CN110429286A - Application of the titanium nitride nano stick array in anode of microbial fuel cell - Google Patents

Application of the titanium nitride nano stick array in anode of microbial fuel cell Download PDF

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CN110429286A
CN110429286A CN201910759571.6A CN201910759571A CN110429286A CN 110429286 A CN110429286 A CN 110429286A CN 201910759571 A CN201910759571 A CN 201910759571A CN 110429286 A CN110429286 A CN 110429286A
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anode
fuel cell
titanium nitride
nitride nano
array
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CN110429286B (en
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颜美
刘达
果崇申
常庆环
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Harbin Institute of Technology
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Harbin Institute of Technology
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8663Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • H01M4/8673Electrically conductive fillers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/16Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M2004/8678Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8689Positive electrodes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

Abstract

The invention discloses a kind of application of titanium nitride nano stick array in anode of microbial fuel cell, based on the biocompatibility that titanium nitride is excellent, good chemical stability, high conductivity, preparation is simple, cheap and the nanometer stick array structure of growth in situ on carbon cloth the features such as, rightGeobacter‑soliBacterium efficiently concentrating is produced electricity, accumulation rate is effectively improved the output performance of microbiological fuel cell up to 97.2%.Titanium nitride nano anode pairGeobacter‑ soliThe efficiently concentrating for producing electricity bacterium, it is low fundamentally to overcome present microorganism fuel cell output electric energy, right the disadvantages of fluctuation of serviceGeobacter‑soliThe high accumulation rate of electricity production bacterium is also highest in current studied anode material.Therefore, titanium nitride nano stick array anode of microbial fuel cell be can be applied to, the electricity production power and power output stability of battery are effectively improved.

Description

Application of the titanium nitride nano stick array in anode of microbial fuel cell
Technical field
The invention belongs to material, biology, field of environmental technology, be related to it is a kind of can efficiently concentrating ground bacillus titanium nitride nano Application of the stick array in anode of microbial fuel cell.
Background technique
With the fast development of economic globalization, water pollution problems becomes increasingly severe, and also needs in sewage disposal process The a large amount of energy is consumed, and microbiological fuel cell can be by the biocatalysis of electricity production bacterium, by what is contained in sewage Mass energy is converted into electric energy, and realization is turned waste into wealth, and sewage treatment is changed into self-supporting or production capacity type from energy consumption type.Mesh Before, transfer mode of the electronics between electricity production bacterium and anode have bacterium directly contact with anode transmitting, nano wire mediation it is quick The electron transmission that electron transmission and electron shuttle body mediate, therefore, anode be the key that restrict microbiological fuel cell performance because One of element.Researchers are by developing different anode materials, to improve the transmission efficiency of extracellular electronics, promote microorganism combustion Expect the performance of battery.But whether the promotion of extracellular electron transmission efficiency, to depend on anode to the enrichment degree of electricity production bacterium, and In the electricity production bacterium currently found,Geobacter(ground bacillus) is typically to produce electricity bacterium in mixed bacterial and have stronger production Electric energy power.When research finds many bacterial strains as pure strains cultivation, electricity production power density wants much lower when being mixed relatively, can A variety of floras can play respective advantage and carry out classification degradation to organic pollutant when can be due to mixed culture, recycle electricity production Bacterium by electron transmission to anode, thus by external circuits be transmitted to cathode generate electric current, in addition, in mixed bacterial by anode from The dynamic electricity production bacterium filtered out and biomembrane are also more stable under the system.Therefore while it is known thatGeobacterWith stronger Electricity generation ability, but still cannot be simply just inoculated with progress pure strains cultivation and be used for microbiological fuel cell, and should mix Automatic screening is carried out to it using anode material when inoculation, therefore, developing one kind can effectively be enriched in Mixed MicrobesGeobacterAnode material it is increasingly important.And up to the present it is not yet reported that a kind of out can efficiently concentratingGeobacterIt produces The anode of microbial fuel cell of electric bacterium.Therefore, finding one kind being capable of efficiently concentratingGeobacterThe anode material for producing electricity bacterium is compeled In the eyebrows and eyelashes.
Summary of the invention
In order to overcome existing anode of microbial fuel cell low to electricity production bacterium enrichment degree and restriction micro-organisms fuel cell The deficiency of electricity generation performance, the present invention provides it is a kind of can efficiently concentrating ground bacillus titanium nitride nano stick array in Microbial fuel Application in galvanic anode.
