CN108520963A - Environmental-friendly graphene bioelectrode microbiological fuel cell and preparation method thereof - Google Patents
Environmental-friendly graphene bioelectrode microbiological fuel cell and preparation method thereof Download PDFInfo
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/90—Selection of catalytic material
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- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
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Abstract
The invention belongs to biological fuel cell technical fields, disclose environmental-friendly graphene bioelectrode microbiological fuel cell preparation method.The present invention builds double chamber type microbiological fuel cell first, graphene oxide solution is added in the anode chamber of microbiological fuel cell, graphene oxide is restored in anode using the reduction of anode microorganism, it is interacted with microorganism and is self-assembly of graphene biology anode, battery is subjected to electrode reversion operation, is selected the anodic conversion of graphene biology into graphene biological-cathode by microorganism；Prepared graphene biology anode and graphene are repaiied into biological-cathode and build graphene bioelectrode microbiological fuel cell in pairs as the two poles of the earth, environmental-friendly prepares graphene bioelectrode microbiological fuel cell.The excellent conductive capability of graphene, huge specific surface area are made full use of, the reduction efficiency of anodic oxidation efficiency and cathode oxygen, proton and electronics is improved, accelerates electron transport rate, and then improve electricity generation performance.
Description
Technical field
The present invention relates to microbiological fuel cells, and in particular to a kind of environmental-friendly micro-reduction graphite oxide in situ
The method that graphene modified bioelectrode and the double graphene bioelectrode microbiological fuel cells of structure are self-assembly of after alkene.
Background technology
Microbiological fuel cell (microbial fuel cell, abbreviation MFC) be it is a kind of using microorganism by organic matter turn
Become the new bio electrochemical appliance of electric energy, MFC can be produced electricl energy while handling waste water.
Improve the important directions that the power that MFC outputs generate is always MFC development.MFC electricity generation performances and electrode material, production
Electric bacterium, anode and cathode Tiny ecosystem, electron mediator, MFC configurations and service condition etc. are closely related.Wherein, electricity production bacterium overlay film update and
Cathode, the anode material of electron transmission carrier are one of the key factors of MFC electricity productions, directly determine the interaction of electricity production bacterium and electrode
Effect, influences microorganism overlay film and update, and then influences microbial metabolism growth and electron transmission, coulombic efficiency and power are defeated
Go out.
Graphene (graphene) is a kind of Novel Carbon Nanomaterials, and theoretical specific surface area reaches 2630m2/ g, conductivity are
6000s/cm.It is thus a kind of electrode modified material that can effectively improve MFC electricity generation performances, price is relatively low, before great application
Scape.
But the reduction methods such as chemical method, electrochemical process, heat treating process prepare graphene or need to use toxic reagent (such as at present
Hydrazine hydrate) or need hot conditions, environment unfriendly.And the graphene prepared has very strong hydrophobicity, in aqueous solution
Be difficult to disperse, cannot direct modified electrode, and easily reunite, significantly reduce its specific surface area and electric conductivity.It usually requires
Graphene uniform could be fixed by the auxiliary of organic polymer conducting polymer (such as Nafion, polyaniline and polypyrrole)
In electrode surface.So not only so that the manufacture difficulty increase of Graphene electrodes, increases electrode manufacturing cost, counteract graphite
Alkene advantage of low cost；But also gained Graphene electrodes internal resistance increases, graphene high conductivity advantage is counteracted.
Prior art MFC cathodes and anode microorganism be all difficult on the extremely strong graphene of electrode surface hydrophobicity implantation cover
Film, it is difficult to the graphene bioelectrode for preparing suitable microorganism implantation overlay film, to be unable to give full play graphene and micro- life
Object collective effect improves the production capacity of microbiological fuel cell.
Invention content
Above-mentioned in order to overcome the problems, such as, the main purpose of the present invention is to provide environmental-friendly graphene bioelectricity
Atomic biological fuel cell and preparation method thereof.The method is by microorganism in situ redox graphene in electrode surface self assembly
Form the electricity production efficiency that microbiological fuel cell can be improved in graphene modified bioelectrode.
