Heterogeneous graphene oxide moisture-induced power generator and manufacturing method therefor

Abstract

Disclosed in embodiments of the present invention are a heterogeneous graphene oxide moisture-induced power generator and a manufacturing method therefor. The heterogeneous graphene oxide moisture-induced power generator comprises: an integrally formed heterostructure composed of a first component and a second component and arranged horizontally or vertically, wherein the first component is made of graphene oxide, and the second component is made of reduced graphene oxide. The heterogeneous graphene oxide moisture-induced power generator provided by the present invention has a relatively high open-circuit voltage and excellent cycle stability, and has the potential to be applied in flexible batteries; and by connecting the heterogeneous graphene oxide moisture-induced power generator in series or parallel, an ultra-high voltage generator set can be obtained, and a reduction device can be additionally mounted on an industrial coating line for preparing graphene oxide, thereby enabling large-scale mass production.

Description

Heterogeneous graphene oxide wet generator and preparation method thereof TECHNICAL FIELD

[0001] Embodiments of the present application relate to the technical field of wet power generation, in particular to a heterogeneous graphene oxide wet generator and a preparation method thereof. BACKGROUND

[0002] Recent research shows that the interaction between two-dimensional materials represented by graphene and water molecules can produce charge transfer and transmission due to quantum confinement effect and environment-sensitive surface effect caused by large specific surface area, thereby hoping to collect energy from rainwater, waves, flow and natural evaporation in the water cycle, which is the "wet power generation effect". Two-dimensional materials have large in-plane electron mobility, good thermal conductivity, high mechanical strength and toughness, can be used to prepare flexible devices, and have many advantages such as green environmental protection, wide source, simple structure, safety, non-toxicity and low cost. It is expected to build new flexible power generation and energy storage devices for micro and flexible devices. The implementation of this project and the promotion of related results are expected to enrich the types of new energy industry, cultivate new economic growth momentum, and promote the development of new energy industry. It has important significance for alleviating energy crisis and solving environmental pollution problems.

[0003] In existing wet power generation technology, carbon black and functionalized graphite surfaces are usually used to realize the regulation of wet power generation performance output power. There are also wet power generation devices based on two-dimensional graphene materials, which generate weak current by moving sodium chloride solution on the surface of two-dimensional graphene sheets. By adjusting the solution moving speed, moving direction and sodium chloride molar amount in the solution, the size and direction of the induced current are regulated. However, the current wet power generation technology has too low power density, and is severely dependent on the directional movement of water molecules on the surface of functionalized two-dimensional materials, or requires a large gradient of humidity environment. The generated power is a pulse voltage signal, which cannot continuously and stably improve high-power power, and cannot be packaged or mass produced. SUMMARY

[0004] Therefore, embodiments of the present application provide a heterogeneous graphene oxide wet generator and a preparation method thereof.

[0005] In order to achieve the above purpose, embodiments of the present application provide the following technical solutions:

[0006] According to the first aspect of the embodiments of the present application, the present application provides a heterogeneous graphene oxide wet generator, which comprises a one-piece heterogeneous structure arranged left and right or up and down composed of a first component and a second component, the material of the first component is graphene oxide, and the material of the second component is reduced graphene oxide.

[0007] Further, the integrated heterostructure is a planar membrane structure or a three-dimensional structure.

[0008] Further, the graphene oxide is prepared from graphene by a chemical oxidation method.

[0009] The chemical oxidation method for preparing graphene oxide is a conventional method in the art. As an example, flake graphite, potassium permanganate, and concentrated sulfuric acid are mixed in a ratio of 1 g:4 g:25 ml, stirred, and subjected to low-temperature reaction (0 ℃, 30 min), medium-temperature reaction (40 ℃, 3 h), high-temperature reaction (95 ℃, 5 min) with the addition of deionized water, and high-temperature reaction (95 ℃, 5 min) with the addition of hydrogen peroxide to exfoliate graphene oxide layers, thereby obtaining a yellow graphene oxide solution, which is repeatedly washed and centrifuged to obtain graphene oxide slurry.

[0010] Further, the reduced graphene oxide is prepared from graphene oxide by thermal reduction, chemical reduction, or laser reduction.

