CN105680056B - A kind of preparation method of the anode assembly of microbiological fuel cell - Google Patents
A kind of preparation method of the anode assembly of microbiological fuel cell Download PDFInfo
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- CN105680056B CN105680056B CN201610033184.0A CN201610033184A CN105680056B CN 105680056 B CN105680056 B CN 105680056B CN 201610033184 A CN201610033184 A CN 201610033184A CN 105680056 B CN105680056 B CN 105680056B
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9008—Organic or organo-metallic compounds
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
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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
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Abstract
The present invention provides a kind of preparation method of the anode assembly of microbiological fuel cell, and step is as follows：Methacrylic acid is dissolved in dichloromethane, add in dicyclohexylcarbodiimide, amine alkyl osmium bipyridine chlorination reactant salt, after washing by organic phase it is dry monomer Y；2 methylacryoyloxyethyl phosphocholines, 2 metering system butyl esters, 4 vinylphenylboronic acids and monomer Y are dissolved in absolute ethyl alcohol, add in azodiisobutyronitrile reaction, product in chloroform/ether in the mixed solvent is precipitated, after being re-dissolved in deionized water and being evaporated under reduced pressure, obtains copolymer p MBVY；Copolymer p MBVY and the culture solution for being loaded with Shewanella are mixed into obtain component I, polyvinyl alcohol with aseptic culture fluid is mixed to obtain to component II, is put the electrodes into mold, adds in isometric component I and II, treat gel solidification after mixing, by electrode with electrode plate, substrate, screen packs to obtain the final product.The method of the invention realizes the recyclings of material, maintain easily.
Description
Technical field
The invention belongs to biological fuel cell fields, and in particular to a kind of preparation of the anode assembly of microbiological fuel cell
Method.
Background technology
Microbiological fuel cell（MFC）It is a kind of dress for utilizing microbiological oxidation organic substrates and electronics being provided for electrode
It puts, this kind of device can provide electric energy while purification may generate the organic pollution of adverse effect to environment, have huge
Big economic and social benefit.
In MFC, in anodic oxidation organic substrates to generate electronics and proton, electronics is transferred to anode and leads to microorganism
It crosses the circuit being connected with cathode chamber and flows to cathode, cathode chamber includes oxidant（Such as oxygen）, electronics and proton are by the oxidant
Reduction, so as to generate the potential difference between anode and cathode and drive current through external circuit.
Microorganism is mostly fixed on electrode surface by the anode of existing MFC using film, and is passed through redox medium and realized
One of transmission of the electronics from microbial activity center to electrode, the disadvantages of this method are that limitations are larger, can only utilize electricity
The electric current that several microns to tens microns of pole surface, further drawback are used redox medium in fluid state, once
Leakage can generate secondary pollution, in addition, the survival for the microorganism that existing MFC carries electrode and proliferation still lack effective adjust
Control means.
Invention content
The technical issues of solution：For limitations existing for existing anode of microbial fuel cell are big, oxidation also
Former medium is also easy to produce the shortcomings that secondary pollution and the survival of microorganism and proliferation shortage Effective Regulation means, and the present invention provides one
The preparation method of the anode assembly of kind microbiological fuel cell, the preparation method are prepared anode assembly and are gathered by biocompatibility
It closes object gel and is fixed on electrode material surface, the side chain for forming gelatin polymer has redox medium, to realize electronics
From microbial activity centrally through transmission of the redox medium to electrode material surface.
Technical solution：A kind of the step of preparation method of the anode assembly of microbiological fuel cell, this method, is as follows：
（1）The preparation of monomer Y：By being dissolved in 10mmol methacrylic acids containing a concentration of 0.1mmol/L polymerization inhibitors
In dichloromethane, 0.1mol dicyclohexylcarbodiimides are added, stir 30min, then add in 10mmol amine alkyl osmium connection pyrrole
Pyridine chlorate reacts 2h, is washed, and regathers organic phase and is dried in vacuo and obtains monomer Y or by by 10mmol methyl
Acryloyl chloride is dissolved in the dichloromethane containing a concentration of 0.1mmol/L polymerization inhibitors, and the triethylamine of 10mmol is added in simultaneously at 0 DEG C
The hydroxyalkyl ferrocene of 10mmol is added dropwise, reacts 4h, is washed after filtering with deionized water, regather organic phase and vacuum is done
It is dry, it is washing and is being dried to obtain monomer Y；
（2）The preparation of copolymer p MBVY：By 2- methylacryoyloxyethyls phosphocholine, 2- metering systems butyl ester, 4- second
Alkenyl phenyl boric acid and monomer Y are according to 5:2:1:2 molar ratio is dissolved in absolute ethyl alcohol, the solution of a concentration of 1mol/L is made, so
The azodiisobutyronitrile of 10mmol is added in afterwards, and solution is warming up to 60 DEG C under protection of argon gas and reacts 48h, reaction product is existed
0.1:0.9 chloroform/ether in the mixed solvent precipitates and collects solid product, then solid product is dissolved in deionized water and is depressurized
To get copolymer p MBVY after distillation；
（3）Surface is covered with the preparation of the electrode of graphite fibre：In the graphite rod or graphite cake of diameter or thickness for 0.5-1cm
The graphite fibre layer that thickness is 0.5-1mm is above prepared by high molecular material pyrolysis and sintering and is covered with graphite fibre to get surface
Electrode；
（4）The preparation of anode assembly：1）Copolymer p MBVY and the culture solution for being loaded with Shewanella are mixed, copolymer
The mass percent of PMBVY is 5%, obtains component I；2）Polyvinyl alcohol is mixed with aseptic culture fluid, the quality hundred of polyvinyl alcohol
Divide than being 5%, obtain component II；3）The electrode that surface is covered with to graphite fibre is put into mold, sequentially adds isometric component
I and component II, swing die are uniformly mixed two kinds of components, stand 15 minutes and treat gel solidification；4）Mold is sloughed, by 3）Middle place
Electrode after reason is with electrode plate, substrate, screen packs to get the anode assembly of microbiological fuel cell.