The purpose of the present invention is realized by following proposal：
The component part of environmental-friendly graphene bioelectrode microbiological fuel cell and preparation method thereof has：Cathode
Room, anode chamber, proton exchange membrane, cathode electrode, anode electrode, external resistance, external circuit；The active dirt of cathode chamber and anode chamber
Mud, nutrient solution, trace element, vitamin etc..
Double graphene bioelectrode microbiological fuel cells are repaiied by graphene modified biological-cathode and graphene
The double chamber type microbiological fuel cell of the biological anode composition of decorations.
The graphene modified biology anode is to add graphene oxide solution in anode chamber, utilizes the reduction of microorganism
Graphene oxide is restored and generates graphene by effect, is self-assembly of graphene modified biology anode.
The graphene modified biological-cathode is become by the graphene modified biology anode reversion of microbiological fuel cell
Graphene modified biological-cathode.
Graphene modified biological-cathode has formed and then has repeated the above steps, and graphene oxide is added in anode chamber
Graphene oxide is restored using the reduction of microorganism and generates graphene, is self-assembly of graphene bio-modification by solution
Anode.So far, double graphene bioelectrode microbiological fuel cells are formed.
The anode of microbiological fuel cell is closing anaerobic environment, the gas that external exhaust apparatus discharge generates；Cathode is
Aerobic environment maintains dissolved oxygen in 6~8mg/L or so.
In anode chamber and anode chamber's internal carbon source is 500~1000mg/L of a concentration of COD equivalents.
The electricity production bacterium is inoculated with the activated sludge of sewage treatment plant, in the cathode chamber and sun of microbiological fuel cell
Pole room carries out aerobic and anaerobic acclimation and is formed by mixing electricity production flora respectively.
The electricity production flora is grown with graphene in electrode surface in the form of biomembrane.
The operation in thermostatic chamber (30 ± 2 DEG C) using double chamber type microbiological fuel cell.By activated sludge according to reactor
The 10%~20% of volume is inoculated in cathode chamber and the anode chamber of reactor respectively；Anode adds carbon source and culture solution and maintains to detest
The gas that anaerobism generates is discharged and so that extraneous air is entered by oxygen environment, external exhaust apparatus；Cathode then add carbon source and
Culture solution simultaneously continues to be aerated, and maintains dissolved oxygen in 6~8mg/L；Outer conductor connects external resistance, and acquires output electricity with data collecting card
Pressure starts microbiological fuel cell.In the anode chamber of microbiological fuel cell, graphene oxide solution is added；Microorganism is gone back
Original work become graphene with by graphene oxide reduction so that the process of reduction obtains together with the process for forming graphene anode
Step, wait for graphene anode electrode formed after by graphene biology anode reversion electrode become graphene biological-cathode electrode；It is former
First anode chamber becomes cathode chamber, carries out aeration and maintains dissolved oxygen in 6~8mg/L, original cathode chamber becomes anode chamber, closed
The external exhaust apparatus of anaerobism, then add graphene oxide solution in anode chamber；The activated sludge is derived from municipal sewage treatment.
The nutrient composition is that phosphate buffer (being shown in Table 1), trace element (being shown in Table 2) and vitamin (being shown in Table 3) are matched
Than as follows, added in right amount according to reactor size.
The anode chamber and the material (such as polymethyl methacrylate) that cathode chamber material is antiacid caustic corrosion.
The cathode electrode and anode electrode is suspended on position among electrode chamber.
The anode electrode and cathode electrode material are carbon material or other base electrode materials, and anode electrode and cathode are electric
Pole material may be the same or different.The carbon material or other base electrode materials can be graphite felt, mesoporous carbon fiber or carbon nanometer
One or more in pipe, porous carbon materials large specific surface area is conducive to the apposition growth of microorganism species.
The external circuit refers to cathode electrode and anode electrode and is connected with external resistance by plain conductor.Selected plain conductor
Have many advantages, such as that anticorrosive, electric conductivity is excellent, price is cheap.
In the graphene modified electrode microbiological fuel cell During Process of Long-term Operation, the reparation of graphene modified electrode can
By adding graphene oxide solution in anode chamber again, graphene modified biology anode is formed, then carry out following for polarity reversion
Ring mode of operation is completed.
