CN103199289A - Graphite-electrode-based film-free microfluid microbial battery - Google Patents
Graphite-electrode-based film-free microfluid microbial battery Download PDFInfo
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- CN103199289A CN103199289A CN2013100816481A CN201310081648A CN103199289A CN 103199289 A CN103199289 A CN 103199289A CN 2013100816481 A CN2013100816481 A CN 2013100816481A CN 201310081648 A CN201310081648 A CN 201310081648A CN 103199289 A CN103199289 A CN 103199289A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention provides a graphite-electrode-based film-free microfluid microbial battery, comprising a bottom plate, a top plate, an anode electrode, a cathode electrode, a front isolating plate and a rear isolating plate. The graphite-electrode-based film-free microfluid microbial battery is characterized in that the anode electrode and the cathode electrode are in parallel; the front isolating plate and the rear isolating plate are arranged between the anode electrode and the cathode electrode, so that a microfluid flowing channel is formed between the anode electrode and the cathode electrode; a micro-channel is processed in the biochemical reaction surface of the electrodes by a low-speed wire cutting mode; an upper pad is arranged above the anode electrode and the cathode electrode; the top plate is arranged above the upper pad; a lower pad is arranged below the anode electrode and the cathode electrode; the bottom plate is arranged below the lower pad; a culture liquid inlet is formed at the front end of the top plate and near an anode side; an electronic acceptor inlet is formed at the front end of the top plate and near a cathode side; the culture liquid inlet and the electronic acceptor inlet are communicated with the microfluid flowing channel; and an outlet is formed at the rear end of the bottom plate and is communicated with the microfluid flowing channel.
Description
Technical field
The present invention relates to microbiological fuel cell, be specifically related to the no film microfluid microorganism battery based on graphite electrode.
Background technology
Microbiological fuel cell (Microbial fuel cell) has that raw material sources are extensive, reaction condition is gentle, good biocompatibility, is a kind of new fuel cell that can electrogenesis when disposing of sewage.On the one hand, microbiological fuel cell can be used as waste water treatment and the renewable energy source generating device of amplificationization; On the other hand, the microminiature microbiological fuel cell can come fast detecting water environment index for the portable electric appts power supply or as biology sensor.Yet because performance is lower, manufacturing process is expensive, the development of miniature microbiological fuel cell has been subjected to restriction.
In existing miniature microbiological fuel cell, battery adopts photoetching (Chen usually, Y.P., Y.Zhao, et al. (2011) .Biosensors and Bioelectronics26 (6): 2841-2846) and soft lithographic (Hou, H., L.Li, et al. (2009) .PLoS ONE4 (8): technology processing e6570).Though shape, the size of microchannel can be accurately controlled in photoetching, have to adopt the gold that is easy to photoetching as electrode material in the most studies.Except with high costs, gold electrode also can cause biocompatibility relatively poor, namely increases owing to the electric transmission loss causes the internal resistance of cell, and power of battery density descends, and has directly limited the use of miniature microbiological fuel cell.Because outstanding conductivity, biocompatibility and chemical stability admirably, graphite electrode is widely used in the microbiological fuel cell of amplification.At present also for seeing the report that graphite is applied to miniature microbiological fuel cell.Adopt proton exchange membrane to separate anode and cathode unlike other miniature microbiological fuel cell, be introduced in the microbiological fuel cell based on the microfluid concept of laminar flow.
Microfluid fuel cell (Microfluidic fuel cell) is the characteristics of utilizing fluid to flow at the minute yardstick underflow, makes two fluid streams that comprise fuel and oxidant respectively separate naturally, can work at normal temperatures and pressures.Microfluid fuel cell based on laminar flow extensively adopts formic acid, methyl alcohol etc. as chemical fuel, and Li, Z., Y.Zhang, et al will introduce in the microbiological fuel cell based on the microfluid concept of laminar flow first.Compare with traditional miniature microbiological fuel cell, the microbiological fuel cell under the microfluidic control does not need proton exchange membrane, has avoided the fuel infiltration relevant with film, film is dry, film is degenerated and problem such as negative electrode water management,
Summary of the invention
Technical problem to be solved by this invention is to provide the no film microfluid microorganism battery based on graphite electrode, to obtain higher fuel availability and battery performance.