[0011] The reduction method for preparing reduced graphene oxide is a conventional method in the art. As an example, thermal reduction: graphene oxide is exposed to air or a reducing atmosphere by high-temperature heat treatment to remove oxygen groups, thereby reducing graphene. For example, heat treatment or thermal decomposition is used in an inert atmosphere. The reduction temperature is 200-1200°C, and the reduction time is 10 s-60 min. Chemical reduction: graphene oxide is reduced to graphene using a chemical reducing agent. Commonly used chemical reducing agents include hydrogen, hydrogen iodide, hydrazine hydrate, etc. These reducing agents can react with oxygen atoms to remove them, thereby reducing graphene. Temperature range: 20-100°C, reaction time: 1 min-24 h. Laser reduction: graphene oxide is locally heated by laser radiation to cause a reduction reaction. Laser power: 10W-30W, laser wavelength: 532 nm or 1064 nm, laser irradiation time: 1 s-1 min.

[0012] According to a second aspect of the embodiments of the present application, the present application provides a preparation method of the above-mentioned hetero graphene oxide wet generator, which comprises the following steps:

[0013] (1) Flake graphite is prepared into graphene oxide slurry by a chemical oxidation method;

[0014] (2) The graphene oxide slurry is batch coated and dried and rolled to obtain a graphene oxide film;

[0015] (3) A part of the graphene oxide film is reduced to obtain a hetero graphene oxide film;

[0016] (4) cut the heterogeneous graphene oxide film into a specific size, and connect the graphene oxide and the reduced graphene oxide with wires, respectively;

[0017] (5) humidify the graphene oxide film, and then package the wires, the heterogeneous graphene oxide and water together to obtain a heterogeneous graphene oxide wet generator.

[0018] Further, the method further comprises: connecting the heterogeneous graphene oxide wet generator in series and in parallel to obtain an integrated power generation array.

[0019] The embodiment of the present application has the following advantages:

[0020] (1) The heterogeneous graphene oxide wet generator prepared by the present application has a heterogeneous gradient structure, the contact area between water molecules and oxygen-containing groups is increased, and an open-circuit voltage of 0.96V can be generated.

[0021] (2) The heterogeneous graphene oxide wet generator prepared by the present application has a power density of 879.2 µW cm -3 , can be stably operated for more than 24 hours, can be recovered after humidification, and has excellent cycle stability.

[0022] (3) The heterogeneous graphene oxide wet generator prepared by the present application can be bent after flexible packaging, and its output performance is not affected after 180° bending, and has the potential to be applied to flexible batteries.

[0023] (4) The heterogeneous graphene oxide wet generator prepared by the present application can obtain a generator set with a voltage higher than that of a single generator after being connected in series and in parallel, and a reduction device can be installed on an industrial coating line for preparing graphene oxide, which is expected to be mass-produced. BRIEF DESCRIPTION OF DRAWINGS

[0024] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or prior art description. Obviously, the drawings in the following description are only exemplary, and for those skilled in the art, other drawings can be obtained without creative labor on the basis of the provided drawings.

[0025] Fig. 1 is a schematic diagram of the heterogeneous graphene oxide wet generator provided by the present application. In the figure: 1 is a water molecule, 2 is graphene oxide, 3 is reduced graphene oxide, 4 is a wire, and 5 is an LED lamp.

[0026] Fig. 2 is a picture of the graphene oxide film coating process provided by the present application.

[0027] Figure 3 is a schematic diagram of the coating line for batch production of heterogeneous graphene oxide provided by the present application (a) and a schematic diagram of cutting the heterogeneous graphene oxide (b).

[0028] Figure 4 is an XRD diagram of the heterogeneous graphene oxide wet generator provided by the present application, GO is graphene oxide, and rGO is reduced graphene oxide.

[0029] Figure 5 is the open-circuit voltage test data of the heterogeneous graphene oxide wet generator provided by the present application, which has a stable open-circuit voltage of 0.96V.

[0030] Figure 6 is a voltage diagram of 15V obtained by connecting the heterogeneous graphene oxide wet generator provided by the present application in series.