The preparation method of microorganism fuel cell, including step in detail below：
Carbon material or other base electrode material electrodes respectively as the anode and cathode of microbiological fuel cell, difference
It is suspended on anode chamber and cathode chamber, is connect with external resistance by plain conductor；With proton exchange membrane between anode chamber and cathode chamber
It separates, anode chamber and cathode chamber add phosphate buffer, trace element and vitamin, and anode chamber and cathode chamber add COD to work as
The carbon source of 500~1000mg/L is measured, anode chamber is adding certain density graphene oxide solution, original work are gone back using microorganism
With graphene modified biology anode is formed, then inverts electrode and form graphene modified biological-cathode；Then it is fired again in microorganism
The anode chamber of material battery continuously adds certain density graphene oxide solution, is allowed to form graphene modified biology anode, wait for
After graphene bio-modification anode is formed, with the micro- life of graphene bio-modification cathode sets Graphene electrodes in pairs formed before
Object fuel cell.
The period completion refers to that the cell output voltage measured by data collecting card is less than setting voltage.
In anode, using carbon source as electron donor, bacterium anaerobic oxidation glucose obtains electronics, and passes to anode, electronics
Cathode is cycled to reach by external circuit again, is reacted with the oxygen of cathode and generates water, electronics flows to form electric current and produce electricity；Invert pole
After property, original anode becomes cathode, and original cathode becomes anode, to form graphene modified biological-cathode, then in sun
Pole room adds graphene oxide solution, is allowed to form graphene anode again, and the operation method of operation in this way overcomes thin
Watersoluble plumbago alkene cannot direct modified electrode this technology barrier, to realize that continuous high-efficient produces electricity.
The present invention mechanism be：
The graphene modified bioelectrode and double graphene bioelectrode microbiological fuel cells of the present invention is using sun
Graphene oxide solution is added in pole, restores graphene oxide to form graphene modified biology sun using the reduction of microorganism
Then pole uses the method for operation of reversed polarity, graphene modified biology anode is become graphene modified biological-cathode.This hair
Bright to add graphene oxide solution in anode chamber twice, the mode of one-time electrode reversion, overcoming hydrophobicity graphene cannot be straight
It connects this technology barrier of modified electrode and takes full advantage of the excellent electric conductivity of graphene and huge specific surface area, in cathode
The contact action for increasing oxygen, proton and electronics increases electron transmission efficiency, to carry out high-efficiency continuous electricity production in anode.
The present invention compared with the prior art, has the following advantages and effect：
(1) graphene modified bioelectrode microbiological fuel cell of the invention is added in the anode of microbiological fuel cell
Add graphene oxide solution, graphene modified anode is formed in situ using the reduction of microorganism, with anode microbe symbiotic
It is longer than electrode surface and forms three-dimensional graphene electrode, then inverting electrode becomes graphene modified biological-cathode, and which overcome dredge
Watersoluble plumbago alkene cannot direct modified electrode this technology barrier, form a kind of environmental-friendly graphene biological-cathode microbiological
Fuel cell.
(2) double graphene bioelectrode microbiological fuel cells of the invention utilize the good electric conductivity and graphite of graphene
The huge specific surface area of alkene makes the electron transport rate being happened on anode and electron transmission efficiency increase, and enhances on anode
Oxidation reaction, while enabling the oxygen being happened on cathode, proton and electronics that there is better reduction reaction, to improve
The anode current transfer performance and cathode catalytic activity of double graphene microbiological fuel cells, and then improve entire Microbial fuel
The power density of battery achievees the purpose that high-efficiency continuous electricity production.
(3) cathode and anode of graphene modified bioelectrode of the invention and double Graphene electrodes microbiological fuel cells
Activated sludge is all made of as biocatalyst, no any metallic catalyst modification or the addition of the artificial mediator of external source, is reduced
Microbiological fuel cell is built and operating cost, enhances the continuous service of microbiological fuel cell, is conducive to follow-up industry amplification.
