CN114678575A - Large-area microbial film moisture power generation device and preparation method and application thereof - Google Patents
Large-area microbial film moisture power generation device and preparation method and application thereof Download PDFInfo
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N3/00—Generators in which thermal or kinetic energy is converted into electrical energy by ionisation of a fluid and removal of the charge therefrom
Abstract
The invention discloses a large-area microbial film moisture power generation device and a preparation method and application thereof. A microbial film moisture power generation device comprises a bottom electrode, a composite microbial film and a top electrode; one surface of the composite microbial film is attached and connected with the top electrode, and the other surface of the composite microbial film is attached and connected with the bottom electrode; the composite microbial film contains electrically active bacteria, conducting agent and water adhesive. The composite microbial film comprises electroactive microbial liquid, a conductive agent and a water-based binder, the addition of the water-based binder increases the film forming property of a large-area film, the overall appearance of the surface of the film is good, the film is not chapped under the condition of air drying, and the film is easy to store; the conductive agent is added, so that the output performance of the photovoltaic device is effectively improved; the microbial film moisture power generation device has high performance output, can be maintained for a long time, meets the requirements of practical application, and is suitable for various application scenes.
Description
Technical Field
The invention belongs to the technical field of new energy, and particularly relates to a large-area microbial film moisture power generation device and a preparation method and application thereof.
Background
In recent years, the water-based technology of outputting electric energy by means of water evaporation or water vapor adsorption into materials in the nature has attracted much attention, since the atmosphere has almost nothingThe water vapor resource is exhausted and has no pollution, so the hydro-voltaic technology is an energy conversion mode with important development potential. The traditional photovoltaic technology mainly depends on emerging materials such as carbon nano tubes, graphene, protein nano wires and the like, but the materials are expensive and complex to prepare, so that the photovoltaic technology is difficult to be applied and developed on a large scale. Therefore, the appearance of the microbial photovoltaic technology provides a new idea for the development of the traditional photovoltaic technology. The microbial photovoltaic device is a novel photovoltaic device which replaces the traditional photovoltaic moisture absorption material by utilizing an electric active microbial bacteria to manufacture a biological membrane. In the current related research, the microbial photovoltaic technology has achieved many breakthrough results, such as preparing protein nanowire thin film by using sulfur-reducing bacillus in the Power generation from biological reagent using protein nanowires (DOI:10.1016/j. nano. 2021.106361), combining the biofilm with metal electrode to form a novel photovoltaic device, the biofilm photovoltaic device generates 0.5V open-circuit voltage, 250nA short-circuit current, and the current density is about 17 muA/cm2But far from meeting the requirements of practical application. The low output power and the small output current are the bottlenecks in the development of the traditional photovoltaic technology, so how to improve the output power and the output current of the photovoltaic device becomes the problem to be solved urgently in the field.
To increase the output current, series-parallel arrangements are a simple, effective and common approach. However, the traditional photovoltaic mostly adopts new expensive materials, and the preparation method is complex; for example, "bioinsed structural Nanofacial Electrode for Silicon Hydrovoltaic Device with Record Power Output" (DOI: 10.1021/acsano.1c00891), an electro-hydraulic Device based on Silicon nanowire arrays (SiNWs) was fabricated by coating the back of the SiNWs with a conductive silver coating as the bottom Electrode and a composite fabric Electrode on the surface of the SiNWs as the top Electrode. The preparation process of the SiNWs comprises the following steps: (1) washing a monocrystalline silicon wafer by using acetone, ethanol and deionized water; (2) corroding the washed silicon wafer with 5% HF water solution at room temperature for 5min to remove silicon dioxide; (3) immersing the silicon wafer in 4.8M HF and 0.01M AgNO3Soaking the components in the solution for 30 to 40 seconds; (4) immersion in 4.8M HF and 0.3M H2O2In the etchant of the composition by changing the etching timePreparing SiNW with different lengths; (5) soaking SiNWs in a nitric acid solution to dissolve redundant silver; (6) rinsed with deionized water and dried. The SiNWs are complex in manufacturing process and high in material cost. Therefore, the finding of the photovoltaic device which is low in price, simple in preparation process and capable of effectively improving the output performance has great significance for the development of green energy and the development of photovoltaic technology.