[0031] Figure 7 is a bending test diagram of the heterogeneous graphene oxide wet generator provided by the present application, which remains stable at different bending degrees.

[0032] Figure 8 is a picture of the heterogeneous graphene oxide wet generator provided by the present application powering an electronic watch. DETAILED DESCRIPTION

[0033] The following describes the embodiments of the present application by specific examples, and those skilled in the art can easily understand other advantages and effects of the present application from the disclosure. Obviously, the described embodiments are part of the embodiments of the present application, not all. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0034] Referring to Figure 1, the present application provides a heterogeneous graphene oxide wet generator, comprising water molecules 1, graphene oxide 2, reduced graphene oxide 3, wire 4, and LED lamp 5. Among them, graphene oxide 2 and reduced graphene oxide 3 are an integral structure without fracture in the plane.

[0035] Example 1

[0036] The present embodiment provides a preparation method of a heterogeneous graphene oxide wet generator, comprising the following steps:

[0037] (1) Prepare graphene oxide slurry from flake graphite by chemical oxidation method

[0038] Specifically, the scale graphite, potassium permanganate and concentrated sulfuric acid are mixed and stirred in a ratio of 1 g:4 g:25 ml according to a modified Hummers method, low-temperature reaction (0 ℃, 30 min) is carried out, medium-temperature reaction (40 ℃, 3h) is carried out, deionized water is added to carry out high-temperature reaction (95 ℃, 5 min), and after the high-temperature reaction is completed, hydrogen peroxide is added to exfoliate the graphene oxide layer to obtain a yellow graphene oxide solution, and after repeated washing and centrifugation, a graphene oxide slurry is obtained;

[0039] (2) The graphene oxide slurry is batch coated, dried and rolled to obtain a graphene oxide film

[0040] Specifically, the solid content and viscosity of the graphene oxide slurry are adjusted, and after coating and drying on a coating production line, a graphene oxide film (200 μm thick) is obtained.

[0041] (3) A part of the graphene oxide film is reduced to obtain reduced graphene oxide

[0042] Specifically, the right part of the graphene oxide film is reduced by thermal reduction, the reduction temperature is set to 450° in an atmospheric atmosphere, and the thermal reduction time is 60 s to obtain reduced graphene oxide.

[0043] (4) The heterogeneous graphene oxide film is cut into 1*3 cm, wherein the length and width of the graphene oxide in the heterogeneous graphene oxide film are 1*1.5 cm, the length and width of the reduced graphene oxide are 1*1.5 cm, the copper wire is connected to the two sides of the heterogeneous graphene oxide film by using conductive silver paste, and the copper wire is placed in a drying oven and dried at 60 ℃ for 1 h.

[0044] (5) The graphene oxide film is humidified, and then the lead wire, the heterogeneous graphene oxide, and the water are packaged together to obtain a heterogeneous graphene oxide wet generator

[0045] Specifically, the left half of the graphene oxide film is dropped into 200 μL of deionized water, and the entire heterogeneous graphene oxide film and lead wire are packaged with a PI film to obtain a heterogeneous graphene oxide wet generator.

[0046] (6) The heterogeneous graphene oxide wet generator is connected in series / parallel to obtain an integrated power generation array.

[0047] Example 2

[0048] The embodiment provides a preparation method of a heterogeneous graphene oxide wet generator, comprising the following steps:

[0049] (1) The scale graphite is prepared into graphene oxide slurry by a chemical oxidation method

[0050] Specifically: the scale graphite, potassium permanganate, concentrated sulfuric acid are mixed and stirred according to the ratio of 1g:4g:25ml, low-temperature reaction (0 ℃, 30 min), medium-temperature reaction (40 ℃, 3h), deionized water is added to high-temperature reaction (95 ℃, 5min), after high-temperature reaction, hydrogen peroxide is added to exfoliate graphene oxide layer to obtain a yellow graphene oxide solution, and the graphene oxide slurry is obtained after repeated washing and centrifugation;

[0051] (2) The graphene oxide slurry is batch coated, dried and rolled to obtain a graphene oxide film