Description of the drawings
Fig. 1 is current density-power density of graphene modified biology anode microbiological fuel cell prepared by embodiment 1
Figure；
Fig. 2 is the polarization curve of graphene modified biology anode microbiological fuel cell prepared by embodiment 1；
Fig. 3 is current density-power density of graphene modified biological-cathode microbiological fuel cell prepared by embodiment 2
Figure；
Fig. 4 is the polarization curve of graphene modified biological-cathode microbiological fuel cell prepared by embodiment 2；
Fig. 5 is current density-power density of double graphene bioelectrode microbiological fuel cells prepared by embodiment 3
Figure；
Fig. 6 is the polarization curve of double graphene bioelectrode microbiological fuel cells prepared by embodiment 3.
Specific implementation mode
To more fully understand the present invention, with reference to embodiment and attached drawing, the invention will be further described, but this hair
Bright embodiment is not limited only to this.
Embodiment 1
(1) structure of microbiological fuel cell and assembling
Microbiological fuel cell is prepared by acid-alkali-corrosive-resisting and polymethyl methacrylate materials easy to process.Pond body is
Single chamber, volume 40cm3, anode chamber and cathode chamber are by proton exchange membrane (PE01, purchased from Zhejiang eternal lasting Group Co., Ltd) point
It is graphite felt every, anode material, cathode material, which is load, to be had the carbon paper of catalyst (catalyst is platinum, load capacity 0.5mg/
cm2).Anode hanging placement parallel with respect to medial septum, and be connected with external resistance by titanium silk, it is connect with cathode with stainless (steel) wire
Constitute circuit.Pond body top end opening is arranged, convenient for operation monitoring, the acquisition of data and sampling analysis.Anode chamber's head cover is additionally set
Set the discharge that a gas vent with pressure reducing valve is convenient for internal gas.Body side bottom end is arranged discharge outlet and is arranged convenient for indoor liquid
Go out, when operation is clamped with tongs.
(2) structure of graphene biology anode microbiological fuel cell
The operation in thermostatic chamber (30 ± 2 DEG C) using two independent single chamber type microbiological fuel cells.Anaerobism activity is dirty
The anode chamber that mud (being derived from Guangzhou Lie De sewage treatment plants) is inoculated in reactor according to the 10% of anode building volume；It adds anode chamber
As the culture solution (so that glucose content is 500mg/L) of organic carbon source and anaerobic environment is maintained using glucose, external exhaust dress
It sets and the gas that anaerobism generates is discharged and so that extraneous air is entered；It (is respectively designated as in two microbiological fuel cells
MFC-A and MFC-B) all addition phosphate buffer (being shown in Table 1), trace element solution (being shown in Table 2), vitamin are molten respectively for anode chamber
Liquid (is shown in Table 3)；Graphene oxide is added in the anode chamber B microbiological fuel cells (MFC-B) so that graphene oxide is a concentration of
1mg/L；External 500 Ω external resistances, and output voltage is acquired with data collecting card, start microbiological fuel cell.With external number
According to the computer monitor and acquisition microbiological fuel cell output voltage, voltage of collector anodic dissolution is replaced less than 50mV.First three
A period adds graphene oxide solution to the anode chambers MFC-B, molten with phosphate buffer, trace element solution, vitamin
Liquid adds together.
1 phosphate buffer solution of table (PBS) is formulated
Remarks：All reagents are that analysis is pure；It is settled to 1L, matches to obtain a concentration of 200mM of PBS, uses a concentration of 50mM.
2 trace element formula of table
Remarks：All reagents are that analysis is pure；It is settled to 1L for use (being placed in 4 DEG C of refrigerators to preserve).When changing water, dilution 100
It uses again.
3 vitamin formula of table
Remarks：All reagents are that analysis is pure；Be settled to 1L, with 100 times of vitamin stock, 100 times of dilution wait for
With (being placed in 4 DEG C of refrigerators to preserve).
The microbiological fuel cell of microorganism in situ redox graphene modified anode runs six periods, to grasp
Moving law, the power density and polarization curve of two microbiological fuel cells of period 6 pair are tested.Fig. 1 is two electricity
The power density curve in pond, power density are to change external resistance by resistance box after MFC opens a way to voltage stabilization
(5000-50 Ω) is recorded after the voltage stabilization under each resistance value and is replaced next resistance, as shown in Figure 1, power density is
The electricity generation performance for evaluating MFC systems, here using area power density, graphene modified microbiological fuel cell (MFC-
B power density) is 1147.2mW/m2, the power density of microbiological fuel cell (MFC-A) as a control group is
712.5mW/m2, this illustrates that micro-reduction graphene modified anode improves 61.0% to the power density of MFC.