Step described above（1）In the chemical structural formula of amine alkyl osmium bipyridine chlorate be
, wherein n=5-12.
Step described above（1）In hydroxyalkyl ferrocene chemical formula be HO-（CH2）n- Fc, wherein n=5-12.
The chemical structural formula of monomer Y described above isOr, wherein n=5-12.
The chemical structural formula of copolymer p MBVY described above is,
Wherein a=0.4-0.5, b=0.1-0.3, c=0.1-0.2, d=0.1-0.2.
Step described above（3）In high molecular material be polyacrylonitrile or carboxymethyl cellulose.
In use for some time, it is reduced when electric current declines when the micro organism quantity in gel and takes out electrode, be put into mold,
The sorbitol solution of 1mol is added in, be centrifuged off microorganism and collects copolymer p MBVY and PVA, repetitive operation 3 by the precipitation method
Complete the replacement of power generation microorganism.
Advantageous effect：A kind of preparation method of the anode assembly of microbiological fuel cell provided by the invention has following
Advantage：
1st, the phenyl boric acid group in the copolymer p MBVY in the present invention can form gel by covalent bond and PVA, no
Other crosslinking agents are needed, property is stablized, and prepares simple；
2nd, the present invention is by the way that by microbial encapsulation, in polymer gel, the porous structure of gel ensure that microorganism with treating
Processing organic substrates come into full contact with, and the phosphocholine group in gel has bionical characteristic, can play protection microorganism, carry
The survival rate of high microorganism, also can restriction micro-organisms excessive proliferation, ensure the output steady in a long-term of microbiological fuel cell；
3rd, the anode assembly that the present invention is prepared realizes electronics by microbial activity center --- electron transmission matchmaker
The transfer chain of Jie's --- graphite fibre --- electrode material, can effectively collect far from electrode surface（0.5-1mm）Microorganism
Electric current, space availability ratio are high；
4th, the electron transmission medium in the anode assembly that the present invention is prepared is bound in polymer lateral chain, avoids electricity
Son transmits secondary pollution caused by medium leakage, more environmentally-friendly and safe；
5. PMBVY-PVA gel rubber systems in the present invention can by adding in and removing sorbierite and invertible dissolution-gel, from
And realize and microorganism is replaced under the premise of electrode overall structure is not destroyed, the recycling of material is realized, is maintained easily.
Specific embodiment
Amine alkyl osmium bipyridine chlorate used in following embodiment is purchased from Sigma Aldrich, two cyclopentadienyl of hydroxyalkyl
Iron is purchased from Tokyo chemical conversion（TCI）.
