CN106532076A - Graphite felt electrode for microbial fuel cell - Google Patents
Graphite felt electrode for microbial fuel cell Download PDFInfo
- Publication number
- CN106532076A CN106532076A CN201611209678.6A CN201611209678A CN106532076A CN 106532076 A CN106532076 A CN 106532076A CN 201611209678 A CN201611209678 A CN 201611209678A CN 106532076 A CN106532076 A CN 106532076A
- Authority
- CN
- China
- Prior art keywords
- graphite felt
- electrode
- polyaniline
- fuel cell
- sulfonated polyaniline
- 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
Classifications
-
- 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
- H01M4/96—Carbon-based electrodes
-
- 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
-
- 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
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Microbiology (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention discloses a sPANI modified graphite felt electrode for a microbial fuel cell and a preparation method thereof. The sPANI modified graphite felt electrode is prepared as follows: polyaniline is sulphonated so as to obtain sulphonated polyaniline, the sulphonated polyaniline is soaked and undergoes ultrasonic treatment by using PVDF at normal temperature, and then the sulphonated polyaniline is loaded on the surface of a graphite felt carrier by using a drying and bonding method so as to prepare the graphite felt electrode. Through adoption of the method preparing the graphite felt electrode, on the one hand, the specific surface area of the electrode is improved, on the other hand, the surface of the sulphonated polyaniline contains nitrogen-containing functional groups and sulfonic acid groups, so that microorganism can grow well, electrode hydrophilia is improved, and ohm impedance of the MFC is lowered remarkably. The graphite felt electrode prepared by the method has good electricity production performance and strong dynamics activity in the MFC.
Description
Technical field
The present invention relates to microbiological fuel cell field, and in particular to a kind of modified graphite felt electrode material.
Background technology
Microbiological fuel cell (MFC) is a kind of metabolism degraded organic pollutants of utilization microorganism, while
The device of electric energy is produced, is received significant attention in water pollution control and resource field at present.Anode is electricity-producing microorganism in MFC
The carrier of attachment, also plays a part of electronics conduction, is to affect one of key factor of MFC electricity generation performances.At present graphite felt because
With high conductivity, high-specific surface area, lower-price characteristic, in fields such as quasiconductor, metallurgy, fiber manufacturing, ceramic industries
It is used widely, and is extensively introduced in the research of MFC electrode materials, but graphite felt surface energy state is high, electron transition is arrived
On electrode, energy barrier is higher, shows higher anode activation overpotential, and secondly graphite felt hydrophilic is poor, is unfavorable for microorganism
The formation of apposition growth and microbial film.Therefore graphite felt electrode to be improved as the performance of anode material, improve graphite felt
Hydrophilic, improves the compatibility with microorganism, becomes one of MFC mains direction of studying.
Sulfonated polyaniline (sPANI) shows excellent properties at aspects such as electric conductivity, biocompatibility, preparation process, and
Its preparation process is relatively easy, is one of focus of material, electrochemical field.
1 (Uwe of documentJuliane Nieβen,Fritz Scholz.A Generation of
Microbial Fuel Cells with Current Outputs Boosted by More Than One Order of
Magnitude[J].Angewandte Chemie,2003,42(25):2880-2883.) in report a kind of polyaniline to Pt
Anode carries out method of modifying and carrys out modified microbe fuel cell, and electric current density reaches 1.5mA/cm2。
2 (Jun-Xian Hou, Zhong-Liang Liu, Yan-Xia Li.Polyaniline Modified of document
Stainless Steel Fiber Felt for High-Performance Microbial Fuel Cell Anodes
[J].Journal of Clean Energy Technologies,2015,3(3):165-169.2016,88(4):318-
324) report in by electrochemical polymerization method synthesized polyaniline, and using its modification stainless steel fibre felt, as a result show the party
Method greatly improved anode specific surface area.
