CN114709432A - High-efficiency microbial fuel cell integrated air cathode and preparation method and application thereof - Google Patents
High-efficiency microbial fuel cell integrated air cathode and preparation method and application thereof Download PDFInfo
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- 239000000446 fuel Substances 0.000 title claims abstract description 55
- 230000000813 microbial effect Effects 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000011592 zinc chloride Substances 0.000 claims abstract description 41
- 239000012528 membrane Substances 0.000 claims abstract description 33
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 33
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 28
- 239000000835 fiber Substances 0.000 claims abstract description 24
- 238000009987 spinning Methods 0.000 claims abstract description 18
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
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- 150000001875 compounds Chemical class 0.000 abstract description 2
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- 239000002134 carbon nanofiber Substances 0.000 description 15
- 239000011148 porous material Substances 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
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- 239000007921 spray Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
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- 239000011701 zinc Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
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Abstract
The invention discloses an integrated air cathode of a high-efficiency microbial fuel cell and a preparation method and application thereof. The preparation method of the high-efficiency microbial fuel cell integrated air cathode comprises the following steps: adding zinc chloride and polyacrylonitrile into N, N-dimethylformamide, and uniformly mixing to obtain a spinning solution; carrying out electrostatic spinning on the spinning solution to obtain a fiber membrane; and drying the fiber membrane, and then sequentially carrying out preoxidation and high-temperature carbonization to obtain the high-efficiency microbial fuel cell integrated air cathode. The nanofiber membrane prepared by the method has self-supporting property, can be used as a cathode of a microbial fuel cell, does not need to additionally add a binder and a conductive agent, can integrate an air diffusion layer and a catalytic layer, is easy to modify or compound, and has important application value; the nanofiber membrane prepared by the method has the advantages of low cost, simplicity in preparation, excellent performance and the like, and has important application value in the field of microbial fuel cells.
Description
Technical Field
The invention relates to the technical field of microbial fuel cells, in particular to an integrated air cathode of a high-efficiency microbial fuel cell and a preparation method and application thereof.
Background
Microbial Fuel Cells (MFCs) are a green technology that utilizes microorganisms to directly convert chemical energy in organic matter into electrical energy. Under the anaerobic environment of the anode chamber, organic compounds are decomposed under the action of microorganisms and electrons and protons are released, the electrons are transferred to the cathode through an external circuit to form current, the protons pass through a proton exchange membrane to the cathode, and an oxidant (generally oxygen) is combined with the protons at the cathode to form water. Cathode performance is considered to be a major limitation of MFCs. The cathode electrode usually consists of a catalyst layer and an air diffusion layer, sometimes a support layer is needed, and the preparation method of the air cathode is widely researched, for example, the Chinese patent CN 113178589A mixes a mixture, a conductive material and a binder and coats the mixture on a conductive substrate to obtain the cathode of the microbial fuel cell; chinese patent CN 108767265A adopts a rolling method to press an activated carbon catalyst layer, a stainless steel mesh current collector and an air diffusion layer together to obtain the cathode of the microbial fuel cell. However, the above method has the following problems: 1. the adhesive is expensive and is mostly a toxic and harmful substance, which can pollute MFC microorganisms, so that the adhesive cannot be used in sediment microbial fuel cells such as oceans, wetlands, lakes and the like; 2. the manufacturing process is complex and time-consuming, is not suitable for industrial standardized production, and the quality level of the manufactured electrode has great difference.
Therefore, the development of the microbial fuel cell air cathode with simple preparation process and high performance has great significance.
Disclosure of Invention
The invention aims to overcome the technical defects, provides an integrated air cathode of a high-efficiency microbial fuel cell, and a preparation method and application thereof, and solves the technical problems that the preparation process of the air cathode of the microbial fuel cell is complex and the binding agent used in the preparation process pollutes MFC microorganisms in the prior art.