[0052] Specifically: the solid content and viscosity of the graphene oxide slurry are adjusted, and the graphene oxide film (200 μm thick) is obtained after coating and drying on a coating production line;

[0053] (3) A part of the graphene oxide film is reduced to obtain reduced graphene oxide

[0054] Specifically: the right part of the graphene oxide film is reduced by thermal reduction in an atmospheric atmosphere, the reduction temperature is set to 450°, and the thermal reduction time is 100s, to obtain reduced graphene oxide;

[0055] (4) The heterogeneous graphene oxide film is cut into 0.5*1 cm, wherein the length and width of the graphene oxide in the heterogeneous graphene oxide film are 0.5*0.5 cm, the length and width of the reduced graphene oxide are 0.5*0.5 cm, the copper wire is connected to the two sides of the heterogeneous graphene oxide film with conductive silver paste, and the copper wire is placed in a drying oven at 60 ℃ for 1h;

[0056] (5) The graphene oxide film is humidified, and then the lead wire, the heterogeneous graphene oxide, and the water are packaged together to obtain a heterogeneous graphene oxide wet generator

[0057] Specifically: the left half of the graphene oxide film is dropped into 200 μL of deionized water, and the entire heterogeneous graphene oxide film and lead wire are packaged with a PI film to obtain a heterogeneous graphene oxide wet generator;

[0058] (6) The heterogeneous graphene oxide wet generator is connected in series / parallel to obtain an integrated power generation array.

[0059] Example 3

[0060] The embodiment provides a preparation method of a heterogeneous graphene oxide wet generator, comprising the following steps:

[0061] (1) The scale graphite is prepared into graphene oxide slurry by a chemical oxidation method

[0062] Specifically, the scale graphite, potassium permanganate and concentrated sulfuric acid are mixed and stirred in a ratio of 1 g:4 g:25 ml according to a modified Hummers method, low-temperature reaction (0 ℃, 30 min) is carried out, medium-temperature reaction (40 ℃, 3h) is carried out, deionized water is added to carry out high-temperature reaction (95 ℃, 5 min), and after the high-temperature reaction is completed, hydrogen peroxide is added to exfoliate the graphene oxide layer to obtain a yellow graphene oxide solution, and after repeated washing and centrifugation, a graphene oxide slurry is obtained;

[0063] (2) The graphene oxide slurry is batch coated, dried and rolled to obtain a graphene oxide film

[0064] Specifically, the solid content and viscosity of the graphene oxide slurry are adjusted, and after coating and drying on a coating production line, a graphene oxide film (400 μm thick) is obtained.

[0065] (3) A part of the graphene oxide film is reduced to obtain reduced graphene oxide

[0066] Specifically, the right part of the graphene oxide film is reduced by thermal reduction in an atmospheric atmosphere, the reduction temperature is set to 450°, and the thermal reduction time is 60s, to obtain reduced graphene oxide.

[0067] (4) The heterogeneous graphene oxide film is cut into 2*6 cm, wherein the length and width of the graphene oxide in the heterogeneous graphene oxide film are 2*3 cm, the length and width of the reduced graphene oxide are 2*3 cm, the copper wire is connected to the two sides of the heterogeneous graphene oxide film with conductive silver paste, and is placed in a drying oven at 60 ℃ for 1h.

[0068] (5) The graphene oxide film is humidified, and then the lead wire, the heterogeneous graphene oxide, and the water are packaged together to obtain a heterogeneous graphene oxide wet generator

[0069] Specifically, the left half of the graphene oxide film is dropped into 200 μL of deionized water, and the entire heterogeneous graphene oxide film and lead wire are packaged with a PI film to obtain a heterogeneous graphene oxide wet generator.

[0070] (6) The heterogeneous graphene oxide wet generator is connected in series / parallel to obtain an integrated power generation array.