In order to solve the problems of the technologies described above, technical scheme of the present invention is that the no film microfluid microorganism battery based on graphite electrode comprises base plate, top board, anode electrode, cathode electrode, preceding division board and back division board; It is characterized in that: anode electrode and cathode electrode be arranged in parallel, simultaneously, division board and back division board before between anode electrode and cathode electrode, being provided with, make between anode electrode and the cathode electrode and form microfluidic flow channels, and adopt the mode of the silk thread cutting of being careful to process micro-channel at electrode generation biochemical reaction face; Be provided with Upper gasket above anode electrode and cathode electrode, the top of Upper gasket arranges top board; Be provided with lower gasket below anode electrode and cathode electrode, the below of lower gasket arranges base plate; Front end at top board is provided with the nutrient solution import near anode-side, front end at top board is provided with the electron acceptor import near cathode side, nutrient solution import and electron acceptor import all communicate with microfluidic flow channels, the rear end of base plate is provided with outlet, this outlet communicates with microfluidic flow channels, biological culture based sols and electron acceptor enter the microfluidic flow channels Laminar Flow by nutrient solution import and electron acceptor import respectively, the biological culture based sols is by the degraded of the Institute of Micro-biology on the anode electrode, and catabolite is discharged outside the battery by outlet.
Wherein, preceding division board plays with the back division board and intercepts the anode and cathode short circuit, guides fluid with the mobile effect of the mode of parallel laminar flow in The initial segment; Pad plays sealing function, prevents that oxygen is leaked to biofilm surface, causes battery performance to descend.
Culture medium solution and electron acceptor flow in interelectrode small conduit, mix by diffusion at the liquid/liquid interface place that forms, flow velocity and the concentration of control culture medium solution and electron acceptor make two fluid streams form Laminar Flow in conduit, and anode electrode and cathode electrode have been isolated, thereby avoided using the material of this costliness of proton exchange membrane, be conducive to reduce the cost of microbiological fuel cell; Simultaneously, because the material that does not need to use proton exchange membrane to completely cut off as negative electrode and anode, also help the transmission rate that improves proton between the negative electrode anode, reduce the internal resistance of cell, replaced proton exchange membrane, reduced the battery cost, and the fuel infiltration of having avoided being caused by proton exchange membrane, film is dry, film is degenerated and a series of problems of problem such as negative electrode water management; Culture medium on the anode electrode surface by microbial consumption, microbe is discharged into anode electrode by the mode of direct contact with electronics, electronics arrives cathode electrode by external circuit, and intact culture medium, product and the electron acceptor of unreacted discharged battery by the outlet on the base plate; Simultaneously, fluid flows on the microbe surface, and culture medium has tangentially played the effect of screening superior microorganism when biofilm surface flows through, make microbe and electrode surface combine closely, and has reduced the internal resistance of cell, has improved battery performance;
According to the preferred version of the no film microfluid microorganism battery based on graphite electrode of the present invention, described anode electrode is graphite flake, carbon cloth, carbon felt, carbon paper, carbon brush or graphite rod; Described cathode electrode is graphite flake, carbon cloth, carbon felt, carbon paper, carbon brush or graphite rod.
Preferred version according to the no film microfluid microorganism battery based on graphite electrode of the present invention, division board and back division board before between anode electrode and cathode electrode, being provided with, make between anode electrode and the cathode electrode and form microfluidic flow channels, described microfluidic flow channels is rectangularl runner or front wide and rear narrow runner or beloid runner.
According to the preferred version of the no film microfluid microorganism battery based on graphite electrode of the present invention, described electron acceptor comprises the potassium ferricyanide, oxygen, six cobaltammines, many iodide ions, potassium peroxydisulfate or potassium permanganate.
According to the preferred version of the no film microfluid microorganism battery based on graphite electrode of the present invention, the biological culture based sols is made of activated sludge and culture medium, and the main component of described culture medium is: 1.13-4.52g L
-1Sodium acetate, 15.3g L
-1Na
2HPO
412H
2O, 3g L
-1KH
2PO
4, 0.5g L
-1N
aCl, 0.1g L
-1NH
4Cl, 0.1g L
-1MgSO
47H
2O, 11mg L
-1CaCl
2And1.0mL L
-1Trace element.
