CN102881906A - Modification method of carbon-based material, and application thereof in microbial fuel cell - Google Patents
Modification method of carbon-based material, and application thereof in microbial fuel cell Download PDFInfo
- Publication number
- CN102881906A CN102881906A CN2012103827411A CN201210382741A CN102881906A CN 102881906 A CN102881906 A CN 102881906A CN 2012103827411 A CN2012103827411 A CN 2012103827411A CN 201210382741 A CN201210382741 A CN 201210382741A CN 102881906 A CN102881906 A CN 102881906A
- Authority
- CN
- China
- Prior art keywords
- carbon
- fuel cell
- based material
- electrode
- microbial fuel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a modification method of a carbon-based material, and an application thereof in a microbial fuel cell. The specific preparation method comprises the steps of performing surface modification on the carbon-based material by using strong reduction hydrazine hydrate; and changing the surface characteristic of the carbon-based material to obtain anodes of the microbial fuel cell. The obtained anodes of the microbial fuel cell are applied to the microbial fuel cell. Compared with an unmodified carbon-based electrode, the modification of the strong reduction hydrazine hydrate can enhance a specific surface area of an electrode material, is beneficial for microbial attachment, improves the peak current of the electrode material, simultaneously changes the surface groups of the electrode, enhances the biocompatibility of the electrode, and increases electron transfer efficiency, so that the electricity production power of the electrode can be greatly increased. Compared with other anode modification methods, the method of performing surface modification on the carbon-based material by using strong reduction hydrazine hydrate is simple and practicable, has low preparation cost, and is helpful for popularized applications in the microbial fuel cell.
Description
Technical field
The invention belongs to new forms of energy and field of environment engineering technology, be specifically related to carbon-based anode material surface modification method and the application in microbiological fuel cell thereof.
Background technology
The problems such as the energy crisis that the use of non-renewable fossil fuel causes, environmental pollution are increasingly serious, seek the extensive concern that renewable green novel energy source more and more is subject to countries in the world.Microbiological fuel cell (MFC) technology can be converted into electric energy with the chemical energy in the organic substance under the catalytic action of microbe.It has can utilize that substrate is extensive, operating condition is simple, the collection pollutant processes and electric energy is recovered as the plurality of advantages such as one, is one of current field of environment engineering study hotspot.But it is still lower to study the power density that microbiological fuel cell so far obtains, and has limited further developing and using of it.
Anode is participated in the metabolic activity of microbe-catalytic oxidization fuel directly, affects electronics transmission efficiency between microbe and the electrode, and its surface nature affects electrogenesis microbial growth density, and then the MFC electrogenesis is measured Main Function.In view of anode material on the vital impact of MFC electricity generation performance, for further improving the MFC power stage, select suitable anode material, it is carried out the surface modified of physics or chemistry, study simultaneously its surface topography and functional group and change the impact that biological attachment, compatibility and electronics are transmitted, the electricity generation performance tool that improves MFC is of great significance.
Chemical modification method is a kind of cheapness and effective surface modifying method.For example, (the J.PowerSources such as Feng, 2010,195:1841-1844) use the acid soak method, heating means or the method that both combine are carried out surface modification to the carbon fiber brush, so that carbon fiber brush specific area increases, material surface N1s/C1s ratio obviously raises, the C-O constituent content descends, and infers that nitrogen-containing functional group is conducive to the anode electron transfer process, and the simultaneously decline of C-O content also impels the raising of microbiological fuel cell power density.Hydrazine hydrate is a kind of strong reductant, in industry, be widely used, cheap, non-secondary pollution, utilize the hydrazine hydrate modification to the carbon-based material surface chemical modification, study the improvement of its Surface Physical Chemistry environment, chemical property and the application in anode of microbial fuel cell and rarely have report.Because carbon-based material has the character such as conductivity, chemical stability, biocompatibility, therefore, can utilize through the carbon-based material of the strong reducing property hydrazine hydrate modification anode material as microbiological fuel cell.
Summary of the invention
The object of the invention is to provide a kind of method of modifying of carbon-based material, its purpose is to improve microbiological fuel cell electrogenesis power, improve the possibility that microbiological fuel cell is used in practice, for the exploitation of electrode of microbial fuel cell provides a kind of new thinking.Main contents of the present invention are as follows:
A kind of method of modifying of carbon-based material, described method of modifying comprise take carbon-based material as matrix, utilize the hydrazine hydrate of strong reducing property that carbon-based material is carried out finishing, prepare a kind of anode material of modification; It is characterized in that said method comprising the steps of:
(1) carbon-based material is immersed in carries out preliminary treatment in the acetone soln, soak time is 12～24h, cleans up with deionized water after taking out, and is positioned over and carries out drying processing in 105 ℃ of baking ovens, obtains dried carbon-based material;
(2) carbon-based material that obtains in the step (1) is impregnated in 20%～50% hydrazine hydrate ethanolic solution, 50～90 ℃ of heating water bath 4～8h obtain the carbon-based material of water bath processing;
(3) carbon-based material that obtains in the step (2) is taken out, put into 105 ℃ of oven dry of baking oven, namely obtain described Surface Modified Electrodes material.
