CN107799797A - A kind of anode of microbial fuel cell and preparation method thereof - Google Patents
A kind of anode of microbial fuel cell and preparation method thereof Download PDFInfo
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- CN107799797A CN107799797A CN201710846907.3A CN201710846907A CN107799797A CN 107799797 A CN107799797 A CN 107799797A CN 201710846907 A CN201710846907 A CN 201710846907A CN 107799797 A CN107799797 A CN 107799797A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- B82—NANOTECHNOLOGY
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
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- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8846—Impregnation
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
- H01M4/8885—Sintering or firing
- H01M4/8889—Cosintering or cofiring of a catalytic active layer with another type of layer
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- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8892—Impregnation or coating of the catalyst layer, e.g. by an ionomer
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- H01M4/00—Electrodes
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- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
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- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8684—Negative electrodes
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention belongs to microbiological fuel cell field, discloses a kind of anode of microbial fuel cell and preparation method thereof.The anode of microbial fuel cell is made up of carbon carrier, catalyst and conducting polymer；The catalyst is at least one of manganese oxide, zinc oxide, tungsten oxide and molybdenum dioxide.Compound containing manganese, zinc, tungsten or molybdenum is added to stirring and dissolving in hydrochloric acid, PH=2~3 of oxalic acid and ammonium sulfate regulation solution is then added, carbon carrier is added in above-mentioned solution, 150 250 DEG C of 10 20h of reaction are heated to after supersound process；Reaction is completed after air atmosphere and 400~500 DEG C of 1~3h of temperature lower calcination, is then added in the monomer solution of conducting polymer, is prepared conducting polymer on the carbon carrier of supported catalyst by being electrodeposited in, obtain the anode of microbial fuel cell.
Description
Technical field
The invention belongs to microbiological fuel cell field, and in particular to a kind of anode of microbial fuel cell and its preparation side
Method.
Background technology
Microbiological fuel cell (MFC) is microbiological oxidation organic matter release electronics, and by electron transmission to external circuit shape
A kind of chemical energy into loop is converted to the new device of electric energy.Based on such a electro-chemical systems, while pollutant is handled
And can produces electric energy, it is considered to be a kind of green environmental protection technique, causes everybody widely to pay close attention in fields such as the energy, environment.But
Because its caused power density is relatively low compared to other fuel cells, its industrialized development is also limited.How to carry
High power density is a major challenge of microbiological fuel cell now.Anode decides the adhesion amount of bacterium, but also is related to
Transmission between electronics and electrode.Therefore, anode is most important to the power density for improving whole battery.Selection tool is potential
Anode modification material, influence of the parsing anode surface characteristic to microorganism electricity generation characteristic, the production to improving microbiological fuel cell
Electric energy power has important theory significance and application value.
The content of the invention
In place of shortcoming and defect existing for above prior art, primary and foremost purpose of the invention is to provide a kind of micro- life
Thing anode of fuel cell.
Another object of the present invention is to provide the preparation method of microorganism fuel cell anode.
The object of the invention is achieved through the following technical solutions：
A kind of anode of microbial fuel cell, it is made up of carbon carrier, catalyst and conducting polymer；The catalyst is oxygen
Change at least one of manganese, zinc oxide, tungsten oxide and molybdenum oxide.
Preferably, the carbon carrier is one kind in carbon felt and carbon cloth.
Preferably, the conducting polymer is at least one of polypyrrole, polyaniline and poly- 3,4-rthylene dioxythiophene.
The preparation method of microorganism fuel cell anode, including following preparation process：
(1) compound containing manganese, zinc, tungsten or molybdenum is added to stirring and dissolving in hydrochloric acid, then adds oxalic acid and ammonium sulfate
PH=2~3 of solution are adjusted, obtain mixed solution；
(2) carbon carrier is added in mixed solution obtained by step (1), 150-250 DEG C of reaction is heated to after supersound process
10-20h；Carbon carrier is taken out after the completion of reaction, clean, dry after air atmosphere and 400~500 DEG C of temperature lower calcinations 1~
3h, obtain the carbon carrier of supported catalyst；
(3) carbon carrier of supported catalyst obtained by step (2) is added in the monomer solution of conducting polymer, passes through electricity
It is deposited on the carbon carrier of supported catalyst and prepares conducting polymer, obtains the anode of microbial fuel cell.