The beneficial effect of the no film microfluid microorganism battery based on graphite electrode of the present invention is: improved the performance of miniature microbiological fuel cell, and reduced the internal resistance of miniature microbiological fuel cell; Electrode material cost of manufacture of the present invention is low, has strengthened the biocompatibility of electrode; Simultaneously, electrode of the present invention adopts the silk thread cutting technique of being careful, and has shortened the Production Time of existing miniature microbiological fuel cell when guaranteeing precision; Microfluid fuel cell involved in the present invention does not need proton exchange membrane, not only have compact conformation, advantage that cost is low, and can screen advantage electrogenesis bacterium, avoid the fuel infiltration relevant with film simultaneously, film is dry, film is degenerated and problem such as negative electrode water management, no matter be as biology sensor or as the compact power for small device power supply, all have a good application prospect.
Description of drawings
Fig. 1 is the no film microfluid microorganism battery assembling relationship figure based on graphite electrode of the present invention.
Fig. 2 is the no film microfluid microorganism battery structural representation based on graphite electrode of the present invention.
Fig. 3 is the structural representation of positive plate, minus plate, preceding dividing plate and rear bulkhead.
Fig. 4 is the structural representation of base plate.
Fig. 5 is the performance curve of the present invention under three kinds of flow velocitys.
Fig. 6 is the performance curve of the present invention under five kinds of potassium ferricyanide concentration.
Embodiment
Be further described specifically below in conjunction with the present invention of embodiment, but embodiments of the present invention are not limited thereto.
Referring to Fig. 1 to Fig. 4, based on the no film microfluid microorganism battery of graphite electrode, by top board 1, base plate 2, anode electrode 3, cathode electrode 4, preceding division board 5, back division board 6, Upper gasket 11 and lower gasket 13 constitute, and fixing by bolt 12; Preceding division board 5 and back division board 6 all adopt transparent material such as Merlon, polymethyl methacrylate etc. to make; Wherein: anode electrode 3 and cathode electrode 4 be arranged in parallel, and division board 5 and back division board 6 before being provided with between anode electrode 3 and cathode electrode 4, make between anode electrode 3 and the cathode electrode 4 and form microfluidic flow channels, and channel pitch is 1mm-4mm; Described microfluidic flow channels can be rectangularl runner or front wide and rear narrow runner or beloid runner;
Be provided with Upper gasket 11 above anode electrode 3 and cathode electrode 4, the top of Upper gasket 11 arranges top board 1; Be provided with lower gasket 13 below anode electrode 3 and cathode electrode 4, the below of lower gasket 13 arranges base plate 2; Upper gasket 11 and lower gasket 13 can adopt the thick silica gel pad of 0.5mm; Front end at top board 1 is provided with nutrient solution import 7 near anode-side, front end at top board 1 is provided with electron acceptor import 8 near cathode side, nutrient solution import 7 and electron acceptor import 8 all communicate with microfluidic flow channels, and the rear end of base plate 2 is provided with outlet 9, and this outlet 9 communicates with microfluidic flow channels; Biological culture based sols and electron acceptor enter the microfluidic flow channels Laminar Flow by nutrient solution import 7 and electron acceptor import 8 respectively, and the assurance electron acceptor can not be diffused into anode and produce microorganism electricity generation inhibition phenomenon; The biological culture based sols is by the degraded of the Institute of Micro-biology on the anode electrode 3, and catabolite is discharged outside the battery by outlet 9.
Described anode electrode 3 adopts graphite flake, carbon cloth, carbon felt, carbon paper, carbon brush or graphite rod to constitute; Described cathode electrode 4 adopts graphite flake, carbon cloth, carbon felt, carbon paper, carbon brush or graphite rod to constitute.Before the use, adopt the mode of the silk thread cutting of being careful in electrode generation biochemical reaction face processing micro-channel earlier, micro-channel can adopt rectangle or front wide and rear narrow conduit or beloid conduit; Use sand papering again, form rough surface, make it be beneficial to adhering to of microbe; The silk thread of being careful cutting is to utilize mobile continuously fine wire to make electrode, and workpiece is carried out pulse sparkover ablation metal, excision forming, and wire travelling speed is lower than 0.2m/s, and precision reaches 0.001mm, stable working, evenly, shake is little, crudy is high.