The purpose of the present invention is what is be achieved through the following technical solutions:
It is a kind of can efficiently concentrating ground bacillus application of the titanium nitride nano stick array in anode of microbial fuel cell, be based on nitrogen Change the excellent biocompatibility of titanium, the preferable stability of transition metal nitride, prepare simple, cheap and unique nanometer The features such as stick array structure, use is using carbon cloth as substrate, and the titanium nitride nano stick array of growth in situ is as Microbial fuel electricity Pond anode pairGeobacter-soliBacterium efficiently concentrating is produced electricity, accumulation rate can effectively improve the performance of battery up to 97.2%, (4.025 W/m are exported with high power density2), electric current output steady in a long-term, signal period continuous discharge is up to 6 ~ 7 d.
It is a kind of defeated using the electricity production power and electric energy of above-mentioned titanium nitride nano stick anode-array improvement microbiological fuel cell The method of stability out, includes the following steps:
Step 1: using titanium nitride nano stick array as anode, which is strung with titanium silk, and carbon fiber brush is as cathode, micro- life For object fuel cell reactor as running gear, the dischargeable capacity of the anode chamber and the cathode chamber is 100 ml, is added 80 ~ 90 in anode chamber Ml anolyte, cathode chamber is interior to be added 100 ml catholytes, anode formula of liquid are as follows: 1.5 ~ 2 g/L anode substrate (anhydrous acetic acids Sodium, glucose, lactate or other substrates), 0.1 ml/L of vitamin solution, 12.5 ml/L of microelement, cathode formula of liquid Are as follows: 16.4 g/L K3[Fe(CN)6], 3.7 g/L KCl;
Step 2: being added 10 ~ 20ml inoculation liquid in anode chamber and be inoculated with, then, the resistance of additional 1000 Ω, by cathode It is connected with anode, forms closed circuit, being placed in 37 DEG C of constant incubator makes its stable operation, uses DAQ6510 number Its voltage output situation of word multimeter real-time monitoring, when voltage drop is as low as 0.05 V, the anode and cathode liquid that more renews respectively;
Step 3: after battery stable operation, pass through anodic scan electron microscope after electrochemical impedance, power density, inoculation And the characterization such as anode Comparison of Microbial Community, show that titanium nitride nano stick anode-array can pass through efficiently concentratingGeobacter- soliBacterium is produced electricity, to effectively improve the power output and operation stability of microbiological fuel cell.
The mixture of the galvanic anode water outlet that in the present invention, inoculation liquid can be anaerobic sludge water, tame or both, example Such as: galvanic anode water outlet that inoculation liquid has been tamed by the anaerobic sludge water and 10 ~ 15 ml of 10 ~ 20 ml (i.e. stable fortune Capable galvanic anode water outlet, specially uses the anaerobic sludge microbe inoculation fuel cell of 10 ~ 20 ml, is then put Enter in 37 DEG C of constant incubators, the anolyte after continuous service 15 ~ 20 days can be used for the starting inoculation of other batteries) group At, in which: anaerobic sludge comes from Harbin peace sewage treatment plant.After battery operation a cycle, voltage drop is as low as 0.05 When V, anolyte and catholyte are replaced respectively, and anolyte is poured out into about 80 ~ 90 ml, retains about 10 ~ 20 ml in anode chamber Stoste add about 80 ~ 90 ml to facilitate the quick start of battery and newly match anolyte, and catholyte is all outwelled, The potassium ferricyanide solution newly matched is added.
In the present invention, the electrochemical impedance spectroscopy test after adhering to mycoderm is the anode table in battery continuous operation about 20 d Face has formed stable mycoderm, under three-electrode system (saturated calomel electrode is used as reference electrode, platinized platinum to electrode), 5 It is tested in the mixed solution of the potassium ferricyanide solution of+5 mM of mM PBS solution.
In the present invention, power density curve test calculates corresponding current density and power density in replacement external resistor When, resistance value drops to 500 Ω hereinafter, the fall of resistance value is less than 50 Ω, inflection phenomenon occurs to prevent power density curve.
In the present invention, anodic scan electron microscope observation sample preparation after being inoculated with, de- by bacteria adhension and gradient It after water, adequately to be dried, then, carry out metal spraying processing, to have clearly object under a scanning electron microscope As about 2 min of metal spraying time or so.
