CN-122026741-A - Preparation method and application of tetra-sulfur hepta-copper monopotassium/hydrogel-based flexible friction nano generator

Abstract

The invention discloses a preparation method and application of a flexible friction nano generator based on tetrathioheptacopper-potassium/hydrogel, belonging to the technical field of conductive hydrogel and novel conductive filler, the silicon rubber is used as a friction layer to prepare the flexible friction nano generator based on the tetra-sulfur hepta-copper-potassium/hydrogel, and the flexible friction nano generator can be applied to the fields of man-machine interaction, biological sensing, biological medical treatment and the like.

Inventors

• ZHANG KAIYOU
• Luo Caixin
• HE SIYUAN
• Zhong Minglang
• ZHAO GUOYOU
• Cheng Weiju
• WANG ZHILI
• LI WEIJIA
• ZHU YAN
• ZHAO YUANLI
• FU XUANCHAO
• LIU WANJIE

Assignees

• 桂林理工大学

Dates

Publication Date

20260512

Application Date

20260205

Claims (10)

1. 1. A flexible friction nano generator based on tetra-sulfur hepta-copper-potassium/hydrogel is characterized in that tetra-sulfur hepta-copper-potassium/hydrogel is used as an electrode layer, and silicon rubber is used as a friction layer.
2. 2. A method for preparing the flexible friction nano generator based on tetra-sulfur heptacopper-potassium/hydrogel, which is characterized in that the flexible friction nano generator based on tetra-sulfur heptacopper-potassium/hydrogel is obtained by encapsulating the tetra-sulfur heptacopper-potassium/hydrogel in silicon rubber.
3. 3. The method for preparing the tetra-sulfur heptacopper monopotassium/hydrogel-based flexible friction nano-generator according to claim 2, wherein the method for preparing the tetra-sulfur heptacopper monopotassium comprises the following steps: mixing anhydrous copper chloride and water, and uniformly stirring to obtain a first solution; mixing sulfur powder, absolute ethyl alcohol, potassium hydroxide and water, and uniformly stirring to obtain a second solution; Mixing the first solution and the second solution, adding hydrazine hydrate, and uniformly stirring to obtain a first mixed solution; And carrying out hydrothermal reaction on the first mixed solution, cooling to room temperature after the reaction is finished, centrifuging, washing and drying a product to obtain the tetra-sulfur heptacopper monopotassium.
4. 4. The preparation method of the tetra-sulfur heptacopper-potassium/hydrogel-based flexible friction nano generator is characterized in that the mass ratio of anhydrous copper chloride to sulfur powder to potassium hydroxide is (1-2) to (20-40).
5. 5. The method for preparing the flexible friction nano generator based on the tetra-sulfur heptacopper-potassium/hydrogel, which is disclosed in claim 3, is characterized in that the temperature of the hydrothermal reaction is 150-180 ℃ and the time is 10-12 hours.
6. 6. The method for preparing the tetra-sulfur heptacopper monopotassium/hydrogel-based flexible friction nano-generator according to claim 2, wherein the method for preparing the tetra-sulfur heptacopper monopotassium/hydrogel comprises the following steps: dissolving polyvinyl alcohol in water, and stirring under a heating state until the polyvinyl alcohol is completely dissolved to obtain a polyvinyl alcohol aqueous solution; dissolving sodium alginate in water, and stirring under a heating state until the sodium alginate is completely dissolved to obtain a sodium alginate aqueous solution; Mixing the polyvinyl alcohol aqueous solution and the sodium alginate aqueous solution, continuously stirring and cooling to room temperature to obtain a second mixed solution; and mixing the tetra-sulfur heptacopper monopotassium and the second mixed solution, uniformly stirring, and freezing to obtain the tetra-sulfur heptacopper monopotassium/hydrogel.
7. 7. The preparation method of the flexible friction nano generator based on the tetra-sulfur heptacopper-potassium/hydrogel, which is disclosed in claim 6, is characterized in that the mass ratio of polyvinyl alcohol to sodium alginate is (1-2) to (1-2).
8. 8. The method for preparing the flexible friction nano generator based on the tetra-sulfur heptacopper-potassium/hydrogel, which is characterized in that the dosage ratio of the tetra-sulfur heptacopper-potassium to the second mixed solution is (0.1-0.2) g to (35-70) mL.
9. 9. The method for preparing the flexible friction nano generator based on the tetra-sulfur heptacopper-potassium/hydrogel, which is characterized by comprising the steps of firstly curing the silicon rubber at room temperature, then placing the tetra-sulfur heptacopper-potassium/hydrogel in the center of the cured silicon rubber, and then placing uncured silicon rubber on the surface of the tetra-sulfur heptacopper-potassium/hydrogel and curing at room temperature.
10. 10. Use of the potassium hepta tetrasulfide/potassium mono-hydrate/hydrogel-based flexible friction nano-generator of claim 1 in the preparation of self-powered wearable electronic equipment.