Disclosure of Invention
In order to overcome the problems of low output power and low output current of the conventional photovoltaic device, the invention aims to provide a microbial film moisture power generation device, a preparation method of the microbial film moisture power generation device and an application of the microbial film moisture power generation device.
The inventor finds that the output power and the current of a photovoltaic device can be effectively improved by increasing the area of the film, but the film forming property of the film is reduced along with the increase of the manufacturing area, and the electricity generating function is failed due to chapping of the surface of the film, so that the technical problem to be solved by the invention is how to improve the area of the film and further improve the output power and the current while ensuring the film forming property of the film.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a microbial film moisture power generation device, which comprises a bottom electrode, a composite microbial film and a top electrode; one surface of the composite microbial film is attached and connected with the top electrode, and the other surface of the composite microbial film is attached and connected with the bottom electrode; the composite microbial film contains electrically active bacteria, conducting agent and water adhesive.
Preferably, the area of the composite microbial film of the microbial film moisture power generation device is 100-10000cm2(ii) a Further preferably, the area of the composite microbial film is 100-5000cm2。
Preferably, the thickness of the composite microbial film of the microbial film moisture power generation device is 5-100 μm; the thickness of the composite microbial film can be reasonably adjusted by a person skilled in the art according to the actual use requirement, so that the corresponding power generation efficiency can be obtained.
Preferably, in the microbial film moisture power generation device, the conductive agent is at least one of carbon fibers (VGCF), carbon nanotubes (GNTs) and acetylene black; further preferably, the conductive agent is acetylene black.
Preferably, the microbial film wet gas power generation device has the water-based binder of at least one of polytetrafluoroethylene emulsion (PTFE), Polyacrylate (PAA), styrene butadiene emulsion (SBR) and carboxymethyl cellulose (CMC); further preferably, the aqueous binder is carboxymethyl cellulose; carboxymethyl Cellulose (CMC) is a white powder with high viscosity after dissolving in water; the inventor finds that when the moisture power generation device is prepared, appropriate amount of carboxymethyl cellulose and acetylene black are added into the electroactive bacterial liquid to improve the output power and the output current of the microbial film moisture power generation device.
Preferably, in the microbial film wet gas power generation device, the electroactive bacteria is one of thiobacillus thioredoccus (PCA) and Shewanella oneidensis (MR-1); further preferably, the electroactive bacterium is Shewanella oneidensis MR-1; electroactive microorganisms (EAMs) are biological resources which are widely existed in nature and can be regenerated, and have strong moisture absorption performance and ionization performance due to the fact that the EAMs contain a large number of oxygen-containing hydrophilic groups and good conductivity. The film prepared by using the electroactive microorganisms contains a large number of nano-voids and oxygen-containing functional groups inside, when the film is contacted with moisture in the air, the oxygen-containing functional groups release ions, and the ions directionally flow to enable two ends of the film to generate electric signals.
Preferably, the bottom electrode of the microbial film moisture power generation device is made of one of ITO conductive glass, titanium, iron, copper, aluminum, gold and silver; further preferably, the bottom electrode is made of one of ITO conductive glass and titanium; those skilled in the art can select other conductive materials according to practical use conditions.
Preferably, in the microbial film moisture power generation device, the material of the top electrode is one of copper, aluminum, titanium, gold and silver; further preferably, the material of the top electrode is one of copper and titanium; still further preferably, the top electrode is made of titanium; those skilled in the art can select other conductive materials according to practical use conditions.
Preferably, the microbial film moisture power generation device is provided with a top electrode with a mesh structure; the mesh number of the mesh structure is 10-400 meshes; further preferably, the mesh structure has a mesh number of 50-350 meshes; still more preferably, the mesh number of the mesh structure is 100-300 meshes; more preferably, the mesh structure has a mesh number of 150-200 meshes; the mesh number in the invention is based on Chinese specification, namely the aperture of 10 meshes is 2.00mm, the term "mesh number" in the invention refers to the mesh number in the area of 1 square inch (25.4mm multiplied by 25.4mm), and the mesh number can be reasonably adjusted by a person skilled in the art according to the actual use condition.
Preferably, the microbial film moisture power generation device has a smaller top electrode area than a bottom electrode area.
