 kPa, 21.5 kPa, 22.7 kPa, 25.8 kPa, and 23.8 kPa, respectively. Figure 3 As shown. The electrochemical double-layer effect of the three-dimensional carbon material framework in an electrolyte environment provides energy recovery performance; therefore, the immersion depth of the carbon nanotube forest may affect its energy recovery performance. For samples with immersion depths of 300 μm, 400 μm, 500 μm, 600 μm, and 700 μm, the peak output power under a pre-pressure of 5 N were 0.055 μW, 0.076 μW, 0.11 μW, 0.145 μW, and 0.2 μW, respectively. Figure 4 As shown. Further testing was conducted on the cyclic adhesion performance of the sample immersed to a depth of 600 μm and its adhesion performance on different substrates, as shown. Figure 5 , 6As shown, the sample maintained an adhesion performance of over 95% during 1000 adhesion-desorption cycles under a 5N pre-pressure. Furthermore, its adhesion performance on glass, stainless steel, copper, PTFE, and aluminum substrates was 25.8 kPa, 20.4 kPa, 21.7 kPa, 21.2 kPa, and 22.9 kPa, respectively. Based on these experimental results, the aforementioned structure and its preparation method can successfully develop an integrated underwater cyclic adhesion-energy recovery material.

[0047] Example 2:

[0048] Example 2 of this invention provides an integrated underwater circulating adhesion-energy recovery material and its preparation method. A carbon nanotube forest is used as the template material, and a gelatin aqueous solution is used as the polymer liquid. Detailed preparation steps are as follows:

[0049] (1) A carbon nanotube forest was grown using water-assisted chemical vapor deposition as a template material. The preparation method of the carbon nanotube forest in Example 2 was the same as in Example 1, with a density of 24 mg / cm³. 3 A carbon nanotube forest with a height of 800 μm was prepared as follows.

[0050] (2) Prepare a gelatin aqueous solution with a mass fraction of 3%, and vertically immerse a portion of the carbon nanotube forest obtained in step (1) in the gelatin aqueous solution for about 2 hours, with an immersion depth of 500 μm.

[0051] (3) Remove the carbon nanotube forest from the solution, rinse the gelatin solution on its surface with deionized water, and then use lint-free paper to absorb the water on the surface of the carbon nanotube forest.

[0052] (4) Place the sample obtained in step (3) in the air or in a low-temperature environment for about 1 hour. The gelatin inside the carbon nanotube forest will solidify, and the sample will be successfully prepared.

[0053] The above samples were assembled into an energy recovery device. Its underwater cyclic adhesion performance was tested using a static mechanical testing instrument, and its energy recovery function was tested using an electrochemical workstation. The sample obtained in Example 2 showed an adhesion strength of approximately 70 kPa under a 5 N pre-pressure underwater, and its adhesion performance remained stable after 1000 adhesion-desorption cycles. Figure 7 As shown. Furthermore, the output voltages of this material under preloads of 5N, 10N, and 15N are 0.3mV, 0.45mV, and 0.6mV, respectively. Figure 8 As shown. Therefore, the above preparation method can successfully prepare materials that simultaneously possess underwater circulation adhesion and energy recovery functions.

[0054] Example 3:

[0055] Example 3 of this invention provides an integrated underwater circulating adhesion-energy recovery material and its preparation method. A carbon nanotube forest is used as the template material, and the polymer liquid is a polyvinyl alcohol-gelatin mixed aqueous solution. Detailed preparation steps are as follows:

[0056] (1) A carbon nanotube forest was grown using water-assisted chemical vapor deposition (VAD) to serve as a three-dimensional carbon material framework. The preparation method of the carbon nanotube forest in Example 3 was the same as in Example 1, with a density of 27 mg / cm³. 3 A forest of carbon nanotubes with a height of 900 μm was prepared as follows.

[0057] (2) Preparation of polyvinyl alcohol-gelatin mixed aqueous solution. Prepare a 3% polyvinyl alcohol aqueous solution and a gelatin aqueous solution respectively. Take 1 mL of the polyvinyl alcohol aqueous solution and 1 mL of the gelatin aqueous solution from each solution and mix them evenly for later use.

[0058] (3) The density obtained in step (1) is 27 mg / cm³. 3 A section of a carbon nanotube forest, 900 μm in height, was immersed in a polyvinyl alcohol-gelatin aqueous solution for about 2 hours, with a immersion depth of 400 μm.

[0059] (4) Take out the sample from step (3), rinse the surface with polyvinyl alcohol-gelatin aqueous solution and absorb the water with lint-free paper, then freeze it in a -20°C environment to allow the polyvinyl alcohol to undergo a physical cross-linking reaction. After 24 hours, take it out and let it thaw naturally, then put it back into a -20°C environment and repeat the freezing-thawing process 3 times. The sample preparation is then complete.

[0060] The above samples were assembled into an energy recovery device. Its underwater cyclic adhesion performance was tested using a static mechanical testing instrument, and its energy recovery function was tested using an electrochemical workstation. The sample obtained in Example 3 showed an adhesion strength of approximately 30 kPa under a 5 N pre-pressure underwater, and its adhesion performance remained stable after 1000 adhesion-desorption cycles. Figure 9 As shown. Furthermore, the output voltages of this material under preloads of 5N, 10N, and 15N are 1.3mV, 1.7mV, and 1.75mV, respectively. Figure 10 As shown. Therefore, the above preparation method can successfully prepare an integrated material with underwater circulating adhesion and energy recovery functions.

