阅读说明：本技术 一种功能化石墨烯卷水伏pn结的制备方法 (Preparation method of functionalized graphene roll-up photovoltaic PN junction ) 是由 苗中正 于 2020-01-09 设计创作，主要内容包括：本发明提供一种功能化石墨烯卷水伏PN结的制备方法。将羧基化石墨烯与氨基化石墨烯分别冷淬得到羧基化石墨烯卷与氨基化石墨烯卷；然后,在基底上设有上电极和下电极的一面,上下各半部分分别涂覆羧基化石墨烯卷浆料与氨基化石墨烯卷浆料,干燥后得到功能化石墨烯卷水伏PN结。本发明所述方法制备的功能化石墨烯卷水伏PN结可以吸收潮湿环境中的水分,形成类似太能能电池中p-n结中的内建电场,从而在外电路中产生电能,这种产电方式绿色环保且稳定,可用于湿度传感器或者湿气发电。(The invention provides a preparation method of a functionalized graphene roll photovoltaic PN junction. Respectively performing cold quenching on the carboxylated graphene and the aminated graphene to obtain a carboxylated graphene roll and an aminated graphene roll; and then, coating the carboxylated graphene roll slurry and the aminated graphene roll slurry on the surface of the substrate, which is provided with the upper electrode and the lower electrode, respectively at the upper half part and the lower half part, and drying to obtain the functionalized graphene roll photovoltaic PN junction. The functionalized graphene roll photovoltaic PN junction prepared by the method can absorb moisture in a humid environment to form a built-in electric field similar to a p-n junction in a solar cell, so that electric energy is generated in an external circuit.)

1. A preparation method of a functionalized graphene roll photovoltaic PN junction comprises the following steps:

(1) dispersing 100mg of graphene oxide or single-sided selective graphene oxide in water, adding 6g of sodium hydroxide and 5g of monochloroacetic acid, and carrying out ultrasonic treatment for 3h to obtain carboxylated graphene;

(2) dispersing 100mg of graphene oxide or single-sided selective graphene oxide in 100mLDMF, adding 15g of ethylenediamine and 5g of dicyclohexylcarbodiimide, and reacting at 120 ℃ for 48 hours to obtain aminated graphene;

(3) heating the prepared carboxylated graphene and aminated graphene solution, putting the solution into liquid nitrogen for cold quenching after the graphene oxide solution is boiled until the solution is completely frozen, taking out the solution, and carrying out in-situ freeze drying to obtain a carboxylated graphene roll and an aminated graphene roll;

(4) respectively dispersing the carboxylated graphene roll and the aminated graphene roll in a solvent to obtain slurry;

(5) coating two graphene oxide layers on the upper and lower sides of a substrate, and performing conventional microwave reduction treatment to obtain an upper electrode and a lower electrode;

(6) the method comprises the steps of coating carboxylated graphene roll slurry and aminated graphene roll slurry on the upper half part and the lower half part of one surface of a substrate, coating the next area after one area is completely dried, and drying to obtain the functionalized graphene roll photovoltaic PN junction, wherein the surface is provided with an upper electrode and a lower electrode.

2. The preparation method according to claim 1, wherein the graphene oxide and the single-side selective graphene oxide in the step (1) can be prepared by an existing method, and can also be directly purchased as a commercial product.

3. The preparation method according to claim 1, wherein the concentration of the graphene oxide solution required for liquid nitrogen quenching in the step (3) is 0.5-8 mg/ml.

4. The preparation method of claim 1, wherein the solvent in the step (4) is methanol, ethanol or deionized water, and the concentration of the carboxylated graphene and the aminated graphene is 0.1-10 mg/mL.

5. The method according to claim 1, wherein the substrate in the step (5) is a flexible substrate and a rigid substrate, the flexible substrate is a polyester resin film, a polyimide film, a polyvinyl chloride film, a polypropylene film, a polytetrafluoroethylene film or a teflon tape, and the rigid substrate is glass, quartz or ceramic.

6. The production method according to claim 1, wherein the electrode separation of the upper electrode and the lower electrode in the step (5) is 1 to 10cm, which functions as a contact with the graphene-based hydrophotovoltaic PN junction and as a lead-out electrode.