Description

Preparation method and application of tetra-sulfur hepta-copper monopotassium/hydrogel-based flexible friction nano generator Technical Field The invention belongs to the technical field of conductive hydrogel and novel conductive filler, and particularly relates to a preparation method and application of a flexible friction nano generator based on tetra-sulfur hepta-copper-potassium/hydrogel. Background The 2012 Wang Zhonglin institute first proposed friction nano-generator (TENG) based on contact electrification and electrostatic inductive coupling, creating a new era of energy harvesting and utilization. TENG is capable of collecting various tiny, low frequency, irregular mechanical energy in the environment. Under the condition of low frequency, the high efficiency of the TENG is incomparable with that of an electromagnetic generator, and the TENG has a series of advantages of good stability, long service life, no magnet and coil device and the like. Therefore TENG was the first time proposed as a research hotspot. In addition, TENG is light in weight, small in size, convenient to move, low in cost, simple in preparation process, very wide in raw material sources, free of environmental pollution, and is a novel green energy conversion device with great development space. The hydrogel is an environment-friendly material with a 3D cross-linked network structure formed by polymer chains, and has excellent biodegradability and biocompatibility. Meanwhile, the 3D network structure of the hydrogel imparts excellent mechanical properties including flexibility, stretchability, elasticity, etc., which have led to the wide application of hydrogels in flexible electronics and green electronics. Based on this, hydrogel-based TENG using a hydrogel as an electrode layer has gradually attracted the interest of researchers. Xu et al （Xu W, Huang L B, Wong M C, et al. Self-powered Sensors: Environmentally Friendly Hydrogel-based Triboelectric Nanogenerators for Versatile Energy Harvesting and Self-powered Sensors[J]. Advanced Energy Materials, 2017, 7(1): 1601529.）, in 2016, first proposed the concept of hydrogel-based TENG. However, hydrogel TENG currently faces many challenges, such as low working efficiency, poor environmental adaptability, and short service life, so that there is still a large space for optimizing the conductivity, environmental adaptability, and self-healing performance. The output performance is optimized by adding the conductive substance to serve as the self-powered sensing equipment, and the strength of the output performance of the hydrogel-based TENG is an important index for measuring the performance of the self-powered sensing equipment. The conductive medium of the conventional hydrogel is water, and ionization of the water as weak electrolyte is weak, so that the use of the conventional hydrogel as an electrode material cannot meet the use requirement of TENG. Therefore, adding conductive filler materials to hydrogels to improve TENG output performance is a popular way. Currently, common hydrogel conductive filling materials include carbon nanotubes, graphene, conductive polymers, liquid metals, nano silver and the like. Sun et al （Sun H L, Zhao Y, Wang C F, et al. Ultra-stretchable, durable and conductive hydrogel with hybrid double network as high performance strain sensor and stretchable triboelectric nanogenerator[J]. Nano Energy, 2020, 76(10): 105035.） developed a Polyacrylamide (PAM) hydrogel using gelatin and PEDOT: PSS, and encapsulated the PAM hydrogel with 2 layers of adhesive Polyurethane (PU) tape, to prepare a high output performance hydrogel-based TENG, the output of which mainly resulted from the contact and separation of the PU tape and external silica gel. Due to the addition of PEDOT: PSS, the open circuit voltage (V OC), short circuit current (I SC) and short circuit transfer charge (Q SC) of the hydrogel-based TENG reached 383.8V, 26.9 μa and 92 nC, respectively. Wang et al （Wang L Y, Daoud W A. Hybrid conductive hydrogels for washable human motion energy harvester and self-poweredtemperature-stress dual sensor[J]. Nano Energy, 2019, 66(12): 104080.） prepared hydrogel-based TENG by introducing silver nanowires (AgNW) into an ionic chitosan hydrogel. Due to the introduction of AgNW, the output voltage and current density of the hydrogel-based TENG reached 218V and 34.44 mA/m 2, respectively. In addition, two-dimensional carbon (nitrogen) compounds (MXene) have been attracting wide attention as an emerging conductive material in the study of hydrogel-based TENG due to their excellent electrochemical properties while having good binding properties with various materials. Liu et al （Liu Z X, Liang G J, Zhao Y X, et al. A soft yet device-level dynamically super-tough supercapacitor enabled by an energy-dissipative dual-crosslinked hydrogel electrolyte[J]. Nano Energy, 2019, 58(4): 732-742.） introduced MXene into a polyvinyl alcohol (PVA)/borax network and wrapped it with si