In the present invention, anode Comparison of Microbial Community, after inoculation when battery continuous and steady operation about 30 d, anode surface Microorganism attachment sufficiently, after forming biomembrane, then carries out DNA and extracts sequencing analysis.
Compared with existing anode of microbial fuel cell, the invention has the following advantages that
(1) titanium nitride nano stick anode-array being capable of efficiently concentratingGeobacter-soli, accounted in anode microbiologic population Than being up to 97.2%.
(2) titanium nitride itself has excellent electric conductivity and biocompatibility, and its generated in-situ nanometer on carbon cloth Stick array structure can be good at improving the roughness of carbon cloth surfaces, so that ground bacillus is easy to grab array and attached using cilium , and its electric conductivity with class noble metal, the electronics passed out by bacterium through metabolism can be quickly transferred to carbon cloth, So as to quickly pass to external circuit, the efficiency of fuel cell generation of battery is promoted.
(3) titanium nitride has class noble metal, has preferable electro catalytic activity, and synthesis technology is simple, low in cost.
(4) titanium nitride has preferable stability, can be applied to anode of microbial fuel cell, is effectively improved microorganism The stability of the long-term power output of fuel cell.
(5) biocompatibility excellent the present invention is based on titanium nitride, good chemical stability, high conductivity, preparation are simple It is cheap and the nanometer stick array structure of growth in situ on carbon cloth the features such as, it is rightGeobacter-soliIt is efficiently rich to produce electricity bacterium Collection, accumulation rate are effectively improved the output performance of microbiological fuel cell up to 97.2%, and maximum power density output is 4.025 W/m2, it is as many as 2.2 times of control group carbon cloth anode, and signal period continuous discharge is up to 6 ~ 7 d.
(7) titanium nitride nano stick anode-array pairGeobacter-soliThe efficiently concentrating for producing electricity bacterium, fundamentally overcomes The disadvantages of present microorganism fuel cell output electric energy is low, fluctuation of service is rightGeobacter-soliProduce electricity the height of bacterium Accumulation rate is also highest in current studied anode material.Therefore, titanium nitride nano stick array can be fired applied to microorganism Expect galvanic anode, is effectively improved the electricity production power and power output stability of battery.
Detailed description of the invention
Fig. 1 is the X-ray diffraction spectrogram of titanium nitride nano stick array;
Fig. 2 is the scanning electron microscope diagram of titanium nitride nano stick anode-array;
Fig. 3 is the scanning electron microscope diagram on titanium nitride nano stick anode-array after attached microbial;
Fig. 4 is the scanning electron microscope diagram on naked carbon cloth anode after attached microbial;
Fig. 5 is the voltage output curve graph of continuous operation;
Fig. 6 is polarization curve and power density curve graph;
Fig. 7 is that anode adheres to electrochemical impedance spectrogram after mycoderm;
Fig. 8 is sequencer map of the microorganism in kind of level on anode.
Specific embodiment
Further description of the technical solution of the present invention with reference to the accompanying drawing, and however, it is not limited to this, all to this Inventive technique scheme is modified or replaced equivalently, and without departing from the spirit and scope of the technical solution of the present invention, should all be covered Within the protection scope of the present invention.
The present invention provides it is a kind of can efficiently concentrating ground bacillus titanium nitride nano stick array in microbiological fuel cell sun The application of pole, steps are as follows for concrete application:
Step 1: titanium nitride nano stick anode-array is prepared, and prepares carbon brush cathode, anode chamber and cathode chamber.
Step 2: it is inoculated with using mixing sludge.
Step 3: 37 DEG C of constant incubators are put into, its stable operation is made.
Step 4: after battery operation is stablized, battery performance test and anode microbiologic population composition analysis are carried out.
In above-mentioned steps one, used titanium nitride nano stick anode-array is nanometer rods of the growth in situ in carbon cloth surfaces Array, the material be commission east reflect Scientific Research Platform be made (finding also has relevant preparation method in document: Lu X, Wang G, Zhai T, et al. Stabilized TiN nanowire arrays for high-performance and Flexible supercapacitors [J] Nano Lett, 2012,12 (10): 5376-81.).Pass through X-ray diffraction Test (Fig. 1) shows that the crystal form of this titanium nitride nano stick is cube, by Fig. 2 it can be seen that titanium nitride nano stick is uniformly grown On the carbon fiber of carbon cloth.Used microbiological fuel cell reactor is double chamber type, and the volume of anode chamber and cathode chamber For 100 ml.