[0071] Example 4

[0072] The embodiment provides a preparation method of a heterogeneous graphene oxide wet generator, comprising the following steps:

[0073] (1) The scale graphite is prepared into graphene oxide slurry by a chemical oxidation method

[0074] Specifically, the scale graphite, potassium permanganate and concentrated sulfuric acid were mixed and stirred in a ratio of 1 g:4 g:25 ml according to a modified Hummers method, low-temperature reaction (0 ℃, 30 min) was carried out, medium-temperature reaction (40 ℃, 3h) was carried out, deionized water was added to carry out high-temperature reaction (95 ℃, 5 min), and after the high-temperature reaction was completed, hydrogen peroxide was added to exfoliate the graphene oxide layer to obtain a yellow graphene oxide solution, and after repeated washing and centrifugation, a graphene oxide slurry was obtained;

[0075] (2) The graphene oxide slurry was batch coated, dried and rolled to obtain a graphene oxide film

[0076] Specifically, the solid content and viscosity of the graphene oxide slurry were adjusted, and after coating and drying on a coating production line, a graphene oxide film (400 μm thick) was obtained.

[0077] (3) A part of the graphene oxide film was reduced to obtain reduced graphene oxide

[0078] Specifically, the right part of the graphene oxide film was reduced by laser reduction, the laser switch was turned on, the current was set to 2.5 A, the output power was set to 25 W, and the laser moved on the graphene oxide film to obtain reduced graphene oxide within 1 s.

[0079] (4) The heterogeneous graphene oxide film was cut into 1*3 cm, wherein the length and width of the graphene oxide in the heterogeneous graphene oxide film were 1*1.5 cm, the length and width of the reduced graphene oxide were 1*1.5 cm, the copper wire was connected to the two sides of the heterogeneous graphene oxide film with conductive silver paste, and the copper wire was placed in a drying oven at 60 ℃ for 1 h.

[0080] (5) The graphene oxide film was humidified, and then the lead wire, the heterogeneous graphene oxide, and the water were packaged together to obtain a heterogeneous graphene oxide wet generator

[0081] Specifically, the left half of the graphene oxide film was dropped into 200 μL of deionized water, and the entire heterogeneous graphene oxide film and lead wire were packaged with a PI film to obtain a heterogeneous graphene oxide wet generator.

[0082] (6) The heterogeneous graphene oxide wet generator was connected in series / parallel to obtain an integrated power generation array.

[0083] Example 5

[0084] The embodiment provides a preparation method of a heterogeneous graphene oxide wet generator, comprising the following steps:

[0085] (1) The scale graphite was prepared into graphene oxide slurry by a chemical oxidation method

[0086] Specifically: the scale graphite, potassium permanganate, concentrated sulfuric acid were mixed according to the ratio of 1g:4g:25ml, stirred, and reacted at low temperature (0 ℃, 30 min), medium temperature (40 ℃, 3h), and then deionized water was added to react at high temperature (95 ℃, 5min). After the high-temperature reaction, hydrogen peroxide was added to exfoliate the graphene oxide layer to obtain a yellow graphene oxide solution. After repeated washing and centrifugation, a graphene oxide slurry was obtained.

[0087] (2) The graphene oxide slurry was batch coated, dried and rolled to obtain a graphene oxide film

[0088] Specifically: the solid content and viscosity of the graphene oxide slurry were adjusted, and the graphene oxide film (800 μm thick) was obtained after coating and drying on the coating production line.

[0089] (3) A part of the graphene oxide film was reduced to obtain reduced graphene oxide

[0090] Specifically: a part of the graphene oxide film was reduced by laser reduction. The laser switch was turned on, the current was set to 2.5 A, the output power was set to 25 W, and the laser moved on the graphene oxide film. Reduced graphene oxide was obtained within 1 s.

[0091] (4) The heterogeneous graphene oxide film was cut into 2*6 cm, wherein the length and width of the graphene oxide in the heterogeneous graphene oxide film were 2*3 cm, and the length and width of the reduced graphene oxide were 2*3 cm. The copper wire was connected to the two sides of the heterogeneous graphene oxide film with conductive silver paste, and was dried in a drying oven at 60 ℃ for 1h.

[0092] (5) The graphene oxide film was humidified, and then the lead wire, the heterogeneous graphene oxide, and the water were packaged together to obtain a heterogeneous graphene oxide wet generator

[0093] Specifically: the left half of the graphene oxide film was dropped into 200 μL of deionized water, and the entire heterogeneous graphene oxide film and lead wire were packaged with a PI film to obtain a heterogeneous graphene oxide wet generator.

