CN103199289B - Graphite-electrode-based film-free microfluid microbial battery - Google Patents

Graphite-electrode-based film-free microfluid microbial battery Download PDF

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CN103199289B
CN103199289B CN201310081648.1A CN201310081648A CN103199289B CN 103199289 B CN103199289 B CN 103199289B CN 201310081648 A CN201310081648 A CN 201310081648A CN 103199289 B CN103199289 B CN 103199289B
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electrode
graphite
anode electrode
microfluid
cathode electrode
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CN103199289A (en
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叶丁丁
杨扬
李俊
朱恂
廖强
王宏
陈蓉
王永忠
丁玉栋
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Chongqing University
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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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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

Based on graphite electrode without film microfluid microorganism battery
Technical field
The present invention relates to microbiological fuel cell, be specifically related to based on graphite electrode without film microfluid microorganism battery.
Background technology
Microbiological fuel cell (Microbial fuel cell) has that raw material sources are extensive, reaction condition is gentle, good biocompatibility, be a kind of can the new fuel cell of electrogenesis while disposing of sewage.On the one hand, microbiological fuel cell can as the waste water treatment of amplificationization and renewable energy source generating device; On the other hand, microminiature microbiological fuel cell can be powered for portable electric appts or be carried out fast detecting water environment index as biology sensor.But because performance is lower, manufacturing process is expensive, the development of Minitype microbial fuel cell receives restriction.
In existing Minitype microbial fuel cell, battery adopts photoetching (Chen usually, Y.P., Y.Zhao, and soft lithographic (Hou et al. (2011) .Biosensors and Bioelectronics26 (6): 2841-2846), H., technology processing L.Li, et al. (2009) .PLoS ONE4 (8): e6570).Although photoetching accurately can control shape, the size of microchannel, in most research, have to adopt the gold being easy to photoetching as electrode material.Except with high costs, gold electrode also can cause biocompatibility poor, and namely cause the internal resistance of cell to increase due to electric transmission loss, cell power density declines, and directly limit the use of Minitype microbial fuel cell.Due to outstanding conductivity, admirably biocompatibility and chemical stability, graphite electrode is widely used in the microbiological fuel cell of amplificationization.At present also for seeing report graphite being applied to Minitype microbial fuel cell.Adopt proton exchange membrane to separate anode and cathode unlike other Minitype microbial fuel cell, the microfluid concept based on laminar flow is introduced in microbiological fuel cell.
Microfluid fuel cell (Microfluidic fuel cell) is the feature utilizing fluid to flow at minute yardstick underflow, the two fluids comprising fuel and oxidant is respectively separated 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 the microfluid concept based on laminar flow is introduced in microbiological fuel cell by Li, Z., Y.Zhang, et al first.Compared with traditional Minitype microbial fuel cell, the microbiological fuel cell under microfluidic control does not need proton exchange membrane, avoids that the fuel infiltration relevant to film, film are dry, film is degenerated and the problem such as negative electrode water management,
Summary of the invention
Technical problem to be solved by this invention be to provide based on graphite electrode without film microfluid microorganism battery, 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, based on graphite electrode without film microfluid microorganism battery, comprise base plate, top board, anode electrode, cathode electrode, front division board and rear division board; It is characterized in that: anode electrode and cathode electrode be arranged in parallel, simultaneously, division board and rear division board before being provided with between anode electrode and cathode electrode, make to form microfluidic flow channels between anode electrode and cathode electrode, and adopt the mode of low-speed WEDM in electrode generation biochemical reaction face processing micro-channel; Above anode electrode and cathode electrode, be provided with Upper gasket, the top of Upper gasket arranges top board; The below of anode electrode and cathode electrode is provided with lower gasket, and the below of lower gasket arranges base plate; Nutrient solution import is provided with near anode-side in the front end of top board, electron acceptor import is provided with near cathode side in the front end of top board, 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 microfluidic flow channels Laminar Flow respectively by nutrient solution import and electron acceptor import, biological culture based sols is degraded by the Institute of Micro-biology on anode electrode, and catabolite is discharged outside battery by outlet.
Wherein, front division board and rear division board play the effect intercepting anode and cathode short circuit, guide fluid to flow in the mode of parallel laminar flow in the initial segment; Pad plays sealing function, prevents oxygen to be leaked to biofilm surface, causes battery performance to decline.
Culture medium solution and electron acceptor flow in interelectrode microchannel, at the liquid/liquid interface place formed by diffusion mixing, the flow velocity and the concentration that control culture medium solution and electron acceptor make two fluids form Laminar Flow in conduit, and isolated anode electrode and cathode electrode, thus avoid the material using this costliness of proton exchange membrane, be conducive to the cost reducing microbiological fuel cell; Simultaneously, owing to not needing the material using proton exchange membrane to completely cut off as negative electrode and positive electrode, also help the transmission rate improving proton between cathode anode, reduce the internal resistance of cell, instead of proton exchange membrane, reduce battery cost, and avoid that the fuel infiltration, the film that are caused by proton exchange membrane are dry, film is degenerated and the problem series of problems such as negative electrode water management; Culture medium at anode electrode surface by microbial consumption, electronics is discharged into anode electrode by the mode of directly contact by microbe, electronics arrives cathode electrode by external circuit, and complete culture medium, product and the electron acceptor of unreacted discharges battery by the outlet on base plate; Meanwhile, fluid flows at antimicrobial surface, and culture medium tangentially serves the effect of screening superior microorganism while biofilm surface flows through, and microbe and electrode surface is combined closely, reduces the internal resistance of cell, improve battery performance;
According to the preferred version without 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.
According to the preferred version without film microfluid microorganism battery based on graphite electrode of the present invention, division board and rear division board before being provided with between anode electrode and cathode electrode, make to form microfluidic flow channels between anode electrode and cathode electrode, described microfluidic flow channels is rectangularl runner or front wide and rear narrow runner or beloid runner.