Described electron acceptor can be the 10mM-40mM potassium ferricyanide, oxygen, 0.02-0.2mM six cobaltammines, the many iodide ions of 0.5mM-2mM, 5mM-30mM potassium peroxydisulfate or 20-200mM potassium permanganate.
Described biological culture based sols is made of activated sludge and culture medium, and the main component of described culture medium is: 1.13---4.52g L
-1Sodium acetate, 15.3g L
-1Na
2HPO
412H
2O, 3g L
-1KH
2PO
4, 0.5g L
-1N
aCl, 0.1g L
-1NH
4Cl, 0.1g L
-1MgSO
47H
2O, 11mg L
-1CaCl
2And1.0mL L
-1Trace element.
Connect for convenient, stretch out respectively outside top board and the base plate at anode electrode and cathode electrode two ends, connects resistance respectively and constitute the closed-loop path.
No film microfluid microorganism battery based on graphite electrode of the present invention adopts and is rich in the assorted bacterium of electrogenesis bacterium Geobacter and Shewanella as bacterial classification, employing contains the culture medium simulative organic wastewater of sodium acetate, originate as the bacterium substrate, entire cell does not adopt any precious metal material, has saved cost greatly.
Below in conjunction with specific embodiment, and referring to Fig. 5, Fig. 6 and table one, illustrate the present invention under the various anolyte flow velocitys with various potassium ferricyanide concentration under performance, wherein:
Fig. 5 is the performance curve of the present invention under three kinds of flow velocitys.Wherein, it is 10mL/h that square dot, circular point, triangle form point represent the reactant flow velocity respectively, the performance curve when 20mL/h and 40mL/h.
Fig. 6 is based on the performance curve of no film microfluid microorganism battery under various potassium ferricyanide concentration of graphite electrode.Wherein, square dot, circular point, go up the triangle form point, down triangle form point, Diamond spot to represent potassium ferricyanide concentration respectively be 2.5mM, 5mM, 10mM, 20mM, during 40mM based on the performance curve of graphite electrode microfluid microbiological fuel cell.
The no film microfluid microorganism battery that table one is based on graphite electrode with deliver, the maximum area power density of typical miniature microbiological fuel cell and the comparison of the internal resistance of cell.
Table one
Embodiment one:
In this example, the response area of anode electrode (3) and cathode electrode (4) is 40mm
2, the long 40mm of runner, its cross section are 2mm * 1mm, and potassium ferricyanide concentration is 10mM, and sodium acetate concentration is 1.13g L-1 in the culture medium, and ambient temperature is 30 ℃, the performance of battery is as shown in the figure.From as can be seen, the maximum power density of battery reaches 520mW/m2, is 1.6 times of present miniature microbiological fuel cell maximum area power density.
Embodiment two:
In this example, sodium acetate concentration is 1.13g L-1 in the employing culture medium, and the anode and cathode flow rate of liquid is 10mL/h, and ambient temperature is 30 ℃, and the performance of battery as shown in the figure.As can be seen from the figure, the maximum power density of battery reaches 575mW/cm
2, be 1.74 times of present miniature microbiological fuel cell maximum area power density.
Find out from table one, under the best test operating mode, maximum area power density based on the miniature microbiological fuel cell of graphite electrode is 615mW/m2, be 1.86 times of present miniature microbiological fuel cell maximum area power density, through further test, this internal resistance of cell is 5100 Ω, is 68% of the minimum internal resistance of present miniature microbiological fuel cell.
Can draw from embodiment one, embodiment two and table one, the present invention has improved the performance of miniature microbiological fuel cell, and has reduced the internal resistance of miniature microbiological fuel cell, has a good application prospect.