Fig. 2 is the polarization curve of two microbiological fuel cells, and polarization curve is also the method by above-mentioned change resistance
It obtains, as external resistance is from becoming smaller greatly, during current density increases, polarization curve characterizes under a constant current, MFC energy
Great voltage is accessed, from figure 2 it can be seen that under same potential, graphene modified anode microbiological fuel cell
The current density bigger of MFC-B, this shows that the reducing power of micro-reduction graphene modified anode microbiological fuel cell becomes
By force；Under same current density, the potential difference bigger of MFC-B anode and cathodes illustrates the micro- life of micro-reduction graphene modified anode
The biochemical reaction motive force of object fuel cell MFC-B electrode surfaces is stronger.
The present embodiment is prepared for the single chamber type microbiological fuel cell of graphene modified biology anode, appoints without additional addition
What external source artificial electron's mediator, it is easy to operate, can be in the purpose compared with realization continuous high-efficient production capacity under low operating cost, and environment is friendly
It is good free from environmental pollution.
Embodiment 2
(1) structure of microbiological fuel cell and assembling
The microbiological fuel cell of the present invention is by acid-alkali-corrosive-resisting and polymethyl methacrylate materials structure easy to process
At.Pond body is divided into two Room, and centre is separated by proton exchange membrane, includes electrode in two Room, and electrode material is large specific surface area
Porous graphite felt material, convenient for microorganism on its surface and the internal apposition growth in the form of biomembrane.Two electrodes are relatively intermediate
The parallel hanging placement of diaphragm, and be connected with external resistance by titanium silk, constitute circuit.Entire reactor is solid by clamping plate and screw
It is fixed.The setting of pond body top end opening is convenient for operation monitoring, the acquisition of data and sampling analysis.A band is additionally arranged in anode chamber's head cover
The gas vent of pressure reducing valve is convenient for the discharge of internal gas.Body side bottom end is arranged discharge outlet and is discharged convenient for indoor liquid, operation
When clamped with tongs.
(2) structure of graphene modified biological-cathode microbiological fuel cell
The operation in thermostatic chamber (30 ± 2 DEG C) using two independent double chamber type microbiological fuel cells.According to mass ratio 1
: aerobic activated sludge+anaerobic activated sludge of 1 mixing (is derived from Guangzhou Lie De sewage treatment plants A2The aerobic section of/O techniques and
Anaerobism section) cathode chamber and the anode chamber that are inoculated in reactor respectively according to the 10% of reactor volume；Anode chamber's volume is
240mL, anode chamber's internal carbon source are glucose, a concentration of COD equivalents 500mg/L.Cathode chamber volume is 240mL, cathode indoor carbon
Source is NaHCO3, a concentration of COD equivalents 500mg/L；Anode addition as the culture solution of organic carbon source and maintains anaerobism using glucose
The gas that anaerobism generates is discharged and so that extraneous air is entered by environment, external exhaust apparatus；Cathode is then added with NaHCO3
For carbon source culture solution and continue aeration maintain dissolved oxygen in 6~8mg/L；Cathode chamber adds phosphate buffer with anode chamber
(being shown in Table 1), trace element solution (being shown in Table 2), vitamin solution (being shown in Table 3)；(it is named as MFC-A, separately in microbiological fuel cell
One do not add graphene oxide solution be named as MFC-B) add graphene oxide solution in anode chamber so that graphene oxide
Solution concentration is 1mg/L；External 500 Ω external resistances, and output voltage is acquired with data collecting card, start Microbial fuel electricity
Pond.With the computer monitor of external data collector and acquisition microbiological fuel cell output voltage, voltage less than 50mV replace it is cloudy,
Anodic dissolution.
First three period keeps the above-mentioned method of operation and graphene oxide addition manner, the 4th period, A microorganisms
Fuel cell (MFC-A) and control microbiological fuel cell (MFC-B) start electrode reversion, and original anode is become cathode,
Original cathode becomes anode, and carbon source still maintains new anode chamber's addition glucose, and cathode chamber adds NaHCO3, anode chamber is not
Graphene oxide solution is added again.