The invention provides a preparation method of the microbial film moisture power generation device, which comprises the following steps:
(1) mixing the electroactive bacterial liquid with a water-based binder and a conductive agent to obtain a composite bacterial liquid;
(2) and (2) coating the composite bacterial liquid obtained in the step (1) on one surface of the bottom electrode, drying, forming a composite microbial film on one surface of the bottom electrode, and covering a top electrode on the surface of the composite microbial film to obtain the microbial film moisture power generation device.
Preferably, in the preparation method of the microbial film moisture power generation device, in the step (1), the concentration of the electroactive bacteria is 1g of wet bacteria/(2-6) mL of bacteria liquid; more preferably, the concentration of the electroactive bacteria is 1g wet bacteria/(3-5) mL bacteria liquid; in some preferred embodiments of the invention, the concentration of electroactive bacteria is 1g wet bacteria/4 mL of bacteria solution.
Preferably, in the preparation method of the microbial film moisture power generation device, in the step (1), the mass ratio of the electroactive bacteria, the conductive agent and the aqueous binder is (8-96): (1-2) 1; more preferably, the mass ratio of the electroactive bacteria to the conductive agent to the aqueous binder is (25-96): (1-2) 1; the mass ratio of the electroactive bacteria to the conductive agent to the aqueous binder can be 8:1:1, 16:1:1, 32:1:1, 48:2:1, 56:1:1, 64:1:1, 72:1:1, 80:1:1, 88:1:1, and 96:1: 1; the proportion of the aqueous binder and the conductive agent can be adjusted by those skilled in the art according to the actual situation.
Preferably, in the method for manufacturing the microbial film wet gas power generation device, in the step (2), the drying temperature is 15-90 ℃, and a person skilled in the art can reasonably adjust the drying temperature according to the actually used electroactive bacteria and the bacteria concentration.
The third aspect of the invention provides the application of the microbial film moisture power generation device in power generation.
Preferably, the microbial film moisture power generation device is applied to electrical equipment.
The invention has the beneficial effects that:
the composite microbial film comprises electroactive microbial liquid, a conductive agent and a water-based binder, the addition of the water-based binder increases the film forming property of a large-area film, the overall appearance of the surface of the film is good, the film is not chapped under the condition of air drying, and the film is easy to store; the conductive agent is added, so that the output performance of the photovoltaic device is effectively improved; the area is 100cm2The composite film generates a short-circuit current of about 0.4mA and an open-circuit voltage of 0.4V, keeps stable, is connected to an 800k omega load resistor, and has load output power of 65 muW; the microbial film moisture power generation device has high performance output, can be maintained for a long time, meets the requirements of practical application, and is suitable for various application scenes.
The electro-active bacteria (especially Shewanella) adopted by the invention are widely distributed in nature, the growth period is short, the artificial culture mode is simple and quick, the culture can be quickly carried out in a short time, and the current can be generated by the electro-active bacteria, so the electro-active bacteria have great application value in the aspect of manufacturing the microbial battery. The interior of the electroactive bacterial film contains a large number of oxygen-containing groups, and the film is placed in a moisture environment, so that the oxygen-containing groups adsorb water molecules and release charged ions. After the external circuit is connected, a concentration gradient is generated in the direction of the thin film vertical to the bottom electrode due to the accumulation of charged ions at one end of the thin film, and electric signals are generated by the transfer of charges under the operation of the concentration gradient.
The wet gas power generation device does not need additional energy input in the power generation process, is green and environment-friendly in the power generation process, and can be used as a novel green energy source to supply power for modern electronic equipment.
Drawings
FIG. 1 is a schematic view of a microbial film moisture power plant according to an embodiment of the present invention.
FIG. 2 is a graph showing open circuit voltage and short circuit current at 75% relative humidity of the microbial film moisture electric power plant according to examples 1 to 8 of the present invention.
FIG. 3 shows the open circuit voltage, short circuit current and power of the microbial film moisture power generation device in example 6 of the present invention when discharging to different load resistors at 75% relative humidity.
FIG. 4 is a schematic diagram of a microbial film according to example 9 of the present invention.
FIG. 5 is a graph showing the open circuit voltage and the short circuit current at 75% relative humidity of the microbial film moisture electric power plant in example 9 of the present invention.
FIG. 6 is a graph showing the open-circuit voltage and the short-circuit current of the microbial film moisture power plant according to example 9 of the present invention, which was discharged for a long time at 75% relative humidity.