But, there is following defect in the synthetic method and application reported by above-mentioned document：
(1) such as although its polyaniline-modified electrode prepared of document 1,2 improves the power output of MFC, but which is total
Power density it is still relatively low for 360mW/m2。
(2) as the polyaniline electrode prepared in document 1 is mainly used in the microbiological fuel cell of purebred bacterium, but it is actual
Wastewater treatment process in generally mixed bacterium, the synergism between microorganism species do not account for.
The content of the invention
It is an object of the invention to provide a kind of modified graphite felt electrode for being applied to microbiological fuel cell, modified graphite felt
Electrode has good electricity generation performance of microbial fuel cell, and the advantages of active high, easy recovery, good stability.For
Above-mentioned purpose is realized, the technical scheme that the present invention takes is：
A kind of sulfonated polyaniline modified graphite felt electrode for being applied to microbiological fuel cell, will will be made using template-free method
The polyaniline sulfonation for obtaining, after ultrasonic at normal temperatures with Kynoar (PVDF), drying bonding is supported on graphite felt load
Body surface face.
Wherein the load capacity of sulfonated polyaniline is 1-10mg/cm2。
Above-mentioned sulfonated polyaniline is supported on graphite felt carrier in the following way and comprises the following steps that：
(1) template-free method prepares polyaniline；
(2) using oleum as sulfonating agent, by polyaniline obtained in step (1), temperature be reaction 1 at 80 DEG C～
5h, obtains sulfonated polyaniline；
(3) graphite felt is sequentially placed into into ultrasound 0.5h in second alcohol and water, is repeated 3 times, remove surface impurity；
(4) nitric acid and sulphuric acid mixed acid solution are taken, the graphite felt that step (3) is obtained is immersed in wherein, is 80 DEG C in temperature
Lower reaction 8h；
(5) take PVDF to be dissolved in NMP, then sulfonated polyaniline obtained in taking step (2) is added thereto, stir under room temperature
0.5h,；Graphite felt submergence obtained in step (3) wherein, that is, is obtained into sulfonated polyaniline graphite felt electrode.
Preferably, in step (2), the response time is 3h.
Further, in step (5), described PVDF and sulfonated polyaniline mass ratio are 5:95.
Further, in step (5), in graphite felt immersion processes, by ultrasonic 0.5h, it is dried at 80 DEG C after taking-up
24h so that sulfonated polyaniline is uniformly dispersed on electrode.
Further, in step (4), nitric acid and sulphuric acid mixed acid solution volume ratio are 1:3.
Compared with prior art, advantage is the present invention：
(1) sulfonated polyaniline graphite felt electrode prepared by the present invention increased the specific surface area of electrode, and using ultrasound baking
Dry method so that sulfonated polyaniline is uniformly dispersed on electrode, improves the catalytic performance of material.
(2) sulfonated polyaniline graphite felt electrode surface prepared by the present invention is due to sulfonation group, improving graphite felt
The hydrophilic of electrode, and the electric conductivity of electrode material is increased, so as to improve the electricity generation performance of microbiological fuel cell.
(3) the sulfonated polyaniline graphite felt electrode environmental protection that the present invention is prepared, itself will not be produced during the course of the reaction
Raw secondary pollution, it is easy to reclaim.
(4) synthesis step selected by the present invention is simple to operate, and raw material is easy to get, and is easier to realize large-scale production.
Description of the drawings
Fig. 1 (a), (b) are respectively the SEM figures of the PANI and sPANI of the present invention；
Fig. 2 is the modified graphite felt electrode material FTIR figures of the present invention.
Fig. 3 is the modified graphite felt electrode XRD figure of the present invention.
Fig. 4 is the N of the PANI and sPANI graphite felt electrodes of the present invention2Adsorption desorption isothermal curve.
Fig. 5 is the later polarization curve of MFC stable operations of the invention and power density curve chart.
Fig. 6 is the CV curve charts of the PANI and sPANI graphite felt electrodes of the present invention.
Fig. 7 is the EIS curve charts of the PANI and sPANI graphite felt electrodes of the present invention.
