A humidity-friction dual-mode power generation device and its application

Abstract

The present invention relates to a moisture-triboelectric dual-mode power generation device and its applications. The power generation material of this invention features a unique layered structure and hierarchical porosity. Its components and structural properties are highly controllable, highly adaptable, and have great potential for large-scale production. This effectively ensures the excellent electrical performance and application potential of the dual-mode power generation system. The dual-mode power generation system provided by this invention achieves complementary power collection from moisture and triboelectricity, promoting the research and development of green and sustainable power sources.

Description

Technical Field

[0001] The present invention belongs to the field of new energy power generation, and in particular relates to a moisture-friction dual-mode power generation device and applications thereof. Background Art

[0002] To alleviate the environmental pollution and energy crisis caused by the massive consumption of fossil fuels, the development and utilization of renewable and sustainable energy sources have become a key research topic in today's energy field. Converting ambient energy into electricity offers a practical and sustainable solution to alleviate energy and environmental challenges. Hydroelectric generators (MEGs) and triboelectric nanogenerators (TENGs) are two emerging energy harvesting technologies that can alleviate the energy crisis and, in particular, promote the development of distributed energy and the Internet of Things.

[0003] MEG can spontaneously harvest electrical energy from the atmosphere through the interaction between hygroscopic materials and moisture, providing a sustainable power generation strategy with the advantage of high current output, but has application limitations in low humidity conditions. TENG provides an emerging technology for converting low-frequency mechanical energy into electrical energy, with the advantage of high voltage, but also has drawbacks such as low current output, humidity sensitivity, and mechanical durability. Combining these two strategies into a hybrid device (MEG-TENG) can reconcile voltage and current output to achieve a high power density energy harvester. Due to the structural differences between the two devices and the high humidity sensitivity of TENG, designing a hybrid MEG-TENG energy harvesting system with a reasonable device structure remains a challenge. Summary of the Invention

[0004] In view of the defects of the prior art, the technical problem to be solved by the present invention is to provide a moisture-friction dual-mode power generation device and its application.

[0005] The present invention provides a moisture-friction dual-mode power generation device, which includes: a moisture power generation module and a friction power generation module; the moisture power generation module and the friction power generation module are integrated by inserting electrodes and share the same power generation material; the moisture power generation module also includes an organic ion hydrogel, which is arranged on the lower surface of the power generation material; the composite aerogel is a composite aerogel constructed of nanosheets, nanofibers and hydrophilic polymers.

[0006] Preferably, the nanosheets are two-dimensional nanosheets.

[0007] The two-dimensional nanosheet is one or more of graphene oxide (GO), MXene, montmorillonite (MMT), and molybdenum disulfide (MoS2).

[0008] Further preferably, the two-dimensional nanosheet is MXene, and the MXene is Ti3C2Tx, wherein x is 0-2.

[0009] Preferably, the nanofiber is one or more of cellulose nanofiber (CNF), aramid nanofiber (ANF), and silk nanofiber (SNFs);

[0010] Further preferably, the cellulose is: cellulose nanofiber (CNF);

[0011] Further preferably, the cellulose nanofiber (CNF) is: TEMPO-oxidized cellulose nanofiber (TCNF);

[0012] The hydrophilic polymer is one or more of polyvinyl alcohol (PVA), polyacrylic acid (PAA), and polyethylene glycol (PEG).

[0013] Further preferably, the hydrophilic polymer is: polyvinyl alcohol (PVA);

[0014] The unique structural characteristics of the power generation material of the present invention and the physical / chemical characteristics of the raw materials give the composite aerogel the feasibility of being used as a shared power generation material for a wet gas power generation system and a friction power generation system.

[0015] The composite aerogel power generation material can meet the requirements of both the MEG system and the TENG system.

[0016] Preferably, the mass ratio of nanofibers to flexible hydrophilic polymers in the composite aerogel is 100:1 to 1:100; the mass ratio of nanosheets to nanofibers is 10:1 to 1:100;

[0017] Further preferably, the mass ratio of the nanofibers to the flexible hydrophilic polymer in the composite aerogel is 10:1 to 1:10; and the mass ratio of the nanosheets to the nanofibers is 1:1-50.

[0018] Preferably, the composite aerogel has a layered microstructure with a directional pore network between the layers.

[0019] Furthermore, the composite aerogel's layered and oriented pore structure can better dissipate the stress generated during compression, providing more reliable mechanical support and shape recovery. Furthermore, hydrophilic polymers can be combined with nanofibers through physical mixing or chemical modification to further enhance the mechanical flexibility and hydrophilic properties of the composite aerogel.

[0020] Furthermore, the negatively charged nanofibers, acting as nanocarriers, can form a "brick-and-mortar" interlayer bond with the two-dimensional nanosheets through hydrogen bonding, making the composite aerogel's layered structure more compact and ordered, further improving its mechanical properties and stability. At the same time, this interlayer bond prevents the nanosheets from self-stacking, thereby enhancing ion selectivity and ion diffusion rate within the nanosheet layer.

[0021] Furthermore, the continuous directional and ordered microscopic channels can effectively adsorb and migrate moisture, realizing the complementary power collection of moisture and triboelectricity.

[0022] Preferably, the directional pores are one of fully through or semi-through micropores, nanopores, and micro / nano composite pores, and the directional pores are highly directional and arranged along the vertical direction; the vertical direction is that the pores of the aerogel are perpendicular to the surface of the organic ion hydrogel.

[0023] Preferably, the composite aerogel is prepared by a sol-gel method, a combination of hydrothermal synthesis and sol-gel technology, 3D printing, gel polymerization, or gel casting. Further preferably, the aerogel is prepared by a sol-gel method.

[0024] Preferably, the preparation method of the composite aerogel comprises: uniformly stirring the nanofibers and the hydrophilic polymer solution, then adding the nanosheets, stirring and degassing, transferring the obtained sol to a mold for gelation to obtain a pre-gel, and then freezing and drying to obtain the composite aerogel;

[0025] Alternatively, the nanofibers and hydrophilic polymer solution are stirred evenly, and then the nanosheets are added, stirred evenly, 3D printed, frozen and dried to obtain the composite aerogel.