Preferably, the concentration of hydrochloric acid described in step (1) is 1~2mol/L.
Preferably, cleaning refers to be cleaned with deionized water described in step (2), and the drying refers in 60~80 DEG C of temperature
Lower drying.
Preferably, the monomer solution of conducting polymer refers to chromium solution, aniline solution and 3,4- second described in step (3)
At least one of alkene dioxy thiophene solution；The mass concentration of the monomer solution of conducting polymer is 0.5%~5%.
Preferably, the condition of electro-deposition is described in step (3)：It is to electricity by reference electrode, platinum electrode of calomel electrode
Pole and carbon carrier are that working electrode forms a battery, and speed is swept from 0V to 0.6V with 10mV/s.
The present invention principle be：Pass through the attachment of manganese oxide, zinc oxide, tungsten oxide and molybdenum dioxide so that electrode has
Larger specific surface area, and be advantageous to the transmission of electronics and be advantageous to bacterium be attached to its surface formed biomembrane, have
Beneficial to the growth of microorganism.Meanwhile the deposition of conducting polymer is advantageous to the transmission of electronics.So as to improve Microbial fuel electricity
The power density in pond.
The present invention preparation method and resulting anode of microbial fuel cell has the following advantages that and beneficial effect：
(1) the axial homoepitaxial of manganese oxide, zinc oxide, tungsten oxide and molybdenum dioxide nano wire along carbon carrier fiber.
So surface topography has larger specific surface area, and is advantageous to the transmission of electronics and be advantageous to bacterium is attached to its table
Face forms biomembrane.Also, in electro-deposition conducting polymer above, the electric conductivity of electrode can be improved, has ensured the fast of electronics
Speed is transmitted.
(2) electrode for adhering to manganese oxide, zinc oxide, tungsten oxide and molybdenum dioxide nano wire has compared to blank carbon carrier
Good hydrophily.Preferable hydrophilic material is advantageous to the formation of biomembrane, so as to improve the defeated of microbiological fuel cell
Go out power.
Brief description of the drawings
Fig. 1 is the scanning of the final gained anode of microbial fuel cell (b) of the embodiment of the present invention 1 and unmodified carbon felt (a)
Electron microscope.
Fig. 2 is to be used as the micro- of working electrode using the gained anode of microbial fuel cell of embodiment 1 and unmodified carbon felt respectively
The power density curve map of biological fuel cell.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Embodiment 1
The preparation method of the anode of microbial fuel cell of the present embodiment, specific preparation process are as follows：
(1) 2.5g sodium tungstates are added in 1mol/L hydrochloric acid and stir 2h dissolvings, then added oxalic acid and ammonium sulfate is adjusted
The PH=2 of solution is saved, obtains mixed solution；
(2) carbon felt is added in mixed solution obtained by step (1), 150 DEG C of reaction 20h is heated to after being ultrasonically treated 2h；
Carbon felt is taken out after the completion of reaction, cleaned with deionized water, 80 DEG C of dryings after air atmosphere and 500 DEG C of temperature lower calcination 1h,
Obtain loading the carbon felt of tungsten oxide；
(3) carbon felt of load tungsten oxide obtained by step (2) is added in the chromium solution that mass concentration is 5%, passed through
It is electrodeposited in the carbon felt of load tungsten oxide and prepares conducting polymer (condition of electro-deposition is：Using calomel electrode as reference electrode,
It is that working electrode forms a battery to electrode and carbon carrier that platinum electrode, which is, and speed is swept from 0V to 0.6V with 10mV/s), obtain institute
State anode of microbial fuel cell.
Scanning electron microscope (SEM) photograph such as Fig. 1 of the final gained anode of microbial fuel cell (b) of the present embodiment and unmodified carbon felt (a)
It is shown.As seen from Figure 1, present invention gained anode of microbial fuel cell has big ratio surface.