Fig. 8 is the corresponding Tafel curve figure of different sulfonated polyaniline response time of the present invention.
Specific embodiment
(1) microbiological fuel cell sulfonated polyaniline modified graphite felt electrode
The invention provides a kind of application of sulfonated polyaniline modified graphite felt electrode in microbiological fuel cell field, sends out
Existing its can improve electricity generation performance of the graphite felt electrode in MFC.
(2) material property characterization test
Characterization test is carried out to material using XRD, SEM, BET, FTIR etc..
(3 microbiological fuel cell performance tests
MFC polarization curves and power density curve are determined, its EIS is tested, CV, Tafel curve finds that sulfonated polyaniline changes
Property graphite felt electrode can improve the maximum power density of microbiological fuel cell, reduce reaction internal resistance, enhance kinetics
Activity.
The present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
Preparation of the microbiological fuel cell with sulfonated polyaniline modified graphite felt electrode
(1) polyaniline material is prepared using template-free method.Aniline (0.37g, 4mmol) is added in 120mL deionized waters,
30min is vigorously mixed at room temperature for, is subsequently placed in ice-water bath.By Ammonium persulfate. (1.826g, 8mmol) addition 120mL go from
In sub- water, it is placed in ice-water bath and cools down, be then added dropwise in above-mentioned solution, stir, seals, be placed in low temperature thermostat bath
In 0 DEG C reaction 12h.Reaction terminates post-consumer polymer in blackish green, with filtered on buchner funnel, difference deionized water, methanol and second
Ether is rinsed for several times, and then 24h drying at room temperature, obtains polyaniline (PANI).
(2) sulfonated polyaniline adopts oleum and carries out sulfonation to polyaniline for sulfonating agent and is prepared from.Take above-mentioned drying
Polyaniline 1g, add 5mL oleums (20%) and 15mL concentrated sulphuric acids, react 3h in 80 DEG C under agitation, react after terminating
Reactant mixture is slowly dropped to into (ice bath) in the beaker equipped with 200mL methanol, 100mL acetone is subsequently adding, is leaked with Bu Shi
Bucket is filtered, and it is neutral to be washed with methanol to pH, and then 24h drying at room temperature, obtains sulfonated polyaniline (sPANI).
(3) graphite felt by surface area for 3cm × 3cm is sequentially placed into ultrasound 0.5h in second alcohol and water, is repeated 3 times, then
60 DEG C are dried 12h in an oven, are placed in standby in exsiccator.
(4) 30mL nitric acid and 90mL sulphuric acid are taken, the two volume ratio is 1:3, the graphite felt that step (3) is obtained is immersed in into which
In, 8h is reacted in being put into baking oven, reaction temperature is 80 DEG C.Graphite felt is taken out afterwards, and deionized water rinses 30min, until pH
It is changed into neutral, is placed in baking oven 60 DEG C and is dried 12h.
(5) take PVDF to be dissolved in NMP, then take sulfonated polyaniline and polyaniline material powder body obtained in step (1) (2) and be placed in
Wherein, PVDF and the mass ratio of sulfonated polyaniline are 5:95,0.5h is stirred under room temperature, by graphite felt submergence obtained in step (4)
Wherein, ultrasonic 0.5h, after taking-up in an oven 80 DEG C be dried 24h, that is, obtain sulfonated polyaniline load capacity for 3mg/cm2It is modified
Graphite felt electrode.
Embodiment 2
Preparation of the microbiological fuel cell with sulfonated polyaniline modified graphite felt electrode
(1) polyaniline material is prepared using template-free method.Aniline (0.37g, 4mmol) is added in 120mL deionized waters,
30min is vigorously mixed at room temperature for, is subsequently placed in ice-water bath.By Ammonium persulfate. (1.826g, 8mmol) addition 120mL go from
In sub- water, it is placed in ice-water bath and cools down, be then added dropwise in above-mentioned solution, stir, seals, be placed in low temperature thermostat bath
In 0 DEG C reaction 12h.Reaction terminates post-consumer polymer in blackish green, with filtered on buchner funnel, difference deionized water, methanol and second
Ether is rinsed for several times, and then 24h drying at room temperature, obtains polyaniline (PANI).