[0026] Furthermore, the nanofibers are added in the form of nanofiber sol, nanofiber dispersion or nanofiber suspension; wherein the solvent in the nanodispersion or suspension includes one or more of deionized water, hexafluoroisopropanol (HFIP) and dimethyl sulfoxide (DMSO).

[0027] Furthermore, the solvent of the hydrophilic polymer solution is one or more of deionized water, ethanol, glycerol, acetic acid, and ethyl acetate.

[0028] Furthermore, the nanosheets are added in the form of a nanosheet suspension or a nanosheet dispersion, wherein the solvent comprises one or more of deionized water, ethanol, glycerol, acetic acid, ethyl acetate, and dimethyl sulfoxide (DMSO).

[0029] More preferably, the solvent is deionized water.

[0030] Preferably, the freezing is directional freezing.

[0031] Preferably, the drying method is supercritical drying, freeze drying, vacuum drying, atmospheric pressure drying, or microwave drying. Further preferably, the drying method is freeze drying.

[0032] The wet gas power generation module is formed by closely connecting the organic ion hydrogel directly adhered to the power generation material and the bottom electrode to form a wet gas power generation module together with the upper electrode.

[0033] Preferably, the organic ion hydrogel component includes a gel network matrix material, an inorganic salt and a solvent; wherein the mass of the gel network matrix material is 5% to 60% (wt%) of the solvent mass, and the mass of the inorganic salt is 0.01% to 20% (wt%) of the total mass of the solution.

[0034] Preferably, the gel network matrix material includes any one of polyacrylamide (PAM), polyacrylamide (PAM) / polyvinyl alcohol (PVA), polyacrylamide (PAM) / gelatin (GA), and polyacrylamide (PAM) / polystyrene sulfonic acid (PSSA); the inorganic salt includes one or more of LiCl, NaCl, MgCl2, AlCl3, KCl, CaCl2, and CoCl2.

[0035] More preferably, the inorganic salt is any one of LiCl, NaCl, and KCl.

[0036] Preferably, the solvent is a blended solvent of an organic solvent and water; wherein the organic solvent comprises one or more of ethylene glycol, glycerol, and dimethyl sulfoxide; and the mass percentage of water in the blended solvent is 0.1 to 99.9%.

[0037] Furthermore, the gel network material in the organic ion hydrogel is any one of a single-component gel network of polyacrylamide (PAM), a two-component gel network of polyacrylamide (PAM) / polyvinyl alcohol (PVA), polyacrylamide (PAM) / gelatin (GA), and polyacrylamide (PAM) / polystyrene sulfonic acid (PSSA).

[0038] Preferably, the organic ion hydrogel is disposed on the lower surface of the power generation material: the organic ion hydrogel and the power generation material are directly adhered to each other, for example, the organic ion hydrogel is applied to the bottom of the composite aerogel.

[0039] The method for preparing an organic ion hydrogel comprises: mixing and stirring raw materials containing a gel network matrix material monomer, a solvent, a crosslinking agent, and an initiator, then adding an inorganic salt, mixing evenly, and curing under ultraviolet light for 1-30 minutes to obtain the organic ion hydrogel. The crosslinking agent is one or more of N,N-methylenebisacrylamide (MBAA), polyisopropyl acrylate (MBA), and benzoyl peroxide (BPO); the mass ratio of the crosslinking agent to the gel network monomer is 1:10 to 1:500; the initiator is one or more of α-ketoglutaric acid, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propiophenone, and 2-hydroxy-2-methylpropiophenone; and the mass ratio of the initiator to the gel network monomer is 1:10 to 1:500.

[0040] Preferably, the insertion electrodes include a bottom electrode of the wet gas power generation module, an upper electrode of the wet gas power generation module, and a lower electrode of the friction power generation module.

[0041] Preferably, the inserted electrode is one or more of an ITO glass electrode, an FTO glass electrode, a TCO glass electrode, and a metal electrode; wherein the metal electrode is any one of Al, Zn, Fe, Cu, Ag, etc. Further preferably, the bottom inserted electrode is an Al electrode.

[0042] Preferably, the friction power generation module further comprises a friction contact electrode (the upper electrode of the friction power generation module), wherein the friction contact electrode is arranged directly above the power generation material;

[0043] Preferably, the moisture-friction dual-mode power generation device further comprises a circuit connector, wherein the circuit connector is a rectifier circuit, wherein the rectifier circuit couples the rectified AC output and DC output in parallel.

[0044] The circuit connector couples the rectified AC output and DC output in parallel to achieve synchronous collection of wet gas power generation and friction power generation energy.

[0045] Preferably, the friction contact electrode includes a conductive tape and a friction functional layer; wherein the conductive tape includes one or more of a conductive cloth tape, a conductive silicone tape, and a conductive metal tape; the conductive component in the conductive tape includes one or more of platinum, gold, silver, copper, nickel, aluminum, carbon materials, graphene, MXene, carbon nanotubes, and conductive polymers; the friction functional layer material includes one or more of polytetrafluoroethylene (PTFE), polyfluoroethylene propylene (FEP), polydimethylsiloxane (PDMS), polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP), polyvinylidene fluoride (PVDF), polypropylene (PP), polyethylene terephthalate (PET), styrene propylene copolymer, styrene butadiene copolymer, synthetic fiber, polymethacrylate, polyvinyl alcohol (PVA), polyethylene glycol (PEG), polyester, polyisobutylene, polyethylene terephthalate, chloroprene rubber, butadiene propylene copolymer, natural rubber, polyacrylonitrile, acrylonitrile vinyl chloride, stainless steel sheet, iron sheet, copper sheet, and silver sheet.

[0046] More preferably, the friction functional layer is one of polytetrafluoroethylene (PTFE), polyfluoroethylene propylene (FEP), and polyvinylidene fluoride (PVDF).

[0047] More preferably, the friction functional layer and the power generation material in the same power generation system are made of different materials.

[0048] The present invention provides an application of the moisture-friction dual-mode power generation device in the fields of environment, energy, information and national defense.