Embodiment 2
The preparation method of the anode of microbial fuel cell of the present embodiment, specific preparation process are as follows：
(1) 4g sodium manganates are added in 2mol/L hydrochloric acid and stir 1h dissolvings, then add oxalic acid and ammonium sulfate regulation
The PH=3 of solution, obtains mixed solution；
(2) carbon cloth is added in mixed solution obtained by step (1), 250 DEG C of reaction 10h is heated to after being ultrasonically treated 1h；
Carbon carrier is taken out after the completion of reaction, cleaned with deionized water, 60 DEG C of dryings are after air atmosphere and 400 DEG C of temperature lower calcinations
3h, obtain loading the carbon cloth of manganese oxide；
(3) carbon cloth of load manganese oxide obtained by step (2) is added in the aniline solution that mass concentration is 0.5%, led to
Cross to be electrodeposited on the carbon cloth of load manganese oxide and prepare conducting polymer (condition of electro-deposition is：Using calomel electrode as reference electricity
It is that working electrode forms a battery to electrode and carbon carrier that pole, platinum electrode, which are, and speed is swept from 0V to 0.6V with 10mV/s), obtain
To the anode of microbial fuel cell.
Embodiment 3
The preparation method of the anode of microbial fuel cell of the present embodiment, specific preparation process are as follows：
(1) 4g sodium zincates are added in 1.5mol/L hydrochloric acid and stir 1h dissolvings, then added oxalic acid and ammonium sulfate is adjusted
The PH=2.5 of solution is saved, obtains mixed solution；
(2) carbon cloth is added in mixed solution obtained by step (1), 180 DEG C of reaction 16h is heated to after being ultrasonically treated 1h；
Carbon carrier is taken out after the completion of reaction, cleaned with deionized water, 70 DEG C of dryings are after air atmosphere and 400 DEG C of temperature lower calcinations
1h, obtain loading the carbon cloth of zinc oxide；
(3) carbon cloth of load zinc oxide obtained by step (2) is added to the 3,4- ethene dioxythiophenes that mass concentration is 2%
In solution, prepare conducting polymer by being electrodeposited on the carbon cloth of load zinc oxide (condition of electro-deposition is：With calomel electrode
For reference electrode, platinum electrode be to electrode and carbon carrier working electrode formed a battery, with 10mV/s sweep speed from 0V to
0.6V), the anode of microbial fuel cell is obtained.
Embodiment 4
The preparation method of the anode of microbial fuel cell of the present embodiment, specific preparation process are as follows：
(1) 4g sodium molybdates are added in 2mol/L hydrochloric acid and stir 1h dissolvings, then add oxalic acid and ammonium sulfate regulation
The PH=3 of solution, obtains mixed solution；
(2) carbon cloth is added in mixed solution obtained by step (1), 250 DEG C of reaction 16h is heated to after being ultrasonically treated 1h；
Carbon cloth is taken out after the completion of reaction, cleaned with deionized water, 60 DEG C of dryings after air atmosphere and 450 DEG C of temperature lower calcination 2h,
Obtain loading the carbon cloth of molybdenum oxide；
(3) carbon cloth of load molybdenum oxide obtained by step (2) is added in the chromium solution that mass concentration is 3%, passed through
It is electrodeposited on the carbon cloth of load molybdenum oxide and prepares conducting polymer (condition of electro-deposition is：Using calomel electrode as reference electrode,
It is that working electrode forms a battery to electrode and carbon carrier that platinum electrode, which is, and speed is swept from 0V to 0.6V with 10mV/s), obtain institute
State anode of microbial fuel cell.
Electrochemical property test is carried out to the anode of microbial fuel cell of nitrogen modification obtained by the present invention, test condition is such as
Under：
Used by this experiment electro-chemical test Solartron 1480 (Solartron Analytical,
England) carried out on electrochemical workstation.Made respectively with the gained anode of microbial fuel cell of embodiment 1 and unmodified carbon felt
For working electrode.
Power polarization test：Power output is to be drawn by testing the polarization curve of battery with linear voltammetric scan method
, sweep speed 10mVs-1, scanning range is from open circuit 0V to reference 0V.Equally often carry out once linear volt-ampere and sweep test,
Battery all needs first to place 3 days, to obtain stable power output.When finally calculating the power density of battery, the area of electrode is adopted
It is projected area.The polarization curve and power density curve of gained microbiological fuel cell are as shown in Figure 2.By Fig. 2 results
As can be seen that the maximum power density of present invention gained anode of microbial fuel cell is much larger than unmodified carbon felt.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (8)
- A kind of 1. anode of microbial fuel cell, it is characterised in that：It is made up of carbon carrier, catalyst and conducting polymer；It is described Catalyst is at least one of manganese oxide, zinc oxide, tungsten oxide and molybdenum oxide.