In above-mentioned steps two, anaerobic sludge comes from Harbin peace sewage treatment plant, and inoculation liquid is the dirt of 10 ~ 20 ml Muddy water.
In above-mentioned steps three, when battery is run in 37 DEG C of constant incubators, the resistance of additional 1000 Ω, and use Its voltage output situation of DAQ6510 digital multimeter real-time monitoring.When cell voltage is reduced to 0.05 V or less, battery is taken It replaces anolyte and catholyte respectively out, catholyte is all outwelled, rejoin 100 ml and newly match catholyte, anolyte retains About 10 ~ 20 ml stostes are added about 80 ~ 90 ml and newly match anolyte, so that battery being capable of quick start.
In above-mentioned steps four, battery performance test includes output voltage curve and power density curve, from Fig. 5 output voltage Curve knows that the maximum output voltage for nitrogenizing Ni―Ti anode is 0.655 V, hence it is evident that higher than 0.535 V of carbon cloth, and its lasting electric energy is defeated Out for 6 ~ 7 days.Cell power density test method is: after the complete anolyte of battery altering and catholyte, cell voltage liter When to highest, removing external resistor makes its 1 h or so that opens a way, and then connects upper resistance box, resistance successively from 2000,1000, 800,700,600,550,500,450,400,350,300,250 200 Ω are dropped to, and successively recorded corresponding under each resistance Voltage value successively calculates corresponding electric current and power by I=U/R and P=UI.Then, then divided by 2 × 10-4 m2It obtains Corresponding current density and power density.Known by the power density curve of Fig. 6, the maximum power density for nitrogenizing Ni―Ti anode is 4.025 W/m2, it is carbon cloth (1.872 W/m2) as many as 2.2 times.
Based on the reason of the high power output that titanium nitride nano stick anode-array is realized, the present invention exists from microorganism respectively Three aspects of anode electrochemical impedance spectrum and anode microbiologic population composition after attachment speed, attachment mycoderm on anode carry out Characterization.Scanning electron microscope diagram when Fig. 3 is 2.5 ~ 3 d after nitrogenizing Ni―Ti anode inoculation, Fig. 4 are naked carbon cloth anode inoculations Scanning electron microscope diagram when 2.5 ~ 3 d afterwards, it can be seen that titanium nitride anode surface has adhered to a large amount of microorganism, portion Subregion has formed thin mycoderm, and carbon cloth anode is only sparse depends on a small amount of bacterium, this has with its Fig. 5 nitridation Ni―Ti anode The shorter voltage starting time is consistent.The electrochemical impedance spectrogram that Fig. 7 is measured when being battery 25 ~ 30 d of stable operation, can be with See that the Charge-transfer resistance (85.5 Ω) of nitridation Ni―Ti anode is significantly lower than carbon cloth (385.8 Ω) anode, this has with it The excellent power output result having matches.The sequencing result of anode when Fig. 8 is battery 30 d of stable operation, it can be seen that nitrogen Change on Ni―Ti anodeGeobacter-soliElectricity production bacterium accounting is up to 97.2%, to be significantly higher than carbon cloth (70.7%) anode, Just because of titanium nitride nano stick anode-array pairGeobacter-soliThe efficiently concentrating for producing electricity bacterium, so that being received based on titanium nitride Rice stick anode-array has stable high power output.
The present invention is described further combined with specific embodiments below, but does not limit the contents of the present invention:
Embodiment 1
The present invention provides it is a kind of can efficiently concentrating ground bacillus titanium nitride nano stick array in anode of microbial fuel cell Using steps are as follows for concrete application:
Step 1: respectively 1 × 1 cm of clip titanium nitride nano stick anode-array and carbon cloth anode, and using titanium silk by it therefrom Between put on fixation, assemble double-chamber microbiological fuel cell reaction unit, the dischargeable capacity of the anode chamber and the cathode chamber is 100 ml, in anode chamber 80ml anolyte is added, 100 ml catholytes, anode formula of liquid are as follows: 2 g/L anhydrous sodium acetates, vitamin is added in cathode chamber 0.1 ml/L of solution, 12.5 ml/L of microelement, cathode formula of liquid are as follows: 16.4 g/L K3[Fe(CN)6], 3.7 g/L KCl.
Step 2: the anode chamber's water outlet for taking+10 ml of 10 ml anaerobic sludge to tame uses anhydrous acetic acid as inoculation liquid Sodium is as substrate.