[0049] Preferably, the application in the environmental field includes at least one of autonomous collection of environmental energy and application of intelligent environmental detection equipment; the application in the energy field includes at least one of triboelectric energy collection, piezoelectric energy collection, moisture energy collection, autonomous utilization of environmental energy, and quantitative sensing applications; the application in the information field includes at least one of the application of environmental perception, sensing and information interaction equipment; the application in the defense field includes the application of electrical power supply or power generation equipment in extreme environments.

[0050] The present invention provides a composite aerogel power generation material with a layered structure and oriented pores. This material exhibits good mechanical properties, excellent hygroscopicity, and efficient water transport, enabling a hybrid MEG-TENG device to synergistically harvest electricity from moisture and mechanical energy. In a first aspect, the present invention provides a composite aerogel power generation material with a vertically ordered pore structure and a method for preparing the same. The composite aerogel is constructed from nanofibers, two-dimensional nanosheets, and a flexible polymer using directional freeze-drying technology.

[0051] The layered and directional pore structure of the composite aerogel can better dissipate the stress generated during compression, meeting the requirements of the power generation materials in the TENG module to withstand harsh deformation and repeated compression without structural collapse. The "brick and mortar" interlayer bonding formed between the nanofibers and nanosheets can further improve its mechanical properties and stability. In addition, the introduction of two-dimensional nanosheets can improve the dielectric properties of the composite aerogel system, thereby enhancing the triboelectric output during the TENG process.

[0052] In the MEG module, the directional porous structure of the aerogel provides many microchannels for the transmission of moisture and ions, which helps to establish moisture and ion gradients and makes it possible for long-term stable output of MEG. By directly adhering the organic ion hydrogel to the surface of the power generation material to construct a double-layer MEG, the dependence of MEG on environmental humidity is overcome. In addition, the introduction of active ions into the gel can solve the problem of insufficient total ions in ionized water and effectively increase the current output. The electronegative nanochannels improve the selectivity and diffusion rate of cations, further improving the performance output of MEG. The MEG module achieves high-performance output under various humidity conditions and has excellent environmental flexibility.

[0053] This invention provides a dual-mode power generation system based on a shared power generation material. A circuit connector couples the rectified AC output and DC output in parallel, enabling the simultaneous collection of MEG and TENG energy generated by the power generation material described in the first aspect. The unique design of the material's microstructure and its physical and chemical properties ensure the output stability of the dual-mode power generation system.

[0054] Based on the research results of the present invention, a composite aerogel power generation material that can meet the needs of triboelectric power generation and wet gas power generation has been developed, and the wet electric module and the triboelectric module are integrated and share the same power generation material, realizing the synchronous collection of the coupled output of MEG-TENG.

[0055] Beneficial effects

[0056] The power generation material involved in the present invention has a special design with a layered structure and directional pore arrangement. Its components and structural properties are highly controllable, highly universal, and have great potential for large-scale production, effectively ensuring the excellent electrical performance and application potential of the dual-mode power generation system.

[0057] The dual-mode power generation system developed by this invention utilizes a simple design and technology to achieve the synergistic integration and coupled output of humidity-generated and triboelectric power within the system. The system's basic components consist solely of a power generation unit and a connector, which are simple and convenient to install. This method requires minimal experimental equipment and offers low production, assembly, and maintenance costs, facilitating large-scale production and promising broad application prospects.

[0058] The dual-mode power generation system provided by this invention is clean, sustainable, convenient, and environmentally adaptable. It can be applied to powering electrical appliances or large-scale power generation equipment, offering significant economic, environmental, and social benefits and practical application potential. Its excellent electrical performance and practical applicability are of great significance in promoting the research and development of green and sustainable power sources. BRIEF DESCRIPTION OF THE DRAWINGS

[0059] Figure 1 1. The vertical cross-sectional surface (A) and cross-sectional scanning electron micrograph (B) of the CPM-aerogel power generation material prepared by directional freezing in Example 2;

[0060] Figure 2 is a compression cycle diagram of the CPM-aerogel prepared by directional freezing as described in Example 2;

[0061] Figure 3 is a schematic diagram of the dual-mode power generation system of the present invention;

[0062] Figure 4 2. The voltage (A) and current coupled output diagram (B) of the dual-mode power generation system based on CPM-aerogel power generation materials in Example 2;

[0063] Figure 5 This is a voltage output diagram of the dual-mode power generation system based on CPM-aerogel power generation materials in Example 2 within 1000 cycles (humidity: 90%);

[0064] Figure 6 This is a diagram of charging a commercial capacitor based on the voltage-coupled output of the dual-mode power generation system of APM-aerogel power generation materials in Example 9;

[0065] Figure 7 This is a voltage output diagram of the MEG power generation module (humidity: 20%) based on the CPM-aerogel power generation material in Example 10; DETAILED DESCRIPTION

[0066] Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiments are only used to illustrate the present invention and are not used in limiting the scope of the present invention.In addition, should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall equally within the scope limited by the appended claims of the application.

[0067] Related raw materials:

[0068] Polyvinyl alcohol (PVA), polyacrylic acid (PAA), and polyethylene glycol (PEG) were purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; montmorillonite (MMT) was purchased from Guangxi Ningming Mining Co., Ltd.; graphene oxide (GO) and molybdenum disulfide (MoS2) were purchased from Jiangsu Xianfeng Nanomaterial Technology Co., Ltd.; oxidized cellulose nanofibers (TCNF) were purchased from Shansi Technology Co., Ltd.; aramid nanofibers (ANF) were purchased from Shandong Jufang New Materials Co., Ltd.; and silk nanofibers (SNFs) were purchased from Nanjing Tianlu Nanotechnology Co., Ltd.

[0069] MAX phase precursor powder (Ti3AlC2 powder) was purchased from Foshan Xinxin Technology Co., Ltd. The purity of the MAX phase precursor powder is ≥99.9%, and the particle size of the MAX phase precursor powder is 400 mesh.