Described carbon-based material is carbon cloth, carbon paper, carbon cloth or carbon felt.
The application of anode modification material in microbiological fuel cell that the method for modifying of above-mentioned a kind of carbon-based material obtains, take the single chamber air cathode microbial fuel cell as research object, the anode take described anode material as microbiological fuel cell.
It is as follows that the present invention verifies that strong reducing property hydrazine hydrate modified carbon fiber cloth material is applied to the process of anode of microbial fuel cell:
One, the sign of carbon fiber cloth material
Respectively the carbon cloth anode material before and after modifying is carried out the SEM test, observe the change of material surface pattern; Respectively the carbon cloth anode material before and after modifying is carried out electro-chemical test (CV), contrast chemical property difference; Redox is carried out the XPS characterization test to the carbon cloth anode material before and after modifying respectively, and analyzes the variation of its surface-element and functional group.
Two, the assembling of microbiological fuel cell and startup
The anode material that utilizes the manner to obtain is assembled the method for microbiological fuel cell and is carried out according to the following steps: the anode place that the anode material after the modification is mounted to microbiological fuel cell, negative electrode is for carrying the platinum air cathode, negative electrode cover plate, anode cover plate and battery cavity are connected, and fix with bolt.Derive anode and cathode with the titanium silk, data acquisition unit is connected to the external resistance two ends, and output voltage is recorded in the computer automatically.Namely finish the assembling of microbiological fuel cell.
In the start-up course, nutrient solution mixes according to a certain percentage with glucose, anaerobic sludge, phosphate buffer, slaine and vitamin and is added in the single-chamber microbial fuel cell, change matrix every day, until continuous two periodic battery maximum output voltages are basically identical.
Three, the electricity generation performance of microbiological fuel cell test
After microbiological fuel cell starts successfully, move continuously a plurality of cycles, monitoring output voltage and the relation of time, the electrogenesis of investigating the modified anode material is stable; Change the external resistance size when the microbiological fuel cell electricity generation ability is best, the variation of record output voltage obtains polarization curve and the power density curve of microbiological fuel cell; Measure the variation of cycle of operation Inlet and outlet water COD, calculate again the coulombic efficiency of microbiological fuel cell according to the electrogenesis amount.
The carbon fiber cloth material that the inventive method is modified, its specific area increases, the surface nitrogen-containing functional group increases, be beneficial to adhering to and the migration of electronics between microbe and electrode of electrogenesis microbe, it can be improved the electricity generation performance of microbiological fuel cell greatly as the anode of microbiological fuel cell.This inventive method is simple, and is workable, successful.The selected materials good biocompatibility has no adverse effects to the electrogenesis microbe.The electrode material that obtains can be widely used in the microbiological fuel cell field.
Description of drawings
Fig. 1 is that the SEM figure of the carbon fiber cloth electrode before and after modifying compares;
Fig. 2 is that the XPS element of the carbon fiber cloth electrode before and after modifying forms;
Fig. 3 is that the CV figure of the carbon fiber cloth electrode before and after modifying compares;
Fig. 4 is the electricity generation performance contrast of carbon fiber cloth electrode in MFC before and after modifying;
CM represents the carbon fiber cloth electrode of unmodified among the figure, and CM-30% represents the carbon fiber cloth electrode that hydrazine hydrate is modified.
Embodiment
Further describe the present invention below in conjunction with drawings and Examples, its purpose is to understand better content of the present invention, rather than limits the scope of the invention.
Embodiment 1
The first step: preparation and the sign of hydrazine hydrate modifying carbon fibers cloth material
The method of modifying of anode of microbial fuel cell material among the present invention, realize by following steps: (1) is immersed in carbon-based material and carries out preliminary treatment in the acetone soln, soak time is 12h, taking-up cleans up with deionized water, be positioned over and carry out the drying processing in 105 ℃ of baking ovens, obtain dried carbon-based material; (2) carbon-based material that obtains in the step (1) is impregnated in the 30% hydrazine hydrate ethanolic solution, 60 ℃ of heating water bath 6h obtain the carbon-based material of water bath processing; (3) carbon-based material that obtains in the step (2) is taken out, put into 105 ℃ of oven dry of baking oven, namely obtain described Surface Modified Electrodes material.