(2) sulfonated polyaniline adopts oleum and carries out sulfonation to polyaniline for sulfonating agent and is prepared from.Take above-mentioned drying
Polyaniline 1g, add 5mL oleums (20%) and 15mL concentrated sulphuric acids, react 1h in 80 DEG C under agitation, react after terminating
Reactant mixture is slowly dropped to into (ice bath) in the beaker equipped with 200mL methanol, 100mL acetone is subsequently adding, is leaked with Bu Shi
Bucket is filtered, and it is neutral to be washed with methanol to pH, and then 24h drying at room temperature, obtains sulfonated polyaniline (sPANI).
(3) graphite felt by surface area for 3cm × 3cm is sequentially placed into ultrasound 0.5h in second alcohol and water, is repeated 3 times, then
60 DEG C are dried 12h in an oven, are placed in standby in exsiccator.
(4) 30mL nitric acid and 90mL sulphuric acid are taken, the two volume ratio is 1:3, the graphite felt that step (3) is obtained is immersed in into which
In, 8h is reacted in being put into baking oven, reaction temperature is 80 DEG C.Graphite felt is taken out afterwards, and deionized water rinses 30min, until pH
It is changed into neutral, is placed in baking oven 60 DEG C and is dried 12h.
(5) take PVDF to be dissolved in NMP, then take sulfonated polyaniline and polyaniline material powder body obtained in step (1) (2) and be placed in
Wherein, PVDF and the mass ratio of sulfonated polyaniline are 5:95,0.5h is stirred under room temperature, by graphite felt submergence obtained in step (4)
Wherein, ultrasonic 0.5h, after taking-up in an oven 80 DEG C be dried 24h, that is, obtain sulfonated polyaniline load capacity for 3mg/cm2It is modified
Graphite felt electrode.
Embodiment 3
Preparation of the microbiological fuel cell with sulfonated polyaniline modified graphite felt electrode
(1) polyaniline material is prepared using template-free method.Aniline (0.37g, 4mmol) is added in 120mL deionized waters,
30min is vigorously mixed at room temperature for, is subsequently placed in ice-water bath.By Ammonium persulfate. (1.826g, 8mmol) addition 120mL go from
In sub- water, it is placed in ice-water bath and cools down, be then added dropwise in above-mentioned solution, stir, seals, be placed in low temperature thermostat bath
In 0 DEG C reaction 12h.Reaction terminates post-consumer polymer in blackish green, with filtered on buchner funnel, difference deionized water, methanol and second
Ether is rinsed for several times, and then 24h drying at room temperature, obtains polyaniline (PANI).
(2) sulfonated polyaniline adopts oleum and carries out sulfonation to polyaniline for sulfonating agent and is prepared from.Take above-mentioned drying
Polyaniline 1g, add 5mL oleums (20%) and 15mL concentrated sulphuric acids, react 5h in 80 DEG C under agitation, react after terminating
Reactant mixture is slowly dropped to into (ice bath) in the beaker equipped with 200mL methanol, 100mL acetone is subsequently adding, is leaked with Bu Shi
Bucket is filtered, and it is neutral to be washed with methanol to pH, and then 24h drying at room temperature, obtains sulfonated polyaniline (sPANI).
(3) graphite felt by surface area for 3cm × 3cm is sequentially placed into ultrasound 0.5h in second alcohol and water, is repeated 3 times, then
60 DEG C are dried 12h in an oven, are placed in standby in exsiccator.
(4) 30mL nitric acid and 90mL sulphuric acid are taken, the two volume ratio is 1:3, the graphite felt that step (3) is obtained is immersed in into which
In, 8h is reacted in being put into baking oven, reaction temperature is 80 DEG C.Graphite felt is taken out afterwards, and deionized water rinses 30min, until pH
It is changed into neutral, is placed in baking oven 60 DEG C and is dried 12h.