[0070] The preparation method of the MXene dispersion selected in the embodiment is:

[0071] MAX powder was slowly added to a uniform mixture of LiF and HCl and stirred at 40°C for 36 h to obtain a MXene (Ti3C2Tx) suspension. The suspension was then repeatedly washed with deionized water until the pH of the supernatant was approximately 7. Finally, the supernatant was ultrasonically treated to obtain a Ti3C2Tx dispersion, which was then refrigerated and stored for later use.

[0072] Note: The directional freezing involved in the examples and comparative examples is from bottom to top, vertical freezing.

[0073] Example 1

[0074] like Figure 2 As shown, the wet gas-friction dual-mode power generation device includes: a rectifier circuit (connector), a wet gas power generation module and a friction power generation module; the wet gas power generation module and the friction power generation module are integrated by inserting electrodes and share the same power generation material; the wet gas power generation module is also provided with an organic ion hydrogel, which is provided on the lower surface of the power generation material; the friction power generation module is also provided with a friction contact electrode, wherein the friction contact electrode is provided directly above the power generation material;

[0075] The power generation material is a composite aerogel of two-dimensional nanosheets, nanofibers and hydrophilic polymers.

[0076] The inserted electrodes include, from bottom to top, the bottom electrode of the wet gas power generation module, the upper electrode of the wet gas power generation module, and the lower electrode of the friction power generation module; the bottom electrode of the wet gas power generation module is located at the bottom of the organic ion hydrogel; the upper electrode of the wet gas power generation module and the lower electrode of the friction power generation module are both located in the power generation material; and the friction contact electrode is located directly above the power generation material;

[0077] The inserted electrode is one or more of an ITO glass electrode, an FTO glass electrode, a TCO glass electrode, and a metal electrode; the rectifier circuit couples the rectified AC output and DC output in parallel.

[0078] Working method:

[0079] (1) The friction contact electrode is adhered to the surface of the pressure sensor by insulating tape. The moisture-friction dual-mode power generation device is placed vertically directly below the friction contact electrode. The mechanical pressure of the friction power generation unit is provided by a linear motor (0-100N).

[0080] (2) The rectifier circuit is directly connected to a commercial multimeter (Keithley 6510) / capacitor to measure / collect the power output of the dual-mode power generation device.

[0081] Example 2

[0082] In this embodiment, a TCNF / PVA / MXene (CPM)-aerogel power generation material is provided, and its preparation method is as follows: a certain amount of PVA solution (5wt%) is added to the TCNF sol (1wt%), wherein the mass ratio of PVA to TCNF is 1:1. Then a certain amount of MXene dispersion is weighed and added to the above-mentioned TCNF / PVA sol, wherein the mass ratio of MXene to TCNF is 1:4. After stirring evenly (2h) and degassing, the CPM sol is poured into a mold for gelation for 2h, and directionally frozen (-100℃) for 0.5h using liquid nitrogen as a refrigerant. After being completely frozen, it is freeze-dried for 24h to obtain a CPM-aerogel power generation material (height 10mm) with a layered structure and directional full-penetration micro / nano composite multi-level pores.

[0083] In this example, a single-component polyacrylamide (PAM) network organic ion hydrogel was used as the power source for wet gas power generation. Its preparation method was as follows: 1.5g acrylamide, 30mg N,N'-methylenebisacrylamide (MBAA), and 30mg α-ketoglutaric acid were added to 10g of a glycerol / water mixed solvent (50% water by mass). The mixed solution was stirred for 30 minutes, and then 0.75g KCl was added and stirred for 1 hour to obtain a PAM-KCl pre-solution. The prepared solution was drop-cast into a mold of the required size and then cured under UV light for 10 minutes to obtain the PAM-KCl organic ion hydrogel. The PAM-KCl organic ion hydrogel was then applied to the bottom of the CPM aerogel and set aside.

[0084] In this embodiment, the bottom electrode of the wet gas power generation module is an Al electrode and the top electrode is a Cu electrode; the bottom electrode of the triboelectric power generation module is a Cu electrode, and the triboelectric contact electrode is composed of conductive cloth tape and polytetrafluoroethylene (PTFE). The mechanical stress is 20N and the mechanical compression is 60%. In this case, the voltage coupling output of the dual-mode power generation system based on CPM-aerogel power generation material is 120V and the current output is 180μA ( Figure 4 ). And the dual-mode power generation system can maintain a stable voltage output of 120V in 1000 cycles under high humidity (90%). Figure 5 ).

[0085] Example 3

[0086] In this embodiment, an ANF / PAA / GO (APO)-aerogel power generation material is provided, and its preparation method is as follows: a certain amount of PAA solution (5wt%) is added to an ANF aqueous suspension (1wt%), wherein the mass ratio of PAA to ANF is 1:1. A certain amount of GO dispersion is then weighed and added to the above-mentioned ANF / PAA sol, wherein the mass ratio of GO to ANF is 1:2. After stirring evenly (2h) and degassing, the APO sol is poured into a mold and gelled for 2h, and directionally frozen (-100℃) for 0.5h using liquid nitrogen as a refrigerant. After being completely frozen, it is freeze-dried for 24h to obtain an APO-aerogel power generation material (height 12mm) with a layered structure and directional, fully penetrating micro / nano composite multi-level pores.

[0087] In this embodiment, a polyacrylamide (PAM) single-component network organic ion hydrogel is used as the power source for wet gas power generation. Its preparation method is as follows: 1.5g of acrylamide monomer, 50mg of polyisopropyl acrylate (MBA) crosslinker, and 60mg of 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methylacetone initiator are added to 10g of ethylene glycol / water mixed solvent (water mass ratio 20%). The mixed solution is stirred for 30 minutes, and then 0.5g of LiCl is added and stirred for 1 hour to obtain a PAM-LiCl pre-solution. The prepared solution is drop-cast into a mold of the required size and then cured under ultraviolet light for 10 minutes to obtain the PAM-LiCl organic ion hydrogel. The PAM-LiCl organic ion hydrogel is then applied to the bottom of the APO-aerogel for standby use. In this embodiment, the wet gas power generation module has an Al bottom electrode and a Cu top electrode. The triboelectric power generation module has an Ag bottom electrode, and the triboelectric contact electrodes are composed of conductive copper tape and fluorinated ethylene propylene (FEP). The mechanical stress is 10N and the mechanical compression is 40%. In this case, the dual-mode power generation system based on APO-aerogel material has a coupled voltage output of 96V and a current output of 155μA.