Claims (5)
1. based on the no film microfluid microorganism battery of graphite electrode, comprise base plate (2), top board (1), anode electrode (3), cathode electrode (4), preceding division board (5) and back division board (6); It is characterized in that: anode electrode (3) and cathode electrode (4) be arranged in parallel, simultaneously, between anode electrode (3) and cathode electrode (4), be provided with preceding division board (5) and back division board (6), make between anode electrode (3) and the cathode electrode (4) and form microfluidic flow channels, and at electrode generation biochemical reaction face micro-channel is set; Top at anode electrode (3) and cathode electrode (4) is provided with Upper gasket (11), and the top of Upper gasket (11) arranges top board (1); Below at anode electrode (3) and cathode electrode (4) is provided with lower gasket (13), and the below of lower gasket (13) arranges base plate (2); Front end at top board (1) is provided with nutrient solution import (7) near anode-side, front end at top board (1) is provided with electron acceptor import (8) near cathode side, nutrient solution import (7) and electron acceptor import (8) all communicate with microfluidic flow channels, the rear end of base plate (2) is provided with outlet (9), this outlet (9) communicates with microfluidic flow channels, biological culture based sols and electron acceptor enter the microfluidic flow channels Laminar Flow by nutrient solution import (7) and electron acceptor import (8) respectively, the biological culture based sols is by the degraded of the Institute of Micro-biology on the anode electrode (3), and catabolite is discharged outside the battery by outlet (9).
2. the no film microfluid microorganism battery based on graphite electrode according to claim 1 is characterized in that: described anode electrode (3) is graphite flake, carbon cloth, carbon felt, carbon paper, carbon brush or graphite rod; Described cathode electrode (4) is graphite flake, carbon cloth, carbon felt, carbon paper, carbon brush or graphite rod.
3. the no film microfluid microorganism battery based on graphite electrode according to claim 1 and 2, it is characterized in that: between anode electrode (3) and cathode electrode (4), be provided with preceding division board (5) and back division board (6), make between anode electrode (3) and the cathode electrode (4) and form microfluidic flow channels, described microfluidic flow channels is rectangularl runner or front wide and rear narrow runner or beloid runner.
4. the no film microfluid microorganism battery based on graphite electrode according to claim 3, it is characterized in that: described electron acceptor comprises the potassium ferricyanide, oxygen, six cobaltammines, many iodide ions, potassium peroxydisulfate or potassium permanganate.
5. the no film microfluid microorganism battery based on graphite electrode according to claim 4, it is characterized in that: the biological culture based sols is made of activated sludge and culture medium, and the main component of described culture medium is: 1.13-4.52g L
-1Sodium acetate, 15.3g L
-1Na-
2HPO
412H
2O, 3g L
-1KH
2PO
4, 0.5g L
-1N
aCl, 0.1g L
-1NH
4Cl, 0.1gL
-1MgSO
47H
2O, 11mg L
-1CaCl
2And1.0mL L
-1Trace element.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106711487A (en) * | 2017-03-31 | 2017-05-24 | 重庆大学 | Film-free heat regenerative ammonia cell and manufacturing method |
| CN107394237A (en) * | 2016-05-17 | 2017-11-24 | 香港大学 | Cell of fuel cell and fuel cell pack |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102610843A (en) * | 2012-03-29 | 2012-07-25 | 南京大学 | Microbial fuel cell |
| WO2012134104A2 (en) * | 2011-03-25 | 2012-10-04 | 단국대학교 산학협력단 | Microbial fuel cell comprising a microprobe array |
-
2013
- 2013-03-14 CN CN201310081648.1A patent/CN103199289B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012134104A2 (en) * | 2011-03-25 | 2012-10-04 | 단국대학교 산학협력단 | Microbial fuel cell comprising a microprobe array |
| CN102610843A (en) * | 2012-03-29 | 2012-07-25 | 南京大学 | Microbial fuel cell |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107394237A (en) * | 2016-05-17 | 2017-11-24 | 香港大学 | Cell of fuel cell and fuel cell pack |
| CN107394237B (en) * | 2016-05-17 | 2020-06-19 | 香港大学 | Fuel cell unit and fuel cell stack |
| CN106711487A (en) * | 2017-03-31 | 2017-05-24 | 重庆大学 | Film-free heat regenerative ammonia cell and manufacturing method |
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| CN103199289B (en) | 2015-04-08 |
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