(5) take PVDF to be dissolved in NMP, then take sulfonated polyaniline and polyaniline material powder body obtained in step (1) (2) and be placed in
Wherein, PVDF and the mass ratio of sulfonated polyaniline are 5:95,0.5h is stirred under room temperature, by graphite felt submergence obtained in step (4)
Wherein, ultrasonic 0.5h, after taking-up in an oven 80 DEG C be dried 24h, that is, obtain sulfonated polyaniline load capacity for 3mg/cm2It is modified
Graphite felt electrode.
The material property characterization test of 1 sulfonated polyaniline modified graphite felt electrode of embodiment
1st, scanning electron microscope morphology analysis (SEM)
Shown in scanning electron microscope morphology analysis such as Fig. 1 (a) (b), the JEOLJSM- produced using Jeol Ltd.
6380LV scanning electron microscopes carry out morphology characterization to obtained sample, and accelerating potential is 30kV.Fig. 1 (a) (b) is respectively
The SEM figures of polyaniline, the sulfonated polyaniline electrode of the embodiment of the present invention 1, it can be seen that polyaniline, sulfonated polyaniline are in
Irregular agglomerated particle shape, and sulfonated polyaniline is smaller compared to polyaniline surface particle diameter.
2nd, X-ray diffraction analysis (XRD)
The X-ray diffraction analysis of the sulfonated polyaniline electrode of the embodiment of the present invention 1 are as shown in Fig. 2 adopt Germany Bruker
D8Advance type X-ray diffractometers (XRD) of company's production carries out material phase analysis to sample；Test condition is：Graphite monochromatic
Device, Cu-K α radiation, radiation wavelength λ=0.15418nm, tube voltage 40kV, tube current 40mA, scanning speed are 8～10 ° of min-1, 2 θ=10～60 ° of scanning angle scope.Synthesized PANI has obvious Bragg diffraction respectively at 20.5 ° and 26.0 °
Peak, and sPANI only occurs in that a peak at 25.2 °.Calculate PNAI's and sPANI using the integral area of diffraction curve
Degree of crystallinity is respectively 33.2% and 12.2%, and spacing of lattice is respectively 0.183nm and 0.247nm, shows PANI after sulfonation process
Crystal region portions turn for unformed.
3rd, FTIR spectrum analysis (FTIR)
Nicolet of the FTIR spectrum analysis using the production of Thermo Fisher Scientific companies of the U.S.
Is10 Fourier transform infrared spectrometer, is measured to polyaniline, sulfonated polyaniline, will be sample and KBr mixed grindings uniform
Sample preparation afterwards, scanning wave-number range are 400～4000cm-1, scanning times 32 times, resolution is 4cm-1.Fig. 3 is present invention enforcement
The FTIR spectrograms of the PANI and sPANI of the sulfonated polyaniline electrode of example 1, the appearance position of the two characteristic peak are basically identical, but
SPANI is in 1073cm-1And 1222cm-1Place occurs in that new absworption peak, is respectively belonging to-SO3In H, O=S=O's is symmetrical and non-
Symmetric shrinkage vibrates, and 3540cm-1The absworption peak that place occurs is from-SO3The contraction vibration of O-H in H, this shows success
Sulfonic acid group is introduced in PANI.
4th, specific surface area analysis (BET)
Ns of the Fig. 4 for PANI the and sPANI graphite felt electrodes of the sulfonated polyaniline electrode of the embodiment of the present invention 12Adsorption desorption etc.
Warm curve, is determined using 2020 physical adsorption appearances of ASAP that Micromeritics companies of the U.S. produce.As shown in Figure 4, its etc.
Warm curve is IV type isothermal curves, is typical meso-hole structure, is computed, and the specific surface area of sPANI graphite felt electrodes reaches
24.3m2/ g, more than the 13.7m of PANI graphite felts2/ g, illustrates that sulfonated polyaniline improves the specific surface area of graphite felt electrode, is
Graphite felt electrode provides more avtive spots.