[0088] Example 4

[0089] In this embodiment, a CPM-aerogel power generation material is provided, and its preparation method is as follows: a certain amount of PVA solution (10wt%) is added to TCNF sol (5wt%), wherein the mass ratio of PVA to TCNF is 2:1. Then a certain amount of MXene dispersion is weighed and added to the above TCNF / PVA sol, wherein the mass ratio of MXene to TCNF is 1:50, and stirred evenly (2h) to obtain TCNF / PVA ink. The TCNF / PVA ink is printed using a 3D printer (nozzle diameter is 0.41mm, printing speed is set to 3mm / s, ink flow rate is 3.2mL / h) into a mold with a filling density of 30% (2.0×2.0×0.5cm 3 The printed samples were directly frozen (-100°C) for 0.5 hours using liquid nitrogen as a refrigerant. After the samples were completely frozen, they were freeze-dried for 24 hours to obtain a CPM-aerogel power generation material (15 mm) with a layered structure and directional, fully penetrating micropores.

[0090] In this example, a single-component polyacrylamide (PAM) network organic ion hydrogel was used as the power source for wet gas power generation. Its preparation method was as follows: 1.5g acrylamide, 20mg N,N'-methylenebisacrylamide (MBAA), and 25mg α-ketoglutaric acid were added to 10g of a glycerol / water mixed solvent (50% water by mass). The mixed solution was stirred for 30 minutes, and then 0.75g KCl was added and stirred for 1 hour to obtain a PAM-KCl pre-solution. The prepared solution was drop-cast into a mold of the required size and then cured under UV light for 10 minutes to obtain the PAM-KCl organic ion hydrogel. The PAM-KCl organic ion hydrogel was then applied to the bottom of the CPM aerogel and set aside.

[0091] In this example, the wet gas power generation module has an Al bottom electrode and a Cu top electrode. The triboelectric power generation module has a Cu bottom electrode, and the triboelectric contact electrodes are made of conductive cloth tape and polytetrafluoroethylene (PTFE). The mechanical stress is 20N and the mechanical compression is 60%. In this case, the CPM-aerogel-based dual-mode power generation system has a coupled voltage output of 90V and a current output of 145μA.

[0092] Example 5

[0093] In this embodiment, a TCNF / PEG / MMT (TPT)-aerogel power generation material is provided. The preparation method thereof is as follows: a certain amount of PEG solution (5 wt%) is added to a TCNF sol (1 wt%), wherein the mass ratio of PEG to TCNF is 10:1. A certain amount of MMT dispersion is then weighed and added to the above-mentioned TCNF / PEG sol, wherein the mass ratio of MMT to TCNF is 1:1. After uniform stirring (5 h) and degassing, the TPT sol is poured into a mold and directionally frozen (-50°C) for 0.5 h using low-temperature ethanol as a refrigerant. After complete freezing, it is freeze-dried for 24 h to obtain a TPT-aerogel power generation material (height 10 mm) with a layered structure and directional, fully penetrating micropores.

[0094] In the present embodiment, take polyacrylamide (PAM) / polyvinyl alcohol (PVA) two-component network organic ion hydrogel as the power source of wet power generation, its preparation method is as follows: get 1g acrylamide, 0.5g PVA, 50mg benzoyl peroxide (BPO) cross-linking agent, 50mg 2-hydroxy-2-methyl propiophenone and add 15g ethylene glycol / water mixed solvent (mass ratio of water 50%), the mixed solution is stirred for 30min, then add 0.5g CaCl2 stirring 1h can obtain PAM / PVA-CaCl2 pre-solution.The solution for preparing is drop-cast in the mould that meets the required size, and then solidifies for 15min under ultraviolet lamp to obtain PAM / PVA-CaCl2 organic ion hydrogel.Then PAM / PVA-CaCl2 organic ion hydrogel is applied to the TPT-aerogel bottom for standby use.

[0095] In this embodiment, the wet gas power generation module has a bottom electrode made of FTO glass and a top electrode made of ITO glass. The triboelectric power generation module has a bottom electrode made of Cu. The triboelectric contact electrodes are made of conductive cloth tape and fluorinated ethylene propylene (FEP). The mechanical stress is 10N and the mechanical compression is 50%. In this case, the TPT-aerogel-based dual-mode power generation system has a coupled voltage output of 98V and a current output of 142μA.

[0096] Example 6

[0097] In this example, a SNF / PVA / GO (SPG) aerogel material for power generation is provided. The preparation method is as follows: Silk fibers are immersed in a HFIP solution at a mass ratio of 1:20 and stirred thoroughly (60°C for 24 hours) to obtain a silk microfiber (SMF) slurry. Finally, the SMF / water mixture is ultrasonically treated (60 minutes) and centrifuged (10,000 rpm for 20 minutes) to obtain a 1 wt% SNF dispersion. A 2 wt% PVA solution is added to the 1 wt% SNF dispersion, where the PVA:SNF mass ratio is 1:2. A GO dispersion is then weighed and added to the SNF / PVA sol, where the GO:SNF mass ratio is 1:2. After stirring for 2 hours and degassing, the SPG sol is poured into a mold and gelled in a water bath (50°C) for 5 hours. It is then placed in a refrigerator (-20°C) and directly frozen for 24 hours. After being completely frozen, the sample was immersed in ethanol for thawing and solvent replacement to form an alcohol gel. It was then directionally frozen (-100°C) for 0.5 hours using liquid nitrogen as a cryogen. After being completely frozen, it was freeze-dried for 24 hours to obtain an SPG-aerogel power generation material (12 mm high) with a layered structure and directional semi-penetrating micro / nano composite hierarchical pores.