Graphene modified biological-cathode microbiological fuel cell runs two periods to grasp moving law, period 3
The power density and polarization curve of two microbiological fuel cells are tested.Fig. 3 is to be prepared by above-mentioned change resistance method
Current density-power density diagram of graphene biological-cathode microbiological fuel cell, power density are to evaluate the electricity production of MFC systems
Performance, here using area power density, the power of graphene modified biological-cathode microbiological fuel cell (MFC-A) is close
Degree is 62.4mW/m2, the power density of blank biological-cathode microbiological fuel cell (MFC-B) is 57.8mW/m2, this illustrates stone
Black alkene modified biological cathode improves 10% to the power density of MFC.Fig. 4 is the two micro- lifes obtained by above-mentioned change electric-resistivity method
The polarization curve of object fuel cell, as external resistance is from becoming smaller greatly, during current density increases, polarization curve characterizes
Under one constant current, MFC can obtain great voltage, it can be seen from the figure that under same potential, graphene modified biology is cloudy
The current density bigger of pole, this shows that the reducing power of graphene modified biological-cathode becomes strong.
The present embodiment is prepared for the microbiological fuel cell of graphene modified biological-cathode, and the present embodiment is without additional addition
Any external source artificial electron mediator, it is environmental-friendly, it is easy to operate, it can be compared with the mesh for realizing continuous high-efficient production capacity under low operating cost
's.
Embodiment 3
(1) structure of microbiological fuel cell and assembling
The microbiological fuel cell of the present invention is by acid-alkali-corrosive-resisting and polymethyl methacrylate materials structure easy to process
At.Pond body is divided into two Room, and centre is separated by proton exchange membrane, includes electrode in two Room, and electrode material is large specific surface area
Porous graphite felt material, convenient for microorganism on its surface and the internal apposition growth in the form of biomembrane.Two electrodes are relatively intermediate
The parallel hanging placement of diaphragm, and be connected with external resistance by titanium silk, constitute circuit.Entire reactor is solid by clamping plate and screw
It is fixed.The setting of pond body top end opening is convenient for operation monitoring, the acquisition of data and sampling analysis.A band is additionally arranged in anode chamber's head cover
The gas vent of pressure reducing valve is convenient for the discharge of internal gas.Body side bottom end is arranged discharge outlet and is discharged convenient for indoor liquid, operation
When clamped with tongs.
(2) structure of double graphene microbiological fuel cells
The operation in thermostatic chamber (30 ± 2 DEG C) using two independent double chamber type microbiological fuel cells.According to mass ratio 1
: aerobic activated sludge+anaerobic activated sludge of 1 mixing (is derived from Guangzhou Lie De sewage treatment plants A2The aerobic section of/O techniques and
Anaerobism section) be inoculated in reactor respectively with the 10% of reactor volume cathode chamber and anode chamber；Anode chamber's volume is 240mL,
Anode chamber's internal carbon source is glucose, a concentration of COD equivalents 500mg/L；Cathode chamber volume is 240mL, and cathode chamber internal carbon source is
NaHCO3, a concentration of COD equivalents 500mg/L；Anode addition as the culture solution of organic carbon source and maintains anaerobic environment using glucose,
The gas that anaerobism generates is discharged and so that extraneous air is entered by external exhaust apparatus；Cathode is then added with NaHCO3It is inorganic
The culture solution of carbon source simultaneously continues aeration maintenance dissolved oxygen in 6~8mg/L；Cathode chamber adds phosphate buffer with anode chamber
(being shown in Table 1), trace element solution (being shown in Table 2), vitamin solution (being shown in Table 3)；In the anode chamber A microbiological fuel cells (MFC-A)
Middle addition graphene oxide solution so that a concentration of 1mg/L of graphene oxide；External 500 Ω external resistances, and with data collecting card
Output voltage is acquired, microbiological fuel cell is started.With the computer monitor and acquisition Microbial fuel electricity of external data collector
Pond output voltage, voltage replace cathode and anode solution less than 50mV.