FIG. 7 shows the area of 30X 30cm of example 92The microbial film moisture power generation device lights the electronic display screen.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials or apparatuses used in the examples and comparative examples were obtained from conventional commercial sources or may be obtained by a method of the prior art, unless otherwise specified. Unless otherwise indicated, the testing or testing methods are conventional in the art.
The microorganisms referred to in the following examples and comparative examples are shown in Table 1.
TABLE 1 microorganisms used in examples of the present invention and comparative examples
Construction method of large-area microbial film moisture power generation device
The microbial film prepared from the electroactive microorganisms is placed in a water vapor environment, and because a large number of nano-pores and oxygen-containing functional groups are contained in the film, water vapor flows in the nano-pores. When the surface of the film (the contact surface with the top electrode) contacts water molecules in the air, a large number of hydrophilic functional groups such as OH-and-COOH and the like adsorb the water molecules in the air and release charged ions after in-situ decomposition, so that a concentration gradient difference in the vertical direction of the film is generated between the top electrode and the bottom electrode. Under the action of the concentration gradient, the charged ions move directionally in the low concentration direction (contact surface with the bottom electrode). The electrodes at the two ends of the film are connected with an external circuit, and continuous electric energy output is generated as the charged ions are gathered at the top of the film and continuously move to the low-concentration end along with the continuous evaporation of water vapor from the upper half part of the device.
Carboxymethyl cellulose (CMC) is white powder, is easily dissolved in water, is a transparent jelly after being dissolved in water, has high viscosity and strong hygroscopicity, and has the functions of thickening and bonding in an aqueous solution. As large-area films are easy to chap when being manufactured and are difficult to store in a dry environment, the film-forming property of the films is enhanced by adding CMC into the bacterial liquid. Acetylene black (ACET), one of the conductive carbon blacks, is moisture-absorbing and can improve the conductivity and prolong the storage life of the battery in terms of battery fabrication. According to the invention, ACET is added into the bacterial liquid, so that the conductivity of the microbial film is improved.
A schematic structural diagram of a microbial film moisture power generation device is shown in figure 1, the microbial film moisture power generation device adopts a sandwich structure, and the device sequentially comprises a porous top electrode, a composite microbial film and a bottom electrode from top to bottom. In the invention, the titanium mesh is used as a top electrode, and the ITO conductive glass is used as a bottom electrode.
Example 1
The microbial film moisture power generation device comprises a porous top electrode, a bottom electrode and a Shewanella composite biological film.
The preparation method comprises the following steps:
(1) taking the cultured Shewanella bacteria liquid, carrying out 5500rmp centrifugation to obtain Shewanella bacteria, and adding ultrapure water to carry out rapid resuspension to obtain Shewanella bacteria liquid (1g of wet bacteria/4 ml of bacteria liquid).
(2) And (3) according to the wet weight of the thalli, adding CMC powder and ACET powder in a ratio of ACET to CMC (8: 1: 1) into a stone mortar respectively, grinding for 20 minutes, adding the ground medicine powder into the resuspended bacterial liquid, and fully stirring and mixing to obtain the composite bacterial liquid.
(3) Coating 10ml of the composite bacterial liquid obtained in the step (2) on an ITO bottom electrode, and drying at 25 ℃ and room temperature to obtain the Shewanella composite microbial film with the film area of 100cm2. And then placing a porous top electrode titanium mesh (with a mesh structure of 200 meshes) slightly smaller than the area of the bottom electrode on the composite microbial film to obtain the microbial film moisture power generation device.
Example 2
(1) Taking the cultured Shewanella bacteria liquid, carrying out 5500rmp centrifugation to obtain Shewanella bacteria, and adding ultrapure water to carry out rapid resuspension to obtain Shewanella bacteria liquid (1g of wet bacteria/4 ml of bacteria liquid).
(2) And (3) according to the wet weight of the bacteria, adding CMC powder and ACET powder in a ratio of ACET to CMC (16: 1: 1) into a stone mortar respectively, grinding for 20 minutes, adding the ground medicine powder into the resuspended bacteria liquid, and fully stirring and mixing to obtain the composite bacteria liquid.