Embodiment 1
A kind of the step of preparation method of the anode assembly of microbiological fuel cell, this method, is as follows：
（1）The preparation of monomer Y：By being dissolved in 10mmol methacrylic acids containing a concentration of 0.1mmol/L polymerization inhibitors
In dichloromethane, 0.1mol dicyclohexylcarbodiimides are added, stir 30min, then add in amine alkyl osmium bipyridine chlorination
Salt reacts 2h, is washed, and regathers organic phase and vacuum drying obtains monomer Y；
（2）The preparation of copolymer p MBVY：By 2- methylacryoyloxyethyls phosphocholine, 2- metering systems butyl ester, 4- second
Alkenyl phenyl boric acid and monomer Y are according to 5:2:1:2 molar ratio is dissolved in absolute ethyl alcohol, the solution of a concentration of 1mol/L is made, so
The azodiisobutyronitrile of 10mmol is added in afterwards, and solution is warming up to 60 DEG C under protection of argon gas and reacts 48h, reaction product is existed
0.1:0.9 chloroform/ether in the mixed solvent precipitates and collects solid product, then solid product is dissolved in deionized water and is depressurized
To get copolymer p MBVY after distillation, copolymer p MBVY is dissolved in deionized water and is evaporated under reduced pressure removing organic solvent；
（3）Surface is covered with the preparation of the electrode of graphite fibre：In the poly- of the graphite rod surface of a diameter of 0.5cm coating 1mm
Acrylonitrile is pre-sintered to polyacrylonitrile carbonization, and then be transferred in electric arc furnaces and be sintered 2h at 2400 DEG C for 600 DEG C in Muffle furnace, makes
The polyacrylonitrile fibre graphitization of carbonization is covered with the electrode of graphite fibre to get surface；
（4）The preparation of anode assembly：1）Copolymer p MBVY and the culture solution for being loaded with Shewanella are mixed, copolymer
The mass percent of PMBVY is 5%, obtains component I；2）Polyvinyl alcohol is mixed with aseptic culture fluid, the quality hundred of polyvinyl alcohol
Divide than being 5%, obtain component II；3）The electrode that surface is covered with to graphite fibre is put into mold, sequentially adds isometric component
I and component II, swing die are uniformly mixed two kinds of components, stand 15 minutes and treat gel solidification；4）Mold is sloughed, by 3）Middle place
Electrode after reason is with electrode plate, substrate, screen packs to get the anode assembly of microbiological fuel cell.
Embodiment 2
A kind of the step of preparation method of the anode assembly of microbiological fuel cell, this method, is as follows：
（1）The preparation of monomer Y：By being dissolved in 10mmol methacrylic chlorides containing a concentration of 0.1mmol/L polymerization inhibitors
Dichloromethane in, the triethylamine of 10mmol is added at 0 DEG C and the hydroxyalkyl ferrocene of 10mmol is added dropwise, reacts 4h,
It is washed, regather organic phase and is dried in vacuo with deionized water after filtering, washed and be dried to obtain monomer Y；
（2）The preparation of copolymer p MBVY：By 2- methylacryoyloxyethyls phosphocholine, 2- metering systems butyl ester, 4- second
Alkenyl phenyl boric acid and monomer Y are according to 5:2:1:2 molar ratio is dissolved in absolute ethyl alcohol, the solution of a concentration of 1mol/L is made, so
The azodiisobutyronitrile of 10mmol is added in afterwards, and solution is warming up to 60 DEG C under protection of argon gas and reacts 48h, reaction product is existed
0.1:0.9 chloroform/ether in the mixed solvent precipitates and collects solid product, then solid product is dissolved in deionized water and is depressurized
To get copolymer p MBVY after distillation；
（3）Surface is covered with the preparation of the electrode of graphite fibre：In the carboxylic first for the electrode dual coating 1mm that thickness is 0.5cm
Base cellulose is pre-sintered to carboxymethyl cellulose carbonization for 600 DEG C in Muffle furnace, and then is transferred in electric arc furnaces in 2400 DEG C of sintering
2h makes carbon fibre further be graphitized the electrode for being covered with graphite fibre to get surface；
（4）The preparation of anode assembly：1）Copolymer p MBVY and the culture solution for being loaded with Shewanella are mixed, copolymer
The mass percent of PMBVY is 5%, obtains component I；2）Polyvinyl alcohol is mixed with aseptic culture fluid, the quality hundred of polyvinyl alcohol
Divide than being 5%, obtain component II；3）The electrode that surface is covered with to graphite fibre is put into mold, sequentially adds isometric component
I and component II, swing die are uniformly mixed two kinds of components, stand 15 minutes and treat gel solidification；4）Mold is sloughed, by 3）Middle place
Electrode after reason is with electrode plate, substrate, screen packs to get the anode assembly of microbiological fuel cell.
In actual use, when using current reduction, anode assembly is taken out, mold is put into, adds in a mold
1mol sorbitol solutions stand 1h and are dissolved to gel, are centrifuged off microorganism.Ethyl alcohol is added in the solution collects polyethylene alcohol precipitation
It forms sediment, then solution is added in 1:In 9 chloroform/ether solvent, copolymer p MBVY precipitations are collected.Anode is completed in the operation for repeating 4-7
The replacement of microorganism in device.