The SEM figure of the modifying carbon fibers cloth electrode material that this method obtains as can be seen from the figure modifies rear carbon fiber cloth material and compares with unmodified carbon fiber cloth material as shown in Figure 1, its surperficial gully showed increased, and the material specific area increases.Before and after modifying electrode material XPS characterization data as shown in Figure 2, carbon fiber cloth material nitrogen content showed increased after modifying, protonated nitrogen and the tertiary amine of surface functional group when unmodified changes quaternary nitrogen and pyrazoline group into, carbon oxygen singly-bound content reduces simultaneously.These all are beneficial to attached growth of microorganisms and electronics transmission.Test in (seeing Fig. 3) at CV through the carbon fiber cloth electrode of modifying, its peak current illustrates that obviously greater than not modified electrode the chemical property of the carbon fiber cloth electrode that process is modified is enhanced.
Second step: the assembling of microbiological fuel cell and startup
Anode of microbial fuel cell and air cathode are mounted to respectively the two ends of battery cavity, negative electrode cover plate, anode cover plate and battery cavity are connected, and fix with bolt.Derive anode and cathode with the titanium silk, and in external circuit, connect 1000O resistance.Data acquisition unit is connected to the resistance two ends, and output voltage is recorded in the computer automatically.The anode seed sludge pick up from certain sludge of sewage treatment plant concentrated between.
In the start-up course, the matrix that anolyte adopts is the 50mM phosphate buffer of glucose, adds 1.00g glucose, 12.5mL slaine, 5mL vitamin in the 1L buffer solution.Anolyte and anaerobic sludge are according to 3～4: 1 volume ratio is added in the reactor, changes water inlet every day until start successfully.
The 3rd step: electricity generation performance of microbial fuel cell test
The electrode material that obtains before and after modifying contrasts as shown in Figure 4 as the electricity generation performance that anode is applied to obtain in the microbiological fuel cell.As can be seen from Figure 4, the electrogenesis cycle that makes microbiological fuel cell through the anode material behind the hydrazine hydrate modification, the 17h when using the unmodified anode extended to 24h, and maximum output voltage has improved 26mV.Obtain by the polarization curve of measuring MFC, the maximum power density of unmodified anode microbiological fuel cell is 662mW/m
2, be 865mW/m and adopt the maximum power density of the microbiological fuel cell of modified anode
2, improved 30.7%; The hydrazine hydrate modified anode makes the MFC internal resistance be reduced to 176O by 231O.Adopting the coulombic efficiency of the microbiological fuel cell of modified anode is 13.3%, has improved 24.3% than unmodified anode microbiological fuel cell (10.7%).This shows, compare with unmodified anode microbiological fuel cell, the modified anode that this method obtains is applied to improve in the microbiological fuel cell the whole electricity generation performance of battery.
Claims (3)
1. the surface modification method of a carbon-based material is characterized in that said method comprising the steps of:
(1) carbon-based material is immersed in carries out preliminary treatment in the acetone soln, soak time is 12～24h, takes out to clean up with deionized water, is positioned over to carry out drying processing in 105 ℃ of baking ovens, obtains dried carbon-based material;
(2) carbon-based material that obtains in the step (1) is impregnated in 20%～50% hydrazine hydrate ethanolic solution, 50～90 ℃ of heating water bath 4～8h obtain the carbon-based material of water bath processing;
(3) carbon-based material that obtains in the step (2) is taken out, put into 105 ℃ of oven dry of baking oven, namely obtain described Surface Modified Electrodes material.
2. method according to claim 1 is characterized in that described carbon-based material is carbon cloth, carbon paper, carbon cloth, carbon felt or reticulated vitreous carbon.