7. The production method according to claim 1, wherein the drying time in the step (6) is 1s to 1800s, and the drying temperature is 0 to 80 ℃.

8. The method of claim 1, wherein the thickness of the hydrophytic PN junction in the step (6) is 0.1-50 μm, and the humidity of the environment in which the moisture power generating device operates is more than 70%.

Technical Field

The invention relates to the field of preparation of moisture power generation devices, in particular to a preparation method of a functionalized graphene roll-up photovoltaic PN junction.

Background

Water is closely related to energy, maintains the energy circulation of the earth system, balances the temperature of organisms, and is a natural energy absorber, an energy storage device, an energy converter and an energy transfer device. Nearly 70% of the energy of the solar radiation reaching the earth surface is absorbed by water, and the annual average power of the water dynamically absorbing and releasing the energy on the earth is as high as 60 trillion kilowatts, which is 3 orders of magnitude higher than the annual average energy consumption power of the whole human. The traditional water energy utilization mode is greatly limited by natural conditions and is easily influenced by external factors such as terrain, climate and the like, and the construction and the use of large-scale facilities and equipment easily cause ecological damage and cost improvement. Novel energy conversion and storage technologies play an extremely important role in the development of society. Solar cells, wind generators, hydroelectric generators, and the like have been successfully developed to convert this energy into electrical energy to facilitate everyday activities. However, it is not uncommon to use the moisture diffusion process in nature directly for the generation of electrical energy. The nano material has obvious quantum effect and surface effect, can be coupled with water in various forms to output obvious electric signals, for example, graphene can directly convert the energy of dragging and falling water drops into electric energy through the boundary motion of an electric double layer, and can also convert the wave energy of seawater into electric energy. Nano-structured materials such as carbon black can continuously generate electric energy in volt level through natural evaporation of ubiquitous water in atmospheric environment. This phenomenon of direct conversion of water into electrical energy is known as the "hydro-voltaic effect". The hydroelectric effect opens up a brand new direction for capturing the water energy of the earth water circulation in a full-chain manner, and the water energy utilization capacity is improved. Guowanlin, Queliang, Zhang, Tang dynasty, Zhou Jianxin, Zhou Jun and the like make pioneer researches in the fields of wet gas power generation and hydroelectric science and technology. The research on the photovoltaic effect and the moisture power generation is just started, and novel materials and devices with diversified application environments, high energy conversion efficiency and low power generation cost need to be developed.

Disclosure of Invention

The invention aims to provide a preparation method of a functionalized graphene roll photovoltaic PN junction. By taking graphene oxide or single-sided selective graphene oxide as raw materials, carboxylated graphene, aminated graphene and reduced graphene oxide are respectively prepared. The reduced graphene oxide can be obtained by treating graphene oxide or single-sided selective graphene oxide with a conventional reducing agent and a microwave method. And (3) performing cold quenching on the carboxylated graphene and the aminated graphene in liquid nitrogen to prepare the nano coil. The purpose of preparing the nano-coil is to coil two-dimensional graphene oxide into a quasi-one-dimensional structure or shrink the graphene oxide into three-dimensional particles, wherein due to the asymmetry of single-sided selective graphene oxide, the acting force applied on the surface of the graphene oxide is different in the heating and cooling processes, and the coiled structure is formed by a planar structure more easily. The carboxylated graphene roll and the aminated graphene roll can absorb moisture in a humid environment, the surface of the carboxylated graphene roll can be ionized to form positive ions after water is absorbed by the carboxylated graphene roll, so that the surface of the carboxylated graphene roll has negative charges, the surface of the aminated graphene roll can be adsorbed with hydrogen ions after water is absorbed by the aminated graphene roll, so that the surface of the aminated graphene roll has positive charges, the two materials are placed on two sides of a device to form a graphene-based photovoltaic PN junction, the charge distribution is different due to the ionization of water molecules, the carboxylated or aminated graphene roll cannot move after being ionized or adsorbing ions, and the hydrogen ions and hydroxyl ions in an adsorbed water layer can freely move, the separation and combination are finally in a dynamic equilibrium process, a built-in electric field similar to that in a p-n junction in a solar cell is formed, therefore, electric energy is generated in an external circuit, the power generation mode is green, environment-friendly and stable, and the power generation device can be used for humidity sensors or moisture power generation.