Under conditions of embodiment 1, the Shewanella of strain concentration OD600=0.1 is encapsulated in gel electrode, is passed through breast
For sugar as organic substrates, the peak power output density measured after being connected with cathode is 58mW/ ㎡, is significantly better than other films
MFC。
The power density of battery is measured in experiment every 8h, the results are shown in table below, by the Shiva in 72 hours gels
Salmonella still maintains more than 75% survival rate, it was demonstrated that battery has good stability and persistence.
| Experimental period/h | 0 | 8 | 16 | 24 | 32 | 40 | 48 | 56 | 64 | 72 |
| Power density/mW/ ㎡ | 58.10 | 56.63 | 55.19 | 53.79 | 52.43 | 51.10 | 49.80 | 48.54 | 47.31 | 46.11 |
| Survival rate/% | 100 | 97.46 | 94.99 | 92.59 | 90.24 | 87.95 | 85.72 | 83.55 | 81.43 | 79.36 |
Claims (5)
1. a kind of preparation method of the anode assembly of microbiological fuel cell, it is characterised in that the step of this method is as follows：
（1）The preparation of monomer Y：By the way that 10mmol methacrylic acids are dissolved in the dichloro containing a concentration of 0 .1mmol/L polymerization inhibitors
In methane, 0 .1mol dicyclohexylcarbodiimides are added, stir 30min, then add in 10mmol amine alkyl osmium bipyridine chlorine
Salt dissolving is reacted 2h, is washed, and regathers organic phase and is dried in vacuo and obtains monomer Y or by by 10mmol metering systems
Acyl chlorides is dissolved in the dichloromethane containing a concentration of 0 .1mmol/L polymerization inhibitors, at 0 DEG C add in 10mmol triethylamine and by
The hydroxyalkyl ferrocene of 10mmol is added dropwise to, 4h is reacted, is washed after filtering with deionized water, regather organic phase and vacuum is done
It is dry, then wash and be dried to obtain monomer Y；
（2）The preparation of copolymer p MBVY：By 2- methylacryoyloxyethyls phosphocholine, 2- metering systems butyl ester, 4- vinyl
Phenyl boric acid and monomer Y are according to 5:2:1:2 molar ratio is dissolved in absolute ethyl alcohol, and the solution of a concentration of 1mol/L, Ran Houjia is made
Enter the azodiisobutyronitrile of 10mmol, solution is warming up to 60 DEG C under protection of argon gas and reacts 48h, by reaction product 0.1:
0.9 chloroform/ether in the mixed solvent precipitates and collects solid product, then solid product is dissolved in deionized water and is evaporated under reduced pressure
Afterwards to get copolymer p MBVY；
（3）Surface is covered with the preparation of the electrode of graphite fibre：On the graphite rod or graphite cake of diameter or thickness for 0 .5-1cm
The graphite fibre layer that thickness is 0 .5-1mm is prepared by high molecular material pyrolysis and sintering and is covered with graphite fibre to get surface
Electrode；
（4）The preparation of anode assembly：1）Copolymer p MBVY and the culture solution for being loaded with Shewanella are mixed, copolymer p MBVY's
Mass percent is 5%, obtains component I；2）Polyvinyl alcohol is mixed with aseptic culture fluid, the mass percent of polyvinyl alcohol is
5%, obtain component II；3）The electrode that surface is covered with to graphite fibre is put into mold, sequentially adds isometric component I and group
Divide II, swing die is uniformly mixed two kinds of components, stands 15 minutes and treats gel solidification；4）Mold is sloughed, by 3）After middle processing
Electrode and electrode plate, substrate, screen packs to get microbiological fuel cell anode assembly；
A kind of preparation method of the anode assembly of microbiological fuel cell, step（1）In amine alkyl osmium bipyridine
The chemical structural formula of chlorate is：
, wherein n=5-12.
2. a kind of preparation method of the anode assembly of microbiological fuel cell according to claim 1, it is characterised in that：Institute
State step（1）In hydroxyalkyl ferrocene chemical formula be HO-（CH2）N-Fc, wherein n=5-12.
3. a kind of preparation method of the anode assembly of microbiological fuel cell according to claim 1, it is characterised in that：The monomer Y
Chemical structural formula beOr,
Wherein n=5-12.
4. a kind of preparation method of the anode assembly of microbiological fuel cell according to claim 3, it is characterised in that：Institute
The chemical structural formula for stating copolymer p MBVY is：,
Wherein a=0.4-0.5, b=0.1-0.3, c=0.1-0.2, d=0.1-0.2.
5. a kind of preparation method of the anode assembly of microbiological fuel cell according to claim 1, it is characterised in that：Institute
State step（3）In high molecular material be polyacrylonitrile or carboxymethyl cellulose.
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| CN112897704A (en) * | 2020-12-04 | 2021-06-04 | 南京斯博伏特新材料有限公司 | Hydrogel microelectrode for sewage treatment |
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| JP2011222261A (en) * | 2010-04-08 | 2011-11-04 | Sony Corp | Biofuel cell |
| WO2013170217A2 (en) * | 2012-05-10 | 2013-11-14 | Synthetic Genomics, Inc. | Microbial fuel cell |
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