[0098] In this example, a polyacrylamide (PAM) / polystyrene sulfonic acid (PSSA) two-component organic ion hydrogel was used as the power source for wet gas power generation. The preparation method was as follows: 1g acrylamide, 0.5g PSSA, 30mg N,N'-methylenebisacrylamide (MBAA), and 20mg α-ketoglutaric acid were added to 10g of a dimethyl sulfoxide / water mixed solvent (50% water by mass). The mixed solution was stirred for 30 minutes, and then 0.5g CoCl2 was added and stirred for 1 hour to obtain a PAM / PSSA-CoCl2 pre-solution. The prepared solution was drop-cast into a mold of the required size and then cured under ultraviolet light for 20 minutes to obtain the PAM / PSSA-CoCl2 organic ion hydrogel. The PAM / PSSA-CoCl2 organic ion hydrogel was then applied to the bottom of the SPG aerogel for later use.

[0099] In this embodiment, the wet gas power generation module has a Cu bottom electrode and a Cu top electrode; the triboelectric power generation module has a Cu bottom electrode, and the triboelectric contact electrodes are composed of conductive cloth tape and polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP). The mechanical stress is 20N and the mechanical compression is 60%. In this case, the SPG-aerogel-based dual-mode power generation system has a voltage coupled output of 106V and a current output of 152μA.

[0100] Example 7

[0101] In this embodiment, a TCNF / PVA / MoS2 (TPM)-aerogel material power generation material is provided, and its preparation method is as follows: a certain amount of PVA solution (5wt%) is added to the TCNF sol (1wt%), wherein the mass ratio of PVA to TCNF is 1:1. Then a certain amount of MoS2 dispersion is weighed and added to the above-mentioned TCNF / PVA sol, wherein the mass ratio of MoS2 to TCNF is 1:4. After stirring evenly (2h) and degassing, the TPM sol is poured into a mold for gelation for 2h, and directional freezing (-30℃) is carried out for 12h using low-temperature ethanol as a refrigerant. After being completely frozen, it is freeze-dried for 24h to obtain a TPM-aerogel power generation material (6mm high) with a layered structure and directional semi-penetrating micro / nano composite multi-level pores.

[0102] In this embodiment, polyacrylamide (PAM) organic ion hydrogel is used as the power source for wet gas power generation. Its preparation method is as follows: acrylamide monomer (1.5g), MBAA cross-linking agent (50mg), 50mg 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy) phenyl]-1-acetone are added to 15g ethylene glycol / glycerol / water mixed solvent (the mass ratio of water is 50%), the mixed solution is stirred for 30min, and then 0.5g MgCl is added and stirred for 1h to obtain PAM-MgCl pre-solution. The prepared solution is drop-cast into a mold that meets the required size, and then cured under ultraviolet light for 20min to obtain PAM-MgCl organic ion hydrogel. The PAM-MgCl organic ion hydrogel is then applied to the bottom of the TPM-aerogel for standby use.

[0103] In this embodiment, the wet gas power generation module has a TCO glass electrode as the bottom electrode and a Cu electrode as the top electrode. The triboelectric power generation module has an Ag electrode as the bottom electrode, and the triboelectric contact electrodes are made of conductive silicone tape and polyethylene terephthalate (PET). The mechanical stress is 50N and the mechanical compression is 60%. In this case, the TPM-aerogel-based dual-mode power generation system has a coupled voltage output of 105V and a current output of 156μA.

[0104] Example 8

[0105] In this embodiment, a TCNF / PVA / GO (CPG)-aerogel power generation material is provided, and its preparation method is as follows: a certain amount of PVA solution (5wt%) is added to the TCNF sol (1wt%), wherein the mass ratio of PVA to TCNF is 1:1. A certain amount of GO dispersion is then weighed and added to the above-mentioned TCNF / PVA sol, wherein the mass ratio of GO to TCNF is 1:4. After stirring evenly (2h) and degassing, the CPG sol is poured into a mold and gelled for 2h, and directionally frozen (-100℃) for 0.5h using liquid nitrogen as a refrigerant. After being completely frozen, it is freeze-dried for 24h to obtain a CPG-aerogel power generation material (10mm high) with a layered structure and directional, fully penetrating micro / nano composite multi-level pores.

[0106] In this example, a single-component polyacrylamide (PAM) network organic ion hydrogel was used as the power source for wet gas power generation. Its preparation method was as follows: 1.5g acrylamide, 30mg N,N'-methylenebisacrylamide (MBAA), and 30mg α-ketoglutaric acid were added to 10g of a glycerol / water mixed solvent (50% water by mass). The mixed solution was stirred for 30 minutes, and then 0.75g KCl was added and stirred for 1 hour to obtain a PAM-KCl pre-solution. The prepared solution was drop-cast into a mold of the required size and then cured under UV light for 10 minutes to obtain the PAM-KCl organic ion hydrogel. The PAM-KCl organic ion hydrogel was then applied to the bottom of the CPG aerogel and set aside.

[0107] In this embodiment, the wet gas power generation module has an Al bottom electrode and a Cu top electrode. The triboelectric power generation module has a Cu bottom electrode, and the triboelectric contact electrodes are composed of conductive cloth tape and polytetrafluoroethylene (PTFE). The mechanical stress is 20N and the mechanical compression is 60%. In this case, the dual-mode power generation system based on CPG-aerogel power generation materials has a coupled voltage output of 98V and a current output of 162μA.

[0108] Example 9

[0109] This embodiment provides an ANF / PVA / MXene (APM) aerogel power generation material. The preparation method is as follows: 0.5 g of commercially available ANF nanofibers and 1 g of KOH are added to 1 g of DMSO and magnetically stirred at room temperature for 24 hours to obtain an ANF solution (20 wt%). A certain amount of PVA solution (2 wt%) is added to the ANF solution, wherein the mass ratio of PVA to ANF is 2:1. A certain amount of MXene dispersion is then weighed and added to the ANF / PVA sol, wherein the mass ratio of MXene to ANF is 1:1. After stirring for 2 hours and degassing, the APM sol is poured into a mold and gelled for 2 hours. It is then directionally frozen (-196°C) using liquid nitrogen as a refrigerant for 0.5 hours. Once completely frozen, it is freeze-dried for 36 hours to obtain an APM-aerogel power generation material (8 mm in height) with a layered structure and directional, fully perforated micro / nano composite hierarchical pores.