According to the preferred version without 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 without film microfluid microorganism battery based on graphite electrode of the present invention, biological culture based sols is made up 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, 3gL -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 without film microfluid microorganism battery based on graphite electrode of the present invention is: the performance that improve Minitype microbial fuel cell, and the internal resistance reducing Minitype microbial fuel cell; Electrode material cost of manufacture of the present invention is low, enhances the biocompatibility of electrode; Meanwhile, electrode of the present invention adopts low-speed WEDM technique, shortens the Production Time of existing Minitype microbial fuel cell while ensureing precision; Microfluid fuel cell involved in the present invention does not need proton exchange membrane, not only there is compact conformation, advantage that cost is low, and advantage electrogenesis bacterium can be screened, avoid that the fuel infiltration relevant to film, film are dry, film is degenerated and the problem such as negative electrode water management simultaneously, no matter be as biology sensor or as the compact power of powering for tiny devices, all have a good application prospect.
Accompanying drawing explanation
Fig. 1 be of the present invention based on graphite electrode without film microfluid microorganism battery assembling relationship figure.
Fig. 2 be of the present invention based on graphite electrode without film microfluid microorganism battery structural representation.
Fig. 3 is the structural representation of positive plate, minus plate, front 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
Below in conjunction with embodiment, the present invention is further described specifically, but embodiments of the present invention are not limited thereto.
See Fig. 1 to Fig. 4, based on graphite electrode without film microfluid microorganism battery, by top board 1, base plate 2, anode electrode 3, cathode electrode 4, front division board 5, rear division board 6, Upper gasket 11 and lower gasket 13 are formed, and are fixed by bolt 12; Front division board 5 and rear 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 rear division board 6 before being provided with between anode electrode 3 and cathode electrode 4, make to form microfluidic flow channels between anode electrode 3 and cathode electrode 4, channel pitch is 1mm-4mm; Described microfluidic flow channels can be rectangularl runner or front wide and rear narrow runner or beloid runner;
Above anode electrode 3 and cathode electrode 4, be provided with Upper gasket 11, the top of Upper gasket 11 arranges top board 1; The below of anode electrode 3 and cathode electrode 4 is provided with lower gasket 13, and the below of lower gasket 13 arranges base plate 2; Upper gasket 11 and lower gasket 13 can adopt the silica gel pad that 0.5mm is thick; Nutrient solution import 7 is provided with near anode-side in the front end of top board 1, electron acceptor import 8 is provided with near cathode side in the front end of top board 1, 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 microfluidic flow channels Laminar Flow respectively by nutrient solution import 7 and electron acceptor import 8, and ensure electron acceptor to be diffused into anode and produce microorganism electricity generation suppression phenomenon; Biological culture based sols is degraded by the Institute of Micro-biology on anode electrode 3, and catabolite is discharged outside battery by outlet 9.
Described anode electrode 3 adopts graphite flake, carbon cloth, carbon felt, carbon paper, carbon brush or graphite rod to form; Described cathode electrode 4 adopts graphite flake, carbon cloth, carbon felt, carbon paper, carbon brush or graphite rod to form.Before using, first adopt the mode of low-speed WEDM in electrode generation biochemical reaction face processing micro-channel, 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 the attachment of microbe; Low-speed WEDM utilizes the fine wire of continuous moving to make electrode, and carry out pulse spark electric discharge removal metal, excision forming to workpiece, wire travelling speed is lower than 0.2m/s, and precision reaches 0.001mm, stable working, evenly, shake little, crudy is high.
Described electron acceptor can be the 10mM-40mM potassium ferricyanide, oxygen, 0.02-0.2mM six cobaltammine, the many iodide ions of 0.5mM-2mM, 5mM-30mM potassium peroxydisulfate or 20-200mM potassium permanganate.
Described biological culture based sols is made up 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.
For convenience of connecting, anode electrode and cathode electrode two ends are stretched out outside top board and base plate respectively, and contact resistance forms closed-loop path respectively.
Of the present inventionly adopt the miscellaneous bacteria being rich in electrogenesis bacterium Geobacter and Shewanella as bacterial classification based on graphite electrode without film microfluid microorganism battery, adopt the culture medium simulative organic wastewater containing sodium acetate, as bacterium substrate source, whole battery does not adopt any precious metal material, has greatly saved cost.
Below in conjunction with specific embodiment, and see Fig. 5, Fig. 6 and table one, illustrate the present invention under various anolyte flow velocity with the performance under various potassium ferricyanide concentration, wherein:
Fig. 5 is the performance curve of the present invention under three kinds of flow velocitys.Wherein, square dot, circular point, triangle form point represent performance curve when reactant flow velocity is 10mL/h, 20mL/h and 40mL/h respectively.
Fig. 6 be based on graphite electrode without the performance curve of film microfluid microorganism battery under various potassium ferricyanide concentration.Wherein, square dot, circular point, upper triangle form point, lower triangle form point, Diamond spot represent potassium ferricyanide concentration respectively when being 2.5mM, 5mM, 10mM, 20mM, 40mM based on the performance curve of graphite electrode microfluid microbiological fuel cell.
Table one be based on graphite electrode without film microfluid microorganism battery with deliver, the typical maximum area power density of Minitype microbial fuel cell and comparing 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 is 2mm × 1mm, and potassium ferricyanide concentration is 10mM, and in culture medium, sodium acetate concentration is 1.13g L-1, and ambient temperature is 30 DEG C, and the performance of battery as shown in the figure.As can be seen from such as, the maximum power density of battery reaches 520mW/m2, is 1.6 times of current Minitype microbial fuel cell maximum area power density.
Embodiment two:
In this example, adopt sodium acetate concentration in culture medium to be 1.13g L-1, anode and cathode flow rate of liquid is 10mL/h, and ambient temperature is 30 DEG C, 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 current Minitype microbial fuel cell maximum area power density.
Find out from table one, under best measurement condition, maximum area power density based on the Minitype microbial fuel cell of graphite electrode is 615mW/m2, it is 1.86 times of current Minitype microbial fuel cell maximum area power density, through test further, this internal resistance of cell is 5100 Ω, is 68% of the minimum internal resistance of current Minitype microbial fuel cell.
Can draw from embodiment one, embodiment two and table one, invention increases the performance of Minitype microbial fuel cell, and reduce the internal resistance of Minitype microbial fuel cell, have a good application prospect.