MFC battery performance tests
The MFC polarization curves of the sulfonated polyaniline electrode of the embodiment of the present invention 1 and the test of power density curve
Using two-chamber type MFC, using the sPANI graphite felt electrodes of PANI graphite felt electrode sums as microbiological fuel cell
Anode loads in MFC, and negative electrode adopts graphite felt electrode, anode microorganism to take from the MFC water outlets that laboratory runs more than a year.Sun
Pole nutritional solution is 50mmol/L sodium acetate simulated wastewater (NaH2PO4·2H2O：2.96g/L、Na2HPO4·12H2O：11.10g/L、
NaCl：0.50g/L、CaCl2：0.02g/L、MgCl2·6H2O：0.469g/L、KCl：0.13g/L、NH4Cl：0.31g/L、
CH3COONa：1.64g/L, trace element 1mL, pH=7), sterilized 30 minutes in 121 DEG C of high temperature sterilize pots using front；Negative electrode
Using air.Using commercial cation exchange membrane, its IEC is 2.0mmol/g to film, and whole device is placed in (T=in constant water bath box
30℃).Fig. 5 is MFC polarization curves and power density curve after MFC stable operations, it can be seen that sulfonated polyaniline graphite felt
The maximum power density of electrode is 705mW/m2, compared to polyaniline electrode 536mW/m2, improve 31.5%.
The MFC electrochemical property tests of the sulfonated polyaniline electrode of the embodiment of the present invention 1
Electrochemical property test is carried out to the anode of microbiological fuel cell, is produced using Shanghai Chen Hua company limiteies
CHI604D, is circulated volt-ampere curve (CV), electrochemical impedance spectroscopy (EIS) analysis using MFC anodes.Test is using three electrodes
System, its Anodic are working electrode, and negative electrode is that, to electrode, Ag/AgCl electrodes (saturation KCl ,+197mV, vs SHE) are reference
Electrode.CV starting voltages are open-circuit voltage (OCV), and sweep limitss are -1V～+1V, and scanning speed is 1mV/s；Electrochemical impedance
(EIS) response excursion be 5mV, range of scanned frequencies 1-105Hz, scanning current potential are open circuit potential, are fitted number using Zview softwares
According to.Fig. 6 is the CV curve charts of polyaniline graphite felt and sulfonated polyaniline modified graphite felt electrode MFC, it can be seen that sPANI in figure
- 0.177V and -0.233V is respectively with PANI redox potentials, is offset to high potential direction, illustrate the activation loss reacted
Reduce.Fig. 7 is that the intersection point of the EIS figures of polyaniline and sulfonated polyaniline modified graphite felt electrode MFC, curve and X-axis represents ohm
Impedance, it is clear that sPANI ohmages are 11.4 Ω, basically identical with 14.8 Ω of PANI.And straightway represents diffusion impedance, sulphur
Change 63.5 Ω compared to polyaniline of 43.4 Ω of polyaniline, illustrate that sulfonated polyaniline can accelerate extracellular electron transfer mechanism
Carry out, and then reduce diffusion impedance, so as to improve its electricity generation ability in microbiological fuel cell.
The sulfonated polyaniline optimal sulfonating reaction time of the sulfonated polyaniline electrode of embodiment of the present invention 1-3
Sulfonated polyaniline electrode, polyaniline electrode to embodiment 1-3 carries out Tafel curve test, tower phenanthrene curve test
Using three-electrode system, its Anodic be working electrode, negative electrode be Pt silk electrodes, Ag/AgCl electrodes (saturation KCl ,+197mV,
Vs SHE) for reference electrode.Scanning voltage speed be 1mV/s, sweep limitss be with OCP as zero potential, -50mV～+
50mV, using Corrwave software fitting data.Obtain the Tafel curve of 0,1,3,5 hours difference counter electrodes of sulfonating reaction
Figure, as shown in Figure 8：The exchange current density order of four different sulfonating reaction times is sPANI-3>