(3) Coating 10ml of the composite bacterial liquid obtained in the step (2) on an ITO bottom electrode, and drying at 25 ℃ and room temperature to obtain the Shewanella composite microbial film with the film area of 100cm2. Then a porous titanium net with a top electrode (mesh structure is that)200 meshes) to obtain the microbial film moisture power generation device.
Example 3
(1) Taking the cultured Shewanella bacteria liquid, carrying out 5500rmp centrifugation to obtain Shewanella bacteria, and adding ultrapure water to carry out rapid resuspension to obtain Shewanella bacteria liquid (1g of wet bacteria/4 ml of bacteria liquid).
(2) According to the wet weight of the thalli, adding CMC powder and ACET powder in a ratio of ACET to CMC (24: 1: 1) into a stone mortar respectively, grinding for 20 minutes, adding the ground medicine powder into the resuspended bacterial liquid, and fully stirring and mixing to obtain the composite bacterial liquid.
(3) Coating 10ml of the composite bacterial liquid obtained in the step (2) on an ITO bottom electrode, and drying at 25 ℃ and room temperature to obtain the Shewanella composite microbial film with the film area of 100cm2. And then placing a porous top electrode titanium mesh (with a mesh structure of 200 meshes) slightly smaller than the area of the bottom electrode on the composite microbial film to obtain the microbial film moisture power generation device.
Example 4
(1) Taking the cultured Shewanella bacterium solution, carrying out 5500rmp centrifugation to obtain Shewanella thallus, and adding ultrapure water to carry out rapid resuspension to obtain Shewanella bacterium solution (1g of wet thallus/4 ml of solution).
(2) And (3) according to the wet weight of the bacteria, adding CMC powder and ACET powder in a ratio of ACET to CMC (32: 1: 1) into a stone mortar respectively, grinding for 20 minutes, adding the ground medicine powder into the resuspended bacteria liquid, and fully stirring and mixing to obtain the composite bacteria liquid.
(3) Coating 10ml of the composite bacterial liquid obtained in the step (2) on an ITO bottom electrode, and drying at 25 ℃ and room temperature to obtain the Shewanella composite microbial film with the film area of 100cm2. And then placing a porous top electrode titanium mesh (with a mesh structure of 200 meshes) slightly smaller than the area of the bottom electrode on the composite microbial film to obtain the microbial film moisture power generation device.
Example 5
(1) Taking the cultured Shewanella bacteria liquid, carrying out 5500rmp centrifugation to obtain Shewanella bacteria, and adding ultrapure water to carry out rapid resuspension to obtain Shewanella bacteria liquid (1g of wet bacteria/4 ml of bacteria liquid).
(2) And (3) according to the wet weight of the bacteria, adding CMC powder and ACET powder in a ratio of ACET to CMC (48: 1: 1) into a stone mortar respectively, grinding for 20 minutes, adding the ground medicine powder into the resuspended bacteria liquid, and fully stirring and mixing to obtain the composite bacteria liquid.
(3) Coating 10ml of the composite bacterial liquid obtained in the step (2) on an ITO bottom electrode, and drying at 25 ℃ and room temperature to obtain the Shewanella composite microbial film with the film area of 100cm2. And then placing a porous top electrode titanium net (with a mesh structure of 200 meshes) slightly smaller than the area of the bottom electrode on the composite microbial film to obtain the microbial film moisture power generation device.
Example 6
(1) Taking the cultured Shewanella bacteria liquid, carrying out 5500rmp centrifugation to obtain Shewanella bacteria, and adding ultrapure water to carry out rapid resuspension to obtain Shewanella bacteria liquid (1g of wet bacteria/4 ml of bacteria liquid).
(2) And (3) according to the wet weight of the bacteria, adding CMC powder and ACET powder in a ratio of ACET to CMC (48: 2: 1) into a stone mortar respectively, grinding for 20 minutes, adding the ground medicine powder into the resuspended bacteria liquid, and fully stirring and mixing to obtain the composite bacteria liquid.
(3) Coating 10ml of the composite bacterial liquid obtained in the step (2) on an ITO bottom electrode, and drying at 25 ℃ and room temperature to obtain the Shewanella composite microbial film with the film area of 100cm2. And then placing a porous top electrode titanium mesh (with a mesh structure of 200 meshes) slightly smaller than the area of the bottom electrode on the composite microbial film to obtain the microbial film moisture power generation device.