Claims (4)

1. based on graphite electrode without film microfluid microorganism battery, comprise base plate (2), top board (1), anode electrode (3), cathode electrode (4), front division board (5) and rear division board (6), it is characterized in that: anode electrode (3) and cathode electrode (4) be arranged in parallel along microfluidic flow direction, simultaneously, front division board (5) and rear division board (6) is provided with between anode electrode (3) and cathode electrode (4), make to form microfluidic flow channels between anode electrode (3) and cathode electrode (4), and micro-channel is set in electrode generation biochemical reaction face, the top of anode electrode (3) and cathode electrode (4) is provided with Upper gasket (11), and the top of Upper gasket (11) arranges top board (1), the below of anode electrode (3) and cathode electrode (4) is provided with lower gasket (13), and the below of lower gasket (13) arranges base plate (2), nutrient solution import (7) is provided with near anode-side in the front end of top board (1), electron acceptor import (8) is provided with near cathode side in the front end of top board (1), 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 microfluidic flow channels Laminar Flow respectively by nutrient solution import (7) and electron acceptor import (8), biological culture based sols is by the Institute of Micro-biology's degraded on anode electrode (3), catabolite is discharged outside battery by outlet (9).
2. according to claim 1 based on graphite electrode without film microfluid microorganism battery, it is characterized in that: described anode electrode (3) is graphite flake or graphite rod; Described cathode electrode (4) is graphite flake or graphite rod.
3. according to claim 1 and 2 based on graphite electrode without film microfluid microorganism battery, it is characterized in that: between anode electrode (3) and cathode electrode (4), be provided with front division board (5) and rear division board (6), make to form microfluidic flow channels between anode electrode (3) and cathode electrode (4), described microfluidic flow channels is rectangularl runner or front wide and rear narrow runner or beloid runner.
4. according to claim 3 based on graphite electrode without film microfluid microorganism battery, it is characterized in that: described electron acceptor comprises the potassium ferricyanide, oxygen, six cobaltammines, many iodide ions, potassium peroxydisulfate or potassium permanganate.
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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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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

Patent Citations (2)

* Cited by examiner, † Cited by third party
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

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