[0110] In this embodiment, a polyacrylamide (PAM) single-component network organic ion hydrogel is used as the power source for wet gas power generation. Its preparation method is as follows: 1.5g acrylamide, 30mg N,N'-methylenebisacrylamide (MBAA), and 50mg α-ketoglutaric acid are added to 10g of a mixed solvent of ethylene glycol / glycerol / water (water ratio is 60% by mass). The mixed solution is stirred for 30 minutes, and then 0.25g AlCl3 is added and stirred for 1 hour to obtain a PAM-AlCl3 pre-solution. The prepared solution is drop-cast into a mold of the required size and then cured under ultraviolet light for 10 minutes to obtain a PAM-AlCl3 ion hydrogel. The PAM-AlCl3 ion hydrogel is then applied to the bottom of the APM aerogel and set aside.

[0111] In this embodiment, the bottom electrode of the wet gas power generation module is a Zn electrode and the upper electrode is a Cu electrode; the lower electrode of the triboelectric power generation module is a Cu electrode, and the triboelectric contact electrode is composed of conductive cloth tape and polypropylene (PP). The mechanical stress is 20N and the mechanical compression is 60%. In this case, the APM-aerogel-based dual-mode power generation system is directly connected to a commercial capacitor through an external circuit, which can charge the capacitor (4.7μF) ( Figure 6 ).

[0112] Example 10

[0113] In this embodiment, a TCNF / PVA / MXene (CPM)-aerogel power generation material is provided, and its preparation method is as follows: a certain amount of PVA solution (5wt%) is added to a commercial TCNF sol (1wt%), wherein the mass ratio of PVA to TCNF is 1:1. A certain amount of MXene dispersion is then weighed and added to the above-mentioned TCNF / PVA sol, wherein the mass ratio of MXene to TCNF is 1:4. After stirring evenly (2h) and degassing, the CPM sol is poured into a mold and gelled for 2h, and directionally frozen (-100℃) for 0.5h using liquid nitrogen as a refrigerant. After being completely frozen, it is freeze-dried for 24h to obtain a CPM-aerogel power generation material (2mm) with a layered structure and directional, fully penetrating micro / nano composite multi-level pores.

[0114] In this example, a single-component polyacrylamide (PAM) network organic ion hydrogel was used as the power source for wet gas power generation. Its preparation method was as follows: 1.5g acrylamide, 30mg N,N'-methylenebisacrylamide (MBAA), and 30mg α-ketoglutaric acid were added to 10g of a glycerol / water mixed solvent (50% water by mass). The mixed solution was stirred for 30 minutes, and then 0.6g KCl was added and stirred for 1 hour to obtain a PAM-KCl pre-solution. The prepared solution was drop-cast into a mold of the required size and then cured under UV light for 10 minutes to obtain the PAM-KCl organic ion hydrogel. The PAM-KCl organic ion hydrogel was then applied to the bottom of the CPM aerogel and set aside.

[0115] In this embodiment, the bottom electrodes of the wet gas power generation module are Al electrodes and the top electrodes are Cu electrodes. The MEG power generation unit based on CPM-aerogel power generation material can reach a stable voltage output within 4 minutes under low humidity (20%), and the MEG power generation is 0.8V ( Figure 7 ).

[0116] Comparative Example 1

[0117] In this embodiment, a TCNF / PVA / MXene (CPM)-aerogel power generation material is provided. The preparation method thereof is as follows: a certain amount of PVA solution (5 wt%) is added to a TCNF sol (1 wt%), wherein the mass ratio of PVA to TCNF is 1:1. A certain amount of MXene dispersion is then weighed and added to the above-mentioned TCNF / PVA sol, wherein the mass ratio of MXene to TCNF is 1:4. After stirring evenly (2 h) and degassing, the CPM sol is poured into a mold and gelled for 2 h, and then placed in a refrigerator and frozen for 24 h. After being completely frozen, it is freeze-dried for 24 h to obtain a CPM-aerogel power generation material (10 mm high) with non-directional semi-through micron pores.

[0118] In this example, a single-component polyacrylamide (PAM) network organic ion hydrogel was used as the power source for wet gas power generation. Its preparation method was as follows: 1.5g acrylamide, 30mg N,N'-methylenebisacrylamide (MBAA), and 30mg α-ketoglutaric acid were added to 10g of a glycerol / water mixed solvent (50% water by mass). The mixed solution was stirred for 30 minutes, and then 0.75g KCl was added and stirred for 1 hour to obtain a PAM-KCl pre-solution. The prepared solution was drop-cast into a mold of the required size and then cured under UV light for 10 minutes to obtain the PAM-KCl organic ion hydrogel. The PAM-KCl organic ion hydrogel was then applied to the bottom of the CPM aerogel and set aside.

[0119] In this embodiment, the wet gas power generation module has an Al bottom electrode and a Cu top electrode. The triboelectric power generation module has a Cu bottom electrode, and the triboelectric contact electrodes are composed of conductive cloth tape and polytetrafluoroethylene (PTFE). The mechanical stress is 20N and the mechanical compression is 60%. In this case, the dual-mode power generation system based on CPM-aerogel power generation material has a coupled voltage output of 90V and a current output of 56μA.

[0120] Comparative Example 2

[0121] This example provides a TCNF / PVA aerogel power generation material. The preparation method is as follows: a certain amount of PVA solution (5 wt%) is added to a TCNF sol (1 wt%), wherein the mass ratio of PVA to TCNF is 1:1. After stirring for 2 hours and degassing, the TCNF / PVA sol is poured into a mold and gelled for 2 hours. The sol is then directionally frozen (-100°C) using liquid nitrogen for 0.5 hours. Once completely frozen, it is freeze-dried for 24 hours to obtain a TCNF / PVA aerogel power generation material (10 mm) with multi-level pores that penetrate the micro / nano composite.