3. the application of Surface Modified Electrodes material in microbiological fuel cell that obtain of method according to claim 1 is characterized in that the anode take described electrode material as microbiological fuel cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103827411A CN102881906A (en) | 2012-10-11 | 2012-10-11 | Modification method of carbon-based material, and application thereof in microbial fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103827411A CN102881906A (en) | 2012-10-11 | 2012-10-11 | Modification method of carbon-based material, and application thereof in microbial fuel cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102881906A true CN102881906A (en) | 2013-01-16 |
Family
ID=47483154
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012103827411A Pending CN102881906A (en) | 2012-10-11 | 2012-10-11 | Modification method of carbon-based material, and application thereof in microbial fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102881906A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103354291A (en) * | 2013-06-21 | 2013-10-16 | 浙江大学 | Microbial fuel cell anode processing method suitable for large scale application |
| CN104485461A (en) * | 2014-11-03 | 2015-04-01 | 刘奇 | Low-cost functionalized carbon felt preparation method |
| CN107887615A (en) * | 2017-11-07 | 2018-04-06 | 哈尔滨工业大学 | The preprocess method of microorganism electrochemical system carbon-based electrode material |
| CN113371957A (en) * | 2021-05-13 | 2021-09-10 | 西北矿冶研究院 | Method for treating excess sludge based on microbial electrolysis cell |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110048962A1 (en) * | 2009-08-27 | 2011-03-03 | Sun Catalytix Corporation | Compositions, electrodes, methods, and systems for water electrolysis and other electrochemical techniques |
-
2012
- 2012-10-11 CN CN2012103827411A patent/CN102881906A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110048962A1 (en) * | 2009-08-27 | 2011-03-03 | Sun Catalytix Corporation | Compositions, electrodes, methods, and systems for water electrolysis and other electrochemical techniques |
Non-Patent Citations (1)
| Title |
|---|
| TAO JIN, ET AL: "Coupling of anodic and cathodic modification for increased power generation in microbial fuel cells", 《JOURNAL OF POWER SOURCES》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103354291A (en) * | 2013-06-21 | 2013-10-16 | 浙江大学 | Microbial fuel cell anode processing method suitable for large scale application |
| CN104485461A (en) * | 2014-11-03 | 2015-04-01 | 刘奇 | Low-cost functionalized carbon felt preparation method |
| CN107887615A (en) * | 2017-11-07 | 2018-04-06 | 哈尔滨工业大学 | The preprocess method of microorganism electrochemical system carbon-based electrode material |
| CN113371957A (en) * | 2021-05-13 | 2021-09-10 | 西北矿冶研究院 | Method for treating excess sludge based on microbial electrolysis cell |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| He et al. | Mn3O4 anchored on carbon nanotubes as an electrode reaction catalyst of V (IV)/V (V) couple for vanadium redox flow batteries | |
| CN104141147B (en) | Microbiological fuel cell self-driven microorganism electrolysis cell hydrogen-preparing hydrogen-storing method | |
| CN103426649B (en) | The preparation method of different carbon fiber/cobalt hydroxide electrodes and solid-liquid composite electrode system | |
| CN103367766B (en) | The preparation method of graphene/ conductive polymer anode for microbial fuel cell | |
| CN102780010A (en) | Preparation method of composite anode of microbial fuel cell with carbon-base material modified by conductive complex | |
| CN106207239A (en) | The synthetic method of a kind of N doping porous carbon and the application in terms of anode of microbial fuel cell thereof | |
| CN105140528B (en) | A kind of auto-dope anode of microbial fuel cell material and preparation method thereof | |
| CN106941179A (en) | A kind of preparation of graphene Polyaniline-modified carbon cloth electrode material and the method for accelerating biological anode domestication | |
| Liu et al. | Improved microbial fuel cell performance by encapsulating microbial cells with a nickel-coated sponge | |
| CN106450397B (en) | A kind of preparation method of nitrogen-doped graphene electrode material | |
| CN108821257A (en) | A kind of binary based on lotus leaf is mesoporous-micropore multilevel structure biological carbon and its preparation method and application | |
| CN107706428B (en) | Polyaniline nanoflower modified carbon cloth electrode and preparation method and application thereof | |
| CN105609796B (en) | The method of modifying of electrode material for all-vanadium flow battery | |
| Liu et al. | Enhanced performance of microbial fuel cell using carbon microspheres modified graphite anode | |
| CN107732256A (en) | One kind prepares MFC electrode materials and its chemical property using agricultural wastes | |
| CN102881906A (en) | Modification method of carbon-based material, and application thereof in microbial fuel cell | |
| CN109457269A (en) | A kind of MoS2/ graphene-foam nickel cathode preparation method and its application in microorganism electrolysis cell | |
| CN106025296A (en) | Nitrogen-phosphorus double-doped carbon material as well as preparation method and application thereof | |
| CN102208660B (en) | Preparation method of cathode material and application of cathode material in microbial fuel cell | |
| CN103872347A (en) | Preparation method of porous nanofiber-based anode film of microbial fuel battery | |
| CN105845959A (en) | Microbial fuel cell for sewage water degradation | |
| CN104716343B (en) | A kind of high-performance is combined carbon felt | |
| CN103762371B (en) | The carbon foam catalysis electrode system of a kind of MBR and MFC that is coupled | |
| CN109879283A (en) | A kind of preparation method of biomass porous carbon material and its application in anode of microbial fuel cell | |
| CN104810528B (en) | Application of the LiMn2O4 to the surface modification method of carbon material and its in microbiological fuel cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130116 |