Example 7
(1) Taking the cultured Shewanella bacteria liquid, carrying out 5500rmp centrifugation to obtain Shewanella bacteria, and adding ultrapure water to carry out rapid resuspension to obtain Shewanella bacteria liquid (1g of wet bacteria/4 ml of bacteria liquid).
(2) And (3) according to the wet weight of the bacteria, adding CMC powder and ACET powder in a ratio of 96:1:1 to the wet weight of the bacteria into a stone mortar respectively, grinding for 20 minutes, adding the ground medicine powder into the resuspended bacteria liquid, and fully stirring and mixing to obtain the composite bacteria liquid.
(3) Coating 10ml of the composite bacterial liquid obtained in the step (2) on an ITO bottom electrode, and drying at 25 ℃ and room temperature to obtain the Shewanella composite microbial film with the film area of 100cm2. And then placing a porous top electrode titanium net (with a mesh structure of 200 meshes) slightly smaller than the area of the bottom electrode on the composite microbial film to obtain the microbial film moisture power generation device.
Example 8
(1) Taking the cultured Shewanella bacteria liquid, carrying out 5500rmp centrifugation to obtain Shewanella bacteria, and adding ultrapure water to carry out rapid resuspension to obtain Shewanella bacteria liquid (1g of wet bacteria/4 ml of bacteria liquid).
(2) Coating 10ml of pure Shewanella bacteria liquid on an ITO bottom electrode, and drying at 25 ℃ and room temperature to obtain a Shewanella microorganism film with the area of 100cm2. And then placing a porous top electrode titanium mesh (with a mesh structure of 200 meshes) which is slightly smaller than the area of the bottom electrode on the microbial film to obtain the microbial film moisture power generation device.
Example 9
(1) Taking the cultured Shewanella bacteria liquid, carrying out 5500rmp centrifugation to obtain Shewanella bacteria, and adding ultrapure water to carry out rapid resuspension to obtain Shewanella bacteria liquid (1g of wet bacteria/4 ml of bacteria liquid).
(2) And (3) according to the wet weight of the bacteria, adding CMC powder and ACET powder in a ratio of ACET to CMC (48: 2: 1) into a stone mortar respectively, grinding for 20 minutes, adding the ground medicine powder into the resuspended bacteria liquid, and fully stirring and mixing to obtain the composite bacteria liquid.
(3) Coating 90ml of the composite bacterial liquid obtained in the step (2) on an ITO bottom electrode, and drying at 25 ℃ and room temperature to obtain the Shewanella composite microbial film with the film area of 900cm2. And then placing a porous top electrode titanium mesh (with a mesh structure of 200 meshes) slightly smaller than the area of the bottom electrode on the composite microbial film to obtain the microbial film moisture power generation device.
Fig. 4 shows a schematic view of the composite microbial film of the present example.
Comparative example 1
A wet gas power generation device was prepared in the same manner as in example 1. Comparative example 1 differs from example 1 in that: in this example, nanowires were used instead of microbial films.
The preparation method of the nano wire comprises the following steps:
ethanolamine buffer (pH 10.5) was added to the centrifuged geobacillus thioreducens to resuspend the mixture, and the mixture was introduced into a stirrer to be stirred and centrifuged for 7 minutes to obtain a suspended nanowire solution at 6500 rpm. And adding 10% (v/v) ammonium sulfate solution into the nanowire solution to precipitate the nanowire, centrifuging at 13000g, and removing supernatant to obtain the nanowire. The treatment was then repeated (twice or more) using ethanolamine buffer and ammonium sulfate solution to remove impurities. The nanowires obtained can be stored in ultrapure water.
According to multiple experiments, 20mg of sulfur-reducing live bacillus can generate about 1mg of nano-wires, and the preparation process takes 78 hours in total.
The comparative example 1 shows that the Shewanella membrane has simple preparation method, short preparation period and low material price. The photovoltaic device of comparative example 1 generates an open circuit voltage of 0.5V and a short circuit current of 250nA, and has poor output performance, which is far from meeting the requirements of practical application.