[0094] (6) The heterogeneous graphene oxide wet generator was connected in series / parallel to obtain an integrated power generation array.

[0095] Test example

[0096] 1. Chemical component test XRD (X-ray diffraction)

[0097] Test method: The structural properties were determined by X-ray diffraction (XRD) at a scan rate of 5° / min with Cu Ka radiation (λ = 0.15418 nm). The test results show that the characteristic peak at 10° is graphene oxide, and the characteristic peak at 24° is reduced graphene oxide, which proves that the graphene oxide is converted into reduced graphene oxide after reduction treatment.

[0098] 2. Electricity generation test: open circuit voltage test

[0099] Test method: The lead wire of the hetero graphene oxide wet power generation device (1*3 cm) packaged with PI film in step (5) of Example 1 was connected to a multifunctional multimeter (DMM 4050 Digit Precision Multimeter) for testing, the environmental humidity was RH~75%, and the environmental temperature was ~25℃. The results show that the device can generate a stable open circuit voltage of 0.96V.

[0100] 3. Series connection

[0101] Test method: 16 hetero graphene oxide wet power generation devices (1*3 cm) packaged with PI film in step (5) of Example 1 were connected in series, and the battery pack connected in series was connected to a multifunctional multimeter (DMM 4050 Digit Precision Multimeter) for testing, the environmental humidity was RH~75%, and the environmental temperature was ~25℃. The results show that the device can obtain a high voltage of 15V through multi-stage series connection.

[0102] 4. Bending test

[0103] Test method: Four hetero graphene oxide wet power generation devices (0.5*1 cm) packaged with PI film in step (5) of Example 2 were connected in series, and the integrated power generation array was connected to a multimeter, and the bending test was performed by using tweezers. The results show that under the bending of 0°, 30°, and 180°, the voltage does not change obviously and remains stable.

[0104] 5. Electronic watch power supply

[0105] Test method: The hetero graphene oxide wet power generation devices (1*3 cm) packaged with PI film in step (5) of Example 1 were connected in series to obtain five battery watch bands connected in series, and the positive and negative electrodes were connected to an electronic watch to supply power to the watch.

[0106] Although the present application has been described in detail above with general description and specific embodiments, some modifications or improvements can be made on the basis of the present application, which is obvious to those skilled in the art. Therefore, these modifications or improvements made on the basis of not deviating from the spirit of the present application are within the scope of the present application.

Claims

1. A heterogeneous graphene oxide wet generator, characterized in that: It comprises an integrally formed heterogeneous structure consisting of a first component and a second component arranged left to right or up to down, wherein the first component is made of graphene oxide, and the second component is made of reduced graphene oxide.

2. The heterogeneous graphene oxide wet generator according to claim 1, characterized in that: The integrally formed heterogeneous structure is a planar membrane structure or a three-dimensional structure.

3. The heterogeneous graphene oxide wet generator according to claim 1, characterized in that: The graphene oxide is prepared by chemical oxidation using graphene as a raw material.

4. The heterogeneous graphene oxide wet generator according to claim 1, characterized in that: The reduced graphene oxide is prepared from graphene oxide as a raw material through thermal reduction, chemical reduction or laser reduction.

5. A method for preparing a heterogeneous graphene oxide wet generator according to claim 1, characterized in that: The method comprises the following steps: (1) preparing graphene oxide slurry from flake graphite by chemical oxidation; (2) coating the graphene oxide slurry in batches, drying and rolling to obtain a graphene oxide film; (3) reducing a portion of the graphene oxide film to obtain a heterogeneous graphene oxide film; (4) Cutting the heterogeneous graphene oxide film into specific sizes and connecting the graphene oxide and reduced graphene oxide with wires; (5) The graphene oxide film is humidified, and then the wires, heterogeneous graphene oxide, and water are packaged together to obtain a heterogeneous graphene oxide wet generator.

6. The method for preparing a heterogeneous graphene oxide wet generator according to claim 5, wherein: The method further includes: connecting the heterogeneous graphene oxide wet generators in series and parallel to obtain an integrated power generation array.

Images