[0061] Example 4:

[0062] Example 4 of this invention provides an integrated underwater circulating adhesion-energy recovery material and its preparation method. A honeycomb graphene aerogel material is prepared as the template material, and the liquid is an aniline solution. Detailed preparation steps are as follows:

[0063] (1) Preparation of graphene aerogel with a honeycomb structure: The specific steps are as follows: graphene oxide powder is dissolved in deionized water and ultrasonically dispersed for 6 hours to obtain a uniformly dispersed graphene oxide aqueous solution. The graphene oxide aqueous solution is degassed in a vacuum for 30 minutes and then poured into a pre-frozen mold and directionally frozen for at least 24 hours. The frozen sample is then taken out and freeze-dried for 72 hours at a temperature of -70℃ and a pressure of 0.1 Pa. Through the above steps, a graphene aerogel with a height of 1000 μm is prepared.

[0064] (2) Weigh 0.1g of ammonium persulfate, place it in container A, add 1mL of deionized water to fully dissolve the ammonium persulfate, and cool it to 4℃ in a low-temperature environment for later use.

[0065] (3) Take 2 mL of deionized water and place it in container B. Use a pipette to add 920 μL of 50% phytic acid solution to container B and mix well. Then add 350 μL of aniline and use a magnetic stirrer to stir the mixture until it is colorless and transparent. Place it in a low-temperature environment to cool to 4°C for later use.

[0066] (4) Immerse the graphene aerogel obtained in step (1) in the solution obtained in step (3) to a depth of 400 μm and place it in an environment of 4℃ for later use.

[0067] (5) Add the solution obtained in step (2) to the solution in step (4), mix well, and place in a low temperature environment of 4℃ to carry out a chemical cross-linking reaction for ≥8 hours.

[0068] (6) Take out the sample obtained in step (5) and rinse the surface with deionized water to remove excess reaction products.

[0069] The above samples were assembled into an energy recovery device. Its underwater cyclic adhesion performance was tested using a static mechanical testing instrument, and its energy recovery function was tested using an electrochemical workstation. The sample obtained in Example 4 showed an adhesion strength of approximately 16 kPa under a 5 N pre-pressure underwater, and its adhesion performance remained stable after 1000 adhesion-desorption cycles. Figure 11 As shown. Furthermore, the output voltages of this material under preloads of 5N, 10N, and 15N are 0.3mV, 0.53mV, and 0.68mV, respectively. Figure 12 As shown. Therefore, the above preparation method can successfully prepare an integrated material with underwater circulating adhesion and energy recovery functions.

[0070] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.

Claims

1. An underwater adhering energy-recovering function-integrated material, characterized by: The underwater adhesive energy recovery integrated material has a layered structure, with an upper layer being a three-dimensional carbon material skeleton structure and a lower layer having vertically oriented pore channels and surface pore structures; wherein the three-dimensional carbon material skeleton structure is a vertically oriented three-dimensional structure formed by carbon material; the energy recovery is the conversion of mechanical energy into electrical energy.

2. The underwater adhering energy harvesting integrated material according to claim 1, characterized in that: The ratio of the height of the upper structure to the height of the lower structure is 0.1-10.

3. The integrated underwater adhesive energy recovery material according to claim 1 or 2, characterized in that: The carbon material includes one or more of carbon nanotubes, graphene, and activated carbon.

4. The integrated underwater adhesion energy recovery material according to claim 1 or 2, characterized in that: The material of the lower layer is a polymer material, which includes one or more of gelatin, polyvinyl alcohol, and conductive polymers, wherein the conductive polymers include polyaniline and polypyrrole.

5. The preparation method of the underwater adhesive energy recovery integrated material according to claim 1, characterized in that: Includes the following steps: (1) Prepare a vertically oriented three-dimensional carbon material framework and use it as a template material; (2) Immerse part of the template material in the polymer solution and expose the other part to the air; (3) The template material immersed in the polymer solution is sealed by physical and / or chemical action to finally form an integrated underwater adhesion energy recovery material with a layered structure.

6. The preparation method of the integrated underwater adhesive energy recovery material according to claim 5, characterized in that: The viscosity range of the polymer solution is 1 cs-3000 cs.

7. The preparation method of the integrated underwater adhesive energy recovery material according to claim 5 or 6, characterized in that: The physical action refers to physical cross-linking and curing, and the chemical action refers to chemical cross-linking.

8. The use of the material of claim 1 in the preparation of materials having underwater cyclic adhesion and / or energy recovery functions.

9. The application according to claim 8, characterized in that: The three-dimensional carbon material framework structure provides energy recovery functionality, and the vertically oriented pore channels and surface pore structure provide underwater circulation adhesion functionality. The integrated underwater adhesion energy recovery material can be used as a multifunctional material, or it can be used alone as an underwater circulation adhesion material or an energy recovery material. The energy recovery function converts mechanical energy into electrical energy.

10. The application according to claim 9, characterized in that: The underwater adhesion energy recovery integrated material can be assembled with a current collector, a wire, and a counter electrode to form an underwater circulating adhesion-energy recovery integrated device. When the device realizes the energy recovery function, the electrolyte environment includes seawater, lake water, NaCl aqueous solution, and KOH aqueous solution.

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