First three period keeps the above-mentioned method of operation and graphene oxide solution addition manner, and in the 4th period, A is micro-
Biological fuel cell (MFC-A) and control microbiological fuel cell (MFC-B) start electrode reversion, and original anode is become cloudy
Pole, original cathode becomes anode, then continuously adds a concentration of 1mg/L in three periods in the anode chamber of microbiological fuel cell
Graphene oxide, be allowed to form graphene biology anode, after waiting for that graphene modified biology anode is formed, and be formed before
Graphene biological-cathode group Graphene electrodes microbiological fuel cell in pairs.Addition carbon source still maintains new addition Portugal of anode chamber
Grape sugar, cathode chamber add NaHCO3。
Double graphene microbiological fuel cells run two periods to grasp moving law, two micro- lifes of period 3 pair
The power density and polarization curve of object fuel cell are tested.Fig. 5 is micro- for the double graphenes prepared by above-mentioned change resistance method
Current density-power density diagram of biological fuel cell, power density are to evaluate the electricity generation performance of MFC systems, are used here
It is area power density, the power density of double graphene microbiological fuel cells (MFC-A) is 69.6mW/m2, compare microorganism
The power density of fuel cell (MFC-B) is 35.5mW/m2, this illustrates that the power density of double graphene microbiological fuel cells is
Compare 1.96 times of microbiological fuel cell.
Fig. 6 is the polarization curve of two microbiological fuel cells obtained by above-mentioned change electric-resistivity method, with external resistance
From becoming smaller greatly, during current density increases, polarization curve characterizes under a constant current, and MFC can obtain great voltage.
It can be seen from the figure that under same potential, the current density bigger of double graphene modified biological-cathodes, this shows that graphene is given birth to
The reducing power of object cathode becomes strong；Under same potential, the current density bigger of double graphene biology anodes, this shows graphene
The oxidability of biological anode is stronger；This electricity production efficiency for allowing for double graphene microbiological fuel cells obtains significantly
It is promoted.
The present embodiment is prepared for double graphene modified bioelectrode microbiological fuel cells, which is not necessarily to
Any external source artificial electron mediator is additionally added, it is environmental-friendly, it is easy to operate, it can be compared with realizing continuous high-efficient under low operating cost
The purpose of production capacity.
Embodiment of the present invention are not limited by the above embodiments, and other any spirit without departing from the present invention are real
Changes, modifications, substitutions, combinations, simplifications made by under matter and principle, should be equivalent substitute mode, are included in the present invention
Protection domain within.
Claims (10)
1. environmental-friendly graphene bioelectrode microbiological fuel cell, including anode chamber, cathode chamber, proton exchange membrane, sun
Pole electrode and cathode electrode, external circuit, anode chamber and cathode chamber are respectively arranged with activated sludge, nutrient solution and carbon source；
Microbiological fuel cell is prepared by acid-alkali-corrosive-resisting and polymethyl methacrylate materials easy to process.Pond body is single
Room, volume 40cm3, anode chamber and cathode chamber separate by proton exchange membrane, and anode material is graphite felt, and cathode material is load
Having the carbon paper of catalyst, (catalyst is platinum, load capacity 0.5mg/cm2).Anode hanging placement parallel with respect to medial septum, and
It is connected with external resistance by titanium silk, circuit is connected and composed with stainless (steel) wire and cathode.Pond body top end opening is arranged, convenient for operation prison
Control, the acquisition of data and sampling analysis.Additionally one gas vent with pressure reducing valve of setting is convenient for internal gas to anode chamber's head cover
Discharge.Discharge outlet is arranged convenient for indoor liquid discharge in body side bottom end, and when operation is clamped with tongs.
The microbiological fuel cell of the present invention is made of acid-alkali-corrosive-resisting and polymethyl methacrylate materials easy to process.Pond
Body is divided into two Room, and centre is separated by proton exchange membrane, includes electrode in two Room, and electrode material is the porous stone of large specific surface area
Black felt material, the hanging placement parallel with respect to medial septum of two electrodes, and be connected with external resistance by titanium silk, constitute circuit.Entirely
Reactor is fixed by clamping plate and screw.The setting of pond body top end opening is convenient for operation monitoring, the acquisition of data and sampling analysis.Sun
A gas vent with pressure reducing valve is additionally arranged in pole room head cover, is convenient for the discharge of internal gas.The setting draining of body side bottom end
It mouthful is discharged convenient for indoor liquid, when operation is clamped with tongs.