The invention provides a preparation method of an integrated air cathode of a high-efficiency microbial fuel cell, which comprises the following steps:
adding zinc chloride and polyacrylonitrile into N, N-dimethylformamide, and uniformly mixing to obtain a spinning solution;
carrying out electrostatic spinning on the spinning solution to obtain a fiber membrane;
and drying the fiber membrane, and then sequentially carrying out preoxidation and high-temperature carbonization to obtain the high-efficiency microbial fuel cell integrated air cathode.
The second aspect of the invention provides a high-efficiency microbial fuel cell integrated air cathode obtained by the preparation method of the high-efficiency microbial fuel cell integrated air cathode provided by the first aspect of the invention.
A third aspect of the present invention provides a high efficiency microbial fuel cell, the cathode of which is the high efficiency microbial fuel cell integrated air cathode of the second aspect of the present invention.
Compared with the prior art, the invention has the beneficial effects that:
the invention mixes zinc chloride and polyacrylonitrile into a carbon nanofiber membrane, ZnCl, by an electrostatic spinning technology2As an activator, part of Zn volatilizes from the carbon skeleton through high-temperature treatment to generate a large amount of pore structures, so that the specific surface area is increased, and the reaction kinetics are promoted; part of the molten zinc salt may be inserted into the carbon layer by forming ZnO or Zn complex, playing a role of fixing nitrogen, facilitating catalytic oxygen reduction (ORR) reaction; meanwhile, the hydrophobic material is adopted, so that the nutrient solution in the microbial fuel cell cannot leak out, but the passing of air and other ions is not influenced completely;
the nanofiber membrane prepared by the method has self-supporting property, can be used as a cathode of a microbial fuel cell, does not need to additionally add a binder and a conductive agent, can integrate an air diffusion layer and a catalytic layer, is easy to modify or compound, and has important application value;
the nanofiber membrane prepared by the method has the advantages of low cost, simplicity in preparation, excellent performance and the like, and has important application value in the field of microbial fuel cells.
Drawings
FIG. 1 is a schematic flow diagram illustrating the fabrication of one embodiment of the high efficiency microbial fuel cell of the present invention;
FIGS. 2 (a) - (d) are SEM images of electrospun carbon nanofiber membranes in examples 1-4 of the present invention, respectively;
fig. 3 is a nitrogen adsorption desorption isotherm (a) and a pore size distribution diagram (b) of an integrated air cathode of a high efficiency microbial fuel cell in various embodiments of the present invention;
fig. 4 is a graph (a) of output voltage and a graph (b) of polarization curve versus power density for a high efficiency microbial fuel cell in accordance with various embodiments of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, a first aspect of the present invention provides a method for preparing an integrated air cathode of a high efficiency microbial fuel cell, comprising the following steps:
s1, adding zinc chloride and Polyacrylonitrile (PAN) into N, N-Dimethylformamide (DMF) and uniformly mixing to obtain a spinning solution;
s2, carrying out electrostatic spinning on the spinning solution to obtain a fiber membrane;
and S3, drying the fiber membrane, and then sequentially carrying out pre-oxidation and high-temperature carbonization to obtain the high-efficiency microbial fuel cell integrated air cathode.
In the invention, the dosage ratio of zinc chloride to N, N-dimethylformamide is (0.1-0.4) g: 10 mL.
In the invention, the mass ratio of zinc chloride to polyacrylonitrile is (0.1-0.4): 1, preferably (0.25 to 0.3): 1, more preferably 0.3: 1.
In the invention, the steps of adding zinc chloride and polyacrylonitrile into N, N-dimethylformamide and uniformly mixing to obtain the spinning solution comprise: adding zinc chloride into N, N-dimethylformamide, adding polyacrylonitrile after ultrasonic dispersion is uniform, heating, stirring and mixing uniformly until the solution becomes semitransparent, and obtaining the spinning solution. Further, heating and stirring are carried out under the condition of water bath, the temperature of the water bath is 40-80 ℃, further 60 ℃, and the stirring time is 4-8 hours, further 6 hours.