The invention adopts the following technical scheme:

a preparation method of a functionalized graphene roll photovoltaic PN junction comprises the following steps:

(1) dispersing 100mg of graphene oxide or single-sided selective graphene oxide in water, adding 6g of sodium hydroxide and 5g of monochloroacetic acid, and carrying out ultrasonic treatment for 3h to obtain carboxylated graphene;

(2) dispersing 100mg of graphene oxide or single-sided selective graphene oxide in 100mLDMF, adding 15g of ethylenediamine and 5g of dicyclohexylcarbodiimide, and reacting at 120 ℃ for 48 hours to obtain aminated graphene;

(3) heating the prepared carboxylated graphene and aminated graphene solution, putting the solution into liquid nitrogen for cold quenching after the graphene oxide solution is boiled until the solution is completely frozen, taking out the solution, and carrying out in-situ freeze drying to obtain a carboxylated graphene roll and an aminated graphene roll;

(4) respectively dispersing the carboxylated graphene roll and the aminated graphene roll in a solvent to obtain slurry;

(5) coating two graphene oxide layers on the upper and lower sides of a substrate, and performing conventional microwave reduction treatment to obtain an upper electrode and a lower electrode;

(6) the method comprises the steps of coating carboxylated graphene roll slurry and aminated graphene roll slurry on the upper half part and the lower half part of one surface of a substrate, coating the next area after one area is completely dried, and drying to obtain the functionalized graphene roll photovoltaic PN junction, wherein the surface is provided with an upper electrode and a lower electrode.

The graphene oxide and the single-sided selective graphene oxide in the step (1) can be prepared by the existing method, and commercial products can also be directly purchased.

And (4) the concentration of the graphene oxide solution required by the liquid nitrogen cold quenching in the step (3) is 0.5-8 mg/ml.

The solvent in the step (4) is methanol, ethanol or deionized water, and the concentration of the carboxylated graphene and the aminated graphene is 0.1-10 mg/mL.

The substrate in the step (5) is a flexible substrate and a hard substrate, the flexible substrate is a polyester resin film, a polyimide film, a polyvinyl chloride film, a polypropylene film, a polytetrafluoroethylene film or a teflon tape, and the hard substrate is glass, quartz or ceramic.

And (4) the electrode interval between the upper electrode and the lower electrode in the step (5) is 1-10cm, and the electrode is used for contacting the graphene-based photovoltaic PN junction and serving as an extraction electrode.

The drying time in the step (6) is 1s-1800s, and the drying temperature is 0-80 ℃.

The thickness of the photovoltaic PN junction in the step (6) is 0.1-50 μm.

The humidity of the environment in which the moisture power generation device in the step (6) is operated should be more than 70%.

The invention has the following advantages:

(1) the functionalized graphene roll photovoltaic PN junction prepared by the method can absorb moisture in a humid environment, the surface of the carboxylated graphene roll is provided with negative charges, the surface of the aminated graphene roll is provided with positive charges, but the carboxylated or aminated graphene cannot move, hydrogen ions and hydroxyl ions in an adsorbed water layer can move freely, and the separation and combination of the hydrogen ions and the hydroxyl ions are finally in a dynamic balance process to form a built-in electric field similar to a p-n junction in a solar cell, so that electric energy is generated in an external circuit.

(2) Due to the fact that the graphene is curled into the graphene roll, the problem that graphene lamellar junctions are formed to be shielded mutually is avoided, the coating of the functionalized graphene roll photovoltaic PN junction can be thickened, more mobile charges are generated, and the power generation amount is improved.

(3) The method has the advantages of simple preparation process, easily obtained used materials, low requirement on equipment, large-scale production and great significance on the sustainable development of the society.

Drawings

Fig. 1 is a schematic structural diagram of a device according to the method of the present invention.

FIG. 2 is a schematic diagram of the principle of forming an internal p-n junction-like structure of the device according to the method of the present invention.

Detailed Description

For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the purpose of facilitating understanding of the present invention and should not be construed as specifically limiting the present invention.