Step 3: assembled microbiological fuel cell reactor is put into 37 DEG C of constant incubators, is used in combination Its voltage output situation of DAQ6510 digital multimeter real-time monitoring.
Embodiment 2
Unlike the first embodiment, the clip of anode size is not limited to 1 × 1 cm to the present embodiment, can clip according to actual needs.
Embodiment 3
Unlike the first embodiment, microbiological fuel cell reactor is not limited to double chamber type reaction unit to the present embodiment, it is also possible to In air single chamber reaction unit and other kinds of reactor.
Embodiment 4
Unlike the first embodiment, inoculation liquid is not limited to the anode that+10 ml of 10 ml anaerobic sludge has been tamed and goes out the present embodiment Water can also only use the anode water outlet of suitable anaerobic sludge or suitable other batteries tamed.What addition had been tamed Anode is discharged the quick start for facilitating battery, and therefore, the selection of battery inoculation liquid can be determine according to actual needs.
Embodiment 5
Unlike the first embodiment, anode substrate is not limited to anhydrous sodium acetate to the present embodiment, and glucose or lactic acid also can be used Salt and other substrates.

Claims (10)

1. a kind of application of titanium nitride nano stick array in anode of microbial fuel cell.
2. application of the titanium nitride nano stick array according to claim 1 in anode of microbial fuel cell, feature It is that the titanium nitride nano stick array is the titanium nitride nano stick array of growth in situ using carbon cloth as substrate.
3. a kind of stablized using the electricity production power and power output of titanium nitride nano stick anode-array improvement microbiological fuel cell The method of property, it is characterised in that described method includes following steps:
Step 1: using titanium nitride nano stick array as anode, carbon fiber brush is made as cathode, microbiological fuel cell reactor For running gear, 80 ~ 90 ml anolytes are added in anode chamber, 100 ml catholytes are added in cathode chamber;
Step 2: 10 ~ 20 ml inoculation liquids are added in anode chamber and are inoculated with, then, the resistance of additional 1000 Ω will be negative Pole and anode connect, formed closed circuit, being placed in 37 DEG C of constant incubator makes its stable operation, real-time monitoring its Voltage output situation, when voltage drop is as low as 0.05 V, the anode and cathode liquid that more renews respectively.
4. the electricity production power according to claim 3 for improving microbiological fuel cell using titanium nitride nano stick anode-array And the method for power output stability, it is characterised in that the dischargeable capacity of the anode chamber and the cathode chamber of the fuel cell reactor is 100 ml。
5. the electricity production power according to claim 3 for improving microbiological fuel cell using titanium nitride nano stick anode-array And the method for power output stability, it is characterised in that the anode formula of liquid are as follows: 1.5 ~ 2 g/L anode substrates, vitamin 0.1 ml/L of solution, 12.5 ml/L of microelement.
6. the electricity production power according to claim 5 for improving microbiological fuel cell using titanium nitride nano stick anode-array And the method for power output stability, it is characterised in that the anode substrate is anhydrous sodium acetate, glucose or lactate.
7. the electricity production power according to claim 3 for improving microbiological fuel cell using titanium nitride nano stick anode-array And the method for power output stability, it is characterised in that the cathode formula of liquid are as follows: 16.4 g/L K3[Fe(CN)6], 3.7 g/L KCl。
8. the electricity production power according to claim 3 for improving microbiological fuel cell using titanium nitride nano stick anode-array And the method for power output stability, it is characterised in that the galvanic anode water outlet that the inoculation liquid is anaerobic sludge water, has tamed Or both mixture.
9. the electricity production power according to claim 8 for improving microbiological fuel cell using titanium nitride nano stick anode-array And the method for power output stability, it is characterised in that the preparation method of the galvanic anode water outlet tamed is as follows: using The anaerobic sludge microbe inoculation fuel cell of 10 ~ 20 ml, then puts it into 37 DEG C of constant incubators, continuous service Anolyte after 15 ~ 20 days can be used for the starting inoculation of other batteries.
10. the electricity production function according to claim 3 for improving microbiological fuel cell using titanium nitride nano stick anode-array The method of rate and power output stability, it is characterised in that when the voltage drop is as low as 0.05 V, replace anolyte and yin respectively Anolyte is poured out 80 ~ 90 ml, the stoste of 10 ~ 20 ml is retained in anode chamber, 80 ~ 90 ml is added and newly matches by pole liquid Anolyte, catholyte are all outwelled, and the catholyte newly matched is added.
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