In the invention, in the electrostatic spinning process, the applied voltage range is 18-25 kV, and further 20 kV; the extrusion speed of the spinning solution is 0.5-2 mL/h, and further 1 mL/h; the distance between the needle point and the receiving roller is set to be 18-20 cm, and further 18 cm; the diameter of the roller is 70-80 mm, and is further 76.48 mm; the speed of the roller is 25 to 35mm/s, further 30mm/s, the moving speed of the nozzle is 1 to 10mm/s, further 5mm/s, and the reciprocating distance is 70 to 80mm, further 75 mm.
According to the invention, the fiber membrane is dried in a vacuum drying mode, the drying temperature is 40-80 ℃, further 60 ℃, and the drying time is 6-12 hours, further 12 hours.
In the invention, the pre-oxidation temperature is 250-280 ℃, further 250 ℃, and the time is 2-4 h, further 2 h.
In the invention, the high-temperature carbonization conditions are as follows: the temperature rise speed is 3-10 ℃/min, further 5 ℃/min, the target temperature is 700-1000 ℃, further 800 ℃, the heat preservation time is 1-3 h, further 1h, and the high-temperature carbonization is carried out under the protection of nitrogen.
The second aspect of the invention provides a high-efficiency microbial fuel cell integrated air cathode obtained by the preparation method of the high-efficiency microbial fuel cell integrated air cathode provided by the first aspect of the invention.
A third aspect of the present invention provides a high efficiency microbial fuel cell, the cathode of which is the high efficiency microbial fuel cell integrated air cathode of the second aspect of the present invention.
Example 1
(1) 0.1g of ZnCl is weighed2Pouring into 10mL of N, N-dimethylformamide, and carrying out ultrasonic treatment for 2h to obtain ZnCl2A solution;
(2) weighing 1g PAN and adding ZnCl2In the solution, the solution is added with a solvent,heating and stirring for 6h under the condition of water bath at 60 ℃ until the mixture is uniformly mixed, and the solution becomes semitransparent to obtain ZnCl2A PAN solution;
(3) reacting ZnCl2the/PAN solution was poured into a 50mL syringe, the device was connected, 20kV was applied, and ZnCl was added at 1mL/h2The PAN solution is pushed out from a needle head 18cm away from a collecting roller, the PAN solution is collected by the roller, and a fiber membrane is obtained after the spinning solution is consumed; wherein the diameter of the roller is 76.48mm, the speed of the roller is 30mm/s, the moving speed of the spray head is 5mm/s, and the reciprocating distance is 75 mm;
(4) drying the fiber membrane in a vacuum drying oven at 60 ℃ for 12h, then pre-oxidizing the fiber membrane in an oven at 250 ℃ for 2h, finally heating the sample in a tubular furnace in a nitrogen atmosphere at the heating rate of 5 ℃/min to 800 ℃ and preserving the temperature for 1h to prepare the high-efficiency microbial fuel cell integrated air cathode Zn-1-CNF.
Example 2
(1) 0.25g of ZnCl was weighed2Pouring into 10mL of N, N-dimethylformamide, and carrying out ultrasonic treatment for 2h to obtain ZnCl2A solution;
(2) weighing 1g PAN and adding ZnCl2Heating and stirring the solution for 6 hours under the condition of water bath at the temperature of 60 ℃ until the solution is uniformly mixed and becomes semitransparent to obtain ZnCl2A PAN solution;
(3) reacting ZnCl2the/PAN solution was poured into a 50mL syringe, the device was connected, 20kV was applied, and ZnCl was added at 1mL/h2The PAN solution is pushed out from a needle head 18cm away from a collecting roller, the PAN solution is collected by the roller, and a fiber membrane is obtained after the spinning solution is consumed; wherein the diameter of the roller is 76.48mm, the speed of the roller is 30mm/s, the moving speed of the spray head is 5mm/s, and the reciprocating distance is 75 mm;
(4) drying the fiber membrane in a vacuum drying oven at 60 ℃ for 12h, then pre-oxidizing the fiber membrane in an oven at 250 ℃ for 2h, finally heating the sample in a tubular furnace in a nitrogen atmosphere at the heating rate of 5 ℃/min to 800 ℃ and preserving the temperature for 1h to prepare the high-efficiency microbial fuel cell integrated air cathode Zn-2.5-CNF.