[0122] In this example, a single-component polyacrylamide (PAM) network organic ion hydrogel was used as the power source for wet gas power generation. Its preparation method was as follows: 1.5g acrylamide, 30mg N,N'-methylenebisacrylamide (MBAA), and 30mg α-ketoglutaric acid were added to 10g of a glycerol / water mixed solvent (50% water by mass). The mixed solution was stirred for 30 minutes, and then 0.75g KCl was added and stirred for 1 hour to obtain a PAM-KCl pre-solution. The prepared solution was drop-cast into a mold of the required size and then cured under UV light for 10 minutes to obtain the PAM-KCl organic ion hydrogel. The PAM-KCl organic ion hydrogel was then applied to the bottom of the TCNF / PVA aerogel and set aside.

[0123] In this embodiment, the wet gas power generation module has an Al bottom electrode and a Cu top electrode. The triboelectric power generation module has a Cu bottom electrode, and the triboelectric contact electrodes are composed of conductive cloth tape and polytetrafluoroethylene (PTFE). The mechanical stress is 20N and the mechanical compression is 60%. In this case, the dual-mode power generation system based on TCNF / PVA-aerogel materials has a coupled voltage output of 80V and a current output of 36μA.

Claims

1. A moisture-friction dual-mode power generation device, characterized in that: The wet gas-friction dual-mode power generation device includes: a wet gas power generation module and a friction power generation module; the wet gas power generation module and the friction power generation module are integrated by inserting electrodes and share the same power generation material; the wet gas power generation module also includes an organic ion hydrogel, which is arranged on the lower surface of the power generation material; wherein the power generation material is a composite aerogel of nanosheets, nanofibers and hydrophilic polymers; wherein the composite aerogel contains a layered structure, and there is a network composed of directional pores between each layer; the nanosheet is a two-dimensional nanosheet; the inserted electrode includes the bottom electrode of the wet gas power generation module, the upper electrode of the wet gas power generation module and the lower electrode of the friction power generation module; the friction power generation module also includes a friction contact electrode, wherein the friction contact electrode is arranged directly above the power generation material; the friction contact electrode includes a conductive tape and a friction functional layer.

2. The moisture-friction dual-mode power generation device according to claim 1, characterized in that: The mass ratio of the nanofibers to the hydrophilic polymer in the composite aerogel is 100:1 to 1:100; the mass ratio of the nanosheets to the nanofibers is 10:1 to 1:100; The two-dimensional nanosheet is one or more of graphene oxide GO, MXene, montmorillonite MMT, and molybdenum disulfide MoS2; The nanofiber is one or more of cellulose nanofiber CNF, aramid nanofiber ANF, and silk nanofiber SNFs; The hydrophilic polymer is one or more of polyvinyl alcohol (PVA), polyacrylic acid (PAA), and polyethylene glycol (PEG).

3. The moisture-friction dual-mode power generation device according to claim 2, characterized in that: The directional pores are one of fully through or semi-through micron pores, nano pores, and micro / nano composite pores, and the pores are directional and arranged in a vertical direction.

4. The moisture-friction dual-mode power generation device according to claim 2, characterized in that: The preparation method of the composite aerogel comprises: uniformly stirring nanofibers and a hydrophilic polymer solution, then adding nanosheets, stirring and degassing, gelling to obtain a pregel, and then freezing and drying to obtain the composite aerogel; Alternatively, the nanofibers and hydrophilic polymer solution are stirred evenly, and then the nanosheets are added, stirred evenly, 3D printed, frozen and dried to obtain a composite aerogel; and the height of the composite aerogel power generation material is 1~50 mm.

5. The moisture-friction dual-mode power generation device according to claim 4, characterized in that: The solvent of the hydrophilic polymer solution is one or more of deionized water, ethanol, glycerol, acetic acid, and ethyl acetate; The freezing is direct freezing or directional freezing.

6. The moisture-friction dual-mode power generation device according to claim 1, characterized in that: The organic ion hydrogel is provided on the lower surface of the power generation material: the organic ion hydrogel and the power generation material are directly adhered; The organic ion hydrogel components include a gel network matrix material, an inorganic salt, and a solvent; wherein the gel network matrix material includes any one of polyacrylamide (PAM), polyacrylamide (PAM) / polyvinyl alcohol (PVA), polyacrylamide (PAM) / gelatin (GA), and polyacrylamide (PAM) / polystyrene sulfonic acid (PSSA); the inorganic salt includes one or more of LiCl, NaCl, MgCl2, AlCl3, KCl, CaCl2, and CoCl2; the solvent is a blended solvent of an organic solvent and water; wherein the organic solvent includes one or more of ethylene glycol, glycerol, and dimethyl sulfoxide (DMSO); and the mass percentage of water in the blended solvent is 0.1-99.9%.

7. The moisture-friction dual-mode power generation device according to claim 1, characterized in that: The inserted electrode is one or more of an ITO glass electrode, an FTO glass electrode, a TCO glass electrode, and a metal electrode; The moisture-friction dual-mode power generation device further includes a circuit connector, wherein the circuit connector is a rectifier circuit, wherein the rectifier circuit couples the rectified AC output and DC output in parallel.

8. The moisture-friction dual-mode power generation device according to claim 1, characterized in that: The conductive tape includes one or more of a conductive cloth tape, a conductive silicone tape, and a conductive metal tape; the conductive component in the conductive tape includes one or more of platinum, gold, silver, copper, nickel, aluminum, carbon materials, graphene, MXene, carbon nanotubes, and conductive polymers; the friction functional layer material includes one or more of polytetrafluoroethylene (PTFE), polyfluoroethylene propylene (FEP), polydimethylsiloxane (PDMS), polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP), polyvinylidene fluoride (PVDF), polypropylene (PP), polyethylene terephthalate (PET), styrene propylene copolymer, styrene butadiene copolymer, rayon, polymethacrylate, polyvinyl alcohol, polyethylene glycol, polyester, polyisobutylene, polyethylene terephthalate, chloroprene rubber, butadiene propylene copolymer, natural rubber, polyacrylonitrile, acrylonitrile vinyl chloride, stainless steel sheet, iron sheet, copper sheet, and silver sheet.

9. Application of the moisture-friction dual-mode power generation device according to claim 1 in the fields of environmental energy collection and environmental detection.

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