It is characterized in that building double chamber type microbiological fuel cell first, start after running in the anode chamber of microbiological fuel cell
Graphene oxide solution is added, is restored graphene oxide in anode (carbon material electrode using the reduction of anode microorganism
Or other basic electrodes) on interacted with microorganism and be self-assembly of graphene modified biology anode.Then battery is subjected to electrode
Reversion operation, is selected by microorganism, and graphene biology anodic conversion is graphene modified biological-cathode；By prepared graphite
Alkene modified biological anode constructs double graphene biologies with graphene modified biological-cathode as the two poles of the earth of microbiological fuel cell
Electrode microbiological fuel cell is a kind of preparation of environmental-friendly graphene modified bioelectrode and double graphene bioelectrodes
The construction method of microbiological fuel cell.
2. environmental-friendly graphene bioelectrode microbiological fuel cell and preparation method thereof according to claim 1,
It is characterized in that：Double chamber type microbiological fuel cell is built first, and electrode is that carbon material electrode or other basic electrodes, electrode are big
It is small to match with anode chamber and cathode chamber size；Anode chamber is separated with cathode chamber with the partition board for accompanying proton exchange membrane.
3. environmental-friendly graphene bioelectrode microbiological fuel cell and preparation method thereof according to claim 1,
It is characterized in that：The positive electrode and negative electrode is suspended in electrode chamber；Positive electrode and the material of negative electrode are carbon material electricity
Pole or other basic electrodes；The external circuit refers to cathode and anode and is connected with external resistance by plain conductor (such as titanium silk)；
The period completes to refer to detects that cell output voltage sets voltage less than it by voltage data detection card.
4. environmental-friendly graphene bioelectrode microbiological fuel cell and preparation method thereof according to claim 1,
It is characterized in that：The formation of the graphene bio-modification anode, is continuously to add graphene oxide solution in anode chamber, micro-
After biological in-situ is reduced into graphene, is interacted with microorganism and be self-assembly of graphene modified biology anode.
5. environmental-friendly graphene bioelectrode microbiological fuel cell and preparation method thereof according to claim 1,
It is characterized in that：The formation of the graphene modified biological-cathode is to first pass through continuously to add graphene oxide in anode chamber
Solution, microorganism in situ are reduced into graphene, are interacted with microorganism and are self-assembly of graphene modified biology anode, then will be electric
Pond carries out reversion electrode operation, is selected by microorganism, and graphene biology anodic conversion is graphene modified biological-cathode；
After inverting electrode, anode chamber originally becomes cathode chamber, is aerated, and maintains aerobic environment, keeps 6~8mg/ of dissolved oxygen
L or so；
After inverting electrode, cathode chamber originally becomes anode chamber, and closed external exhaust apparatus maintains anaerobic environment.
6. environmental-friendly graphene bioelectrode microbiological fuel cell and preparation method thereof according to claim 1,
It is characterized in that：Cathode chamber and anode chamber add carbon source (such as NaHCO3, glucose etc.)；Cathode chamber and anode chamber add phosphorus
Phthalate buffer, trace element, vitamin.
7. environmental-friendly graphene bioelectrode microbiological fuel cell and preparation method thereof according to claim 1,
It is characterized in that：It is added by graphene oxide solution in the anode chamber of microbiological fuel cell so that anode chamber's internal oxidition graphite
Alkene solution concentration is appropriate.
8. environmental-friendly graphene bioelectrode microbiological fuel cell and preparation method thereof according to claim 1,
It is characterized in that：Anode chamber and the activated sludge that cathode chamber institute microbe inoculation is sewage treatment plant are inoculated with, in Microbial fuel
The cathode chamber of battery and anode chamber carry out domestication and are formed by the functional microorganisms groups such as electricity production bacterium respectively.
9. environmental-friendly graphene bioelectrode microbiological fuel cell and preparation method thereof according to claim 1,
It is characterized in that：In microbiological fuel cell During Process of Long-term Operation, the surface fracture of graphene modified bioelectrode can basis
It is repaired the 5 of claims.
10. a kind of graphene bioelectrode microbiological fuel cell environmental-friendly by claim 1~9 any one of them and
Preparation method.
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