Example 3
(1) 0.3g of ZnCl is weighed2Pouring into 10mL of N, N-dimethylformamide,ultrasonic treatment for 2h to obtain ZnCl2A solution;
(2) weighing 1g PAN and adding ZnCl2Heating and stirring the solution for 6 hours under the condition of water bath at the temperature of 60 ℃ until the solution is uniformly mixed and becomes semitransparent to obtain ZnCl2A PAN solution;
(3) reacting ZnCl2the/PAN solution was poured into a 50mL syringe, the device was connected, 20kV was applied, and ZnCl was added at 1mL/h2The PAN solution is pushed out from a needle head 18cm away from a collecting roller, the PAN solution is collected by the roller, and a fiber membrane is obtained after the spinning solution is consumed; wherein the diameter of the roller is 76.48mm, the speed of the roller is 30mm/s, the moving speed of the spray head is 5mm/s, and the reciprocating distance is 75 mm;
(4) drying the fiber membrane in a vacuum drying oven at 60 ℃ for 12h, then pre-oxidizing the fiber membrane in an oven at 250 ℃ for 2h, finally heating the sample in a tubular furnace in a nitrogen atmosphere at the heating rate of 5 ℃/min to 800 ℃ and preserving the temperature for 1h to prepare the high-efficiency microbial fuel cell integrated air cathode Zn-3-CNF.
Example 4
(1) 0.4g of ZnCl is weighed2Pouring into 10mL of N, N-dimethylformamide, and carrying out ultrasonic treatment for 2h to obtain ZnCl2A solution;
(2) weighing 1g PAN and adding ZnCl2Heating and stirring the solution for 6 hours under the condition of water bath at the temperature of 60 ℃ until the solution is uniformly mixed and becomes semitransparent to obtain ZnCl2A PAN solution;
(3) reacting ZnCl2the/PAN solution was poured into a 50mL syringe, the device was connected, 20kV was applied, and ZnCl was added at 1mL/h2The PAN solution is pushed out from a needle head 18cm away from a collecting roller, the PAN solution is collected by the roller, and a fiber membrane is obtained after the spinning solution is consumed; wherein the diameter of the roller is 76.48mm, the speed of the roller is 30mm/s, the moving speed of the spray head is 5mm/s, and the reciprocating distance is 75 mm;
(4) drying the fiber membrane in a vacuum drying oven at 60 ℃ for 12h, then pre-oxidizing the fiber membrane in an oven at 250 ℃ for 2h, finally heating the sample in a tubular furnace in a nitrogen atmosphere at the heating rate of 5 ℃/min to 800 ℃ and preserving the temperature for 1h to prepare the high-efficiency microbial fuel cell integrated air cathode Zn-4-CNF.
In fig. 2, (a) to (d) are SEM topography views of electrospun carbon nanofiber membranes in examples 1 to 4 of the present invention, respectively. As can be seen from fig. 2, at a high temperature of 800 ℃, the related substances of Zn are transformed into gaseous energy and disappear from the carbon nanofibers, so that the fibers are rough to some extent, which can be seen at a high magnification (100nm), as shown in the inset of fig. 2; it can also be seen from FIG. 2 that there are prominent nodular beads and that with ZnCl2The doping amount is increased from 0.1 to 0.4, the doping amount is gradually increased, the nodules are the least when the doping amount is 10 wt.%, and the nodules are the most when the doping amount is 40 wt.%, and the phenomenon that zinc salt which is not sublimated during high-temperature carbonization is converted into ZnO or Zn complex to be left in the fiber and the complex is similar to agglomeration is generated.