The power generation effect of the microbial film moisture power generation device in the embodiment is verified as follows:
the porous top electrode and the porous bottom electrode of the microbial film moisture power generation device in each embodiment are respectively connected to an electrochemical workstation to form a closed loop, and the closed loop is placed in an environment with the relative humidity of 75% to monitor the generated electric signals in real time. When the relative humidity is 75%, after the microbial film absorbs moisture in the air, hydrophilic functional groups on the surface of the film can absorb water molecules and release charged ions in situ, the charged ions generate directional movement due to concentration gradients at two ends of the film, and the directional movement of the charged ions enables two ends of the film to form a potential difference, so that a stable open-circuit voltage is generated by the microbial film device.
Open circuit voltage and short circuit current of the moisture-based power generation devices of the microbial films of examples 1 to 8 are shown in FIG. 2, and it can be seen from the graph that the moisture-based power generation devices of the microbial films prepared in example 6 have the best output performance, and the generated open circuit voltage and short circuit current are 0.4V and 0.4 mA.
The power of the power generator with moisture in the form of the microbial film constructed in example 6 was 65 μ W when the power generator with moisture in the form of the microbial film was connected to an external resistor of 800 kohm as shown in fig. 3, in which the power generator with moisture in the form of the microbial film was loaded with different resistors at a relative humidity of 75%.
The composite microbial film prepared in example 9 is shown in FIG. 4, and the film area is 30 × 30cm2And the observation of the microbial film shows that the surface is uniform, flat and compact, the appearance is good, and the film is tightly attached to the bottom electrode. The porous top and bottom electrodes of the microbial film moisture power plant constructed in example 9 were connected to an electrochemical workstation to form a closed loop. As shown in FIG. 5, the microbial moisture electric power generating device of example 9 can generate a short-circuit current of 1.17mA and an open-circuit voltage of 0.4V at a relative humidity of 75%, and as shown in FIG. 6, the microbial moisture electric power generating device of example 9 can be stable for a long time.
1 of 30 x 30cm in example 92The large-area microbial film moisture power generation device is connected with the small-sized microbial moisture generator in series and is connected with the electronic display screen, as shown in fig. 7, the left graph is before the circuit is not switched on, and the right graph is after the circuit is switched on, so that the electronic display screen is successfully lightened, and the microbial film moisture power generation device is greatly improved in output current and power compared with a conventional photovoltaic device and can independently supply power for the small-sized electronic device.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The microbial film moisture power generation device is characterized by comprising a bottom electrode, a composite microbial film and a top electrode; one surface of the composite microbial film is attached to the top electrode, and the other surface of the composite microbial film is attached to the bottom electrode; the composite microbial film contains electroactive bacteria, a conductive agent and a water-based binder.
2. The moisture power generation device with microbial films as claimed in claim 1, wherein the area of the composite microbial film is 100-10000cm2。
3. The microbial film moisture vapor generation apparatus of claim 1, wherein the thickness of the composite microbial film is 5-100 μm.
4. A microbial film moisture power plant according to any of claims 1 to 3, wherein said conductive agent is at least one of carbon fiber, carbon nanotube, acetylene black.
5. A microbial film wet gas power plant according to any one of claims 1 to 3, wherein said aqueous binder is at least one of polytetrafluoroethylene emulsion, polyacrylate, styrene-butadiene emulsion, carboxymethyl cellulose.
6. A microbial film moisture power plant according to any of claims 1 to 3, wherein the top electrode has a mesh structure; the mesh number of the mesh structure is 10-400 meshes.
7. A method of manufacturing a microbial film moisture power plant according to any one of claims 1 to 6, comprising the steps of:
(1) mixing the electroactive bacterial liquid with a water-based binder and a conductive agent to obtain a composite bacterial liquid;
(2) and (3) coating the composite bacterial liquid obtained in the step (1) on one surface of a bottom electrode, drying, forming a composite microbial film on one surface of the bottom electrode, and covering a top electrode on the surface of the composite microbial film to obtain the microbial film moisture power generation device.
8. The method for manufacturing a wet gas generator using a microbial film according to claim 7, wherein the concentration of the electroactive bacteria in step (1) is 1g wet cell/(2-6) mL of the bacterial solution.
9. The method for manufacturing a moisture-based power generation device with a microbial film according to claim 7, wherein in the step (1), the mass ratio of the electroactive bacteria to the conductive agent to the aqueous binder is (8-96): (1-2):1.
10. Use of a microbial film moisture power plant according to any one of claims 1 to 6 in the generation of electricity.
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