- A kind of 2. anode of microbial fuel cell according to claim 1, it is characterised in that：The carbon carrier be carbon felt and One kind in carbon cloth.
- A kind of 3. anode of microbial fuel cell according to claim 1, it is characterised in that：The conducting polymer is poly- At least one of pyrroles, polyaniline and poly- 3,4- ethene dioxythiophenes.
- A kind of 4. preparation method of anode of microbial fuel cell described in any one of claims 1 to 3, it is characterised in that including Following preparation process：(1) compound containing manganese, zinc, tungsten or molybdenum is added to stirring and dissolving in hydrochloric acid, then adds oxalic acid and ammonium sulfate regulation PH=2~3 of solution, obtain mixed solution；(2) carbon carrier is added in mixed solution obtained by step (1), 150-250 DEG C of reaction 10- is heated to after supersound process 20h；Carbon carrier is taken out after the completion of reaction, cleans, dry after air atmosphere and 400~500 DEG C of 1~3h of temperature lower calcination, Obtain the carbon carrier of supported catalyst；(3) carbon carrier of supported catalyst obtained by step (2) is added in the monomer solution of conducting polymer, passes through electro-deposition Conducting polymer is prepared on the carbon carrier of supported catalyst, obtains the anode of microbial fuel cell.
- A kind of 5. preparation method of anode of microbial fuel cell according to claim 4, it is characterised in that：Step (1) Described in the concentration of hydrochloric acid be 1~2mol/L.
- A kind of 6. preparation method of anode of microbial fuel cell according to claim 4, it is characterised in that：Step (2) Described in cleaning refer to be cleaned with deionized water, the drying refer at a temperature of 60~80 DEG C dry.
- A kind of 7. preparation method of anode of microbial fuel cell according to claim 4, it is characterised in that：Step (3) Described in the monomer solution of conducting polymer refer in chromium solution, aniline solution and 3,4- ethene dioxythiophene solution at least It is a kind of；The mass concentration of the monomer solution of conducting polymer is 0.5%~5%.
- A kind of 8. preparation method of anode of microbial fuel cell according to claim 4, it is characterised in that：Step (3) Described in the condition of electro-deposition be：It is working electrode shape to electrode and carbon carrier to be as reference electrode, platinum electrode using calomel electrode Into a battery, speed is swept from 0V to 0.6V with 10mV/s.
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| CN201710846907.3A CN107799797A (en) | 2017-09-19 | 2017-09-19 | A kind of anode of microbial fuel cell and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108832146A (en) * | 2018-05-30 | 2018-11-16 | 青岛科技大学 | A kind of preparation method of porous carbon bioelectrode |
| CN109216714A (en) * | 2018-07-24 | 2019-01-15 | 南京航空航天大学 | WO3/NiCo2O4/ carbon cloth combination electrode and its preparation method and application |
| CN113422074A (en) * | 2021-06-24 | 2021-09-21 | 焦作大学 | Pretreatment method of carbon-based electrode material of electrochemical system |
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| CN1592979A (en) * | 2001-09-21 | 2005-03-09 | 纳幕尔杜邦公司 | Anode electrocatalysts for coated substrates used in fuel cells |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108832146A (en) * | 2018-05-30 | 2018-11-16 | 青岛科技大学 | A kind of preparation method of porous carbon bioelectrode |
| CN108832146B (en) * | 2018-05-30 | 2021-01-29 | 青岛科技大学 | Preparation method of porous carbon bioelectrode |
| CN109216714A (en) * | 2018-07-24 | 2019-01-15 | 南京航空航天大学 | WO3/NiCo2O4/ carbon cloth combination electrode and its preparation method and application |
| CN109216714B (en) * | 2018-07-24 | 2021-06-15 | 南京航空航天大学 | WO3/NiCo2O4/carbon cloth composite electrode and preparation method and application thereof |
| CN113422074A (en) * | 2021-06-24 | 2021-09-21 | 焦作大学 | Pretreatment method of carbon-based electrode material of electrochemical system |
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