Fig. 3 shows nitrogen adsorption-desorption isotherms (a) and pore size distribution (b) of integrated air cathodes of high efficiency microbial fuel cells according to various embodiments of the present invention. The Pore Size Distributions (PSDs) and pore volume maps of fig. 3(b) were calculated from the Quenched Solid Density Functional Theory (QSDFT) model based on the nitrogen adsorption desorption isotherm of fig. 3 (a). From PSD, ZnCl2The @ CNFs mostly exhibit a microporous distribution below 2nm, with a certain amount of mesopore distribution, the pore size of which is mainly distributed between 0.5 and 10 nm. The Specific Surface Areas (SSA) of Zn-1-CNF, Zn-2.5-CNF, Zn-3-CNF and Zn-4-CNF were calculated using the (Brunauer-Emmett-Teller, BET) model, and were 231m2/g、362m2/g、435m2G and 590m2(ii) in terms of/g. It can be seen that with ZnCl2Increase in doping amount, ZnCl2The specific surface area of the doped carbon nano-fiber is gradually increased, the total pore volume and the micropore volume are increased, and the Zn-4-CNF can reach 0.28cm3 g-1Illustrating ZnCl on carbon fibers at high temperature sintering2And volatilizing to leave a large amount of pore structures, and increasing the specific surface area of the material. These results show ZnCl2The addition of (2) first favours the formation of micropores, but with ZnCl2With the increase of the added amount, some micropores collapse to form a mesoporous structure. Thus, suitable ZnCl2The addition amount is beneficial to the formation of a multi-level porous structure, wherein mesopores can provide channels for the transportation of ions and air, and micropores are beneficial to the increase of the number of microporesAdding effective specific surface area, interface roughness and active sites.
Test group
The carbon nanofiber membrane is cut into a wafer with the diameter of 3cm to be used as an air cathode, and then the wafer is connected with an anode carbon felt through a titanium wire, and finally the microbial fuel cell (the total volume is 28mL, and the specification is 5 multiplied by 6cm) is assembled. For all bioelectrochemical analyses, data were obtained after the MFC had achieved a stable voltage after medium exchange. And recording the output voltage, the power density and other properties of the MFC after three continuous periods. Polarization curves and power densities were evaluated and the resulting stable output voltage was measured by adding fresh nutrient solution and stabilizing at Open Circuit Potential (OCP) overnight before measuring the power density and polarization curves. The resistors (ranging from 20-33000 omega) connected with different external resistance values are replaced at two ends of the MFC electrode, the voltage values under different resistors are recorded by a universal meter, and the MFC battery runs and then is used with a fresh culture medium for 2 hours. The current density (I) calculation for the MFC cell is based on ohm's law (I ═ U/RA), the power density (P) is represented by PAUI/a and Pv U2v.R estimate, where U (mV) is voltage, I (mA) is current, A (cm)2) For projected surface area, V (m)3) Is the volume of the cathode electrode MFC.
Fig. 4 is a graph (a) of output voltage and a graph (b) of polarization curve versus power density for a high efficiency microbial fuel cell in accordance with various embodiments of the present invention. As can be seen from FIG. 4, ZnCl2When the content is less than 0.25g, the content is changed with ZnCl2The more favorable the addition amount is, the more favorable the catalytic ORR reaction is; but when ZnCl is used2When the content is more than 0.3g, ZnCl2Increasing the amount of addition is detrimental to catalyzing the ORR reaction.
As can be seen in conjunction with FIGS. 3 and 4, with ZnCl2The specific surface area and the pore volume of the material are increased by increasing the adding amount; when ZnCl is used2When the content is too high, some micropores form mesopores, which is not favorable for catalyzing the ORR reaction.
Compared with the prior art, the invention has the beneficial effects that:
the nanofiber membrane has self-supporting property and strong mechanical property, is used for the integrated air cathode of the microbial fuel cell, and nutrient solution is not easy to overflow but does not influence ion transportation and normal oxygen passing; meanwhile, a gas-liquid-solid three-phase interface is constructed, and the transfer rate of extracellular charges is improved; the nanofiber membrane is used as an air cathode, is not only a catalyst layer, but also an air diffusion layer, and has the characteristics of simple manufacturing process, large specific surface area, high porosity, convenience for ion adsorption and passing and the like.
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of an integrated air cathode of a high-efficiency microbial fuel cell is characterized by comprising the following steps:
adding zinc chloride and polyacrylonitrile into N, N-dimethylformamide, and uniformly mixing to obtain a spinning solution;
carrying out electrostatic spinning on the spinning solution to obtain a fiber membrane;
and drying the fiber membrane, and then sequentially carrying out pre-oxidation and high-temperature carbonization to obtain the high-efficiency microbial fuel cell integrated air cathode.
2. The method for preparing the integrated air cathode of the high-efficiency microbial fuel cell according to claim 1, wherein the dosage ratio of the zinc chloride to the N, N-dimethylformamide is (0.1-0.4) g: 10 mL.
3. The preparation method of the integrated air cathode of the efficient microbial fuel cell according to claim 1, wherein the mass ratio of the zinc chloride to the polyacrylonitrile is (0.1-0.4): 1.
4. the preparation method of the integrated air cathode of the efficient microbial fuel cell according to claim 3, wherein the mass ratio of the zinc chloride to the polyacrylonitrile is (0.25-0.3): 1.
5. the method for preparing the air cathode integrated with the efficient microbial fuel cell according to claim 1, wherein the step of adding zinc chloride and polyacrylonitrile into N, N-dimethylformamide and uniformly mixing to obtain the spinning solution comprises the following steps: adding zinc chloride into N, N-dimethylformamide, adding polyacrylonitrile after ultrasonic dispersion is uniform, heating, stirring and mixing uniformly until the solution becomes semitransparent, and obtaining a spinning solution; wherein, the heating and stirring are carried out under the condition of water bath, the temperature of the water bath is 40-80 ℃, and the stirring time is 4-8 h.
6. The method for preparing the air cathode integrated with the high-efficiency microbial fuel cell according to claim 1, wherein in the electrostatic spinning process, the applied voltage is 18-25 kV, the extrusion speed of the spinning solution is 0.5-2 mL/h, the distance between the needle point and the receiving roller is 18-20 cm, the diameter of the roller is 70-80 mm, the speed of the roller is 25-35 mm/s, the moving speed of the nozzle is 1-10 mm/s, and the reciprocating distance is 70-80 mm.
7. The preparation method of the integrated air cathode of the efficient microbial fuel cell according to claim 1, wherein the fiber membrane is dried in a vacuum drying mode, the drying temperature is 40-80 ℃, and the drying time is 6-12 hours; the pre-oxidation temperature is 250-280 ℃, and the time is 2-4 h; the high-temperature carbonization conditions are as follows: the heating speed is 3-10 ℃/min, the target temperature is 700-1000 ℃, the heat preservation time is 1-3 h, and the high-temperature carbonization is carried out under the protection of nitrogen.
8. The method for preparing the integrated air cathode of the high-efficiency microbial fuel cell according to claim 1, wherein the pre-oxidation temperature is 250 ℃ and the time is 2 hours; the high-temperature carbonization conditions are as follows: the heating rate is 5 ℃/min, the target temperature is 800 ℃, and the heat preservation time is 1 h.
9. A high-efficiency microbial fuel cell integrated air cathode, which is obtained by the preparation method of the high-efficiency microbial fuel cell integrated air cathode according to any one of claims 1 to 8.
10. A high efficiency microbial fuel cell, wherein the cathode of the high efficiency microbial fuel cell is the integrated air cathode of claim 9.
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| KR20180096953A (en) * | 2017-02-22 | 2018-08-30 | 경기대학교 산학협력단 | The metal coating layer of the microbial fuel cell was replaced with a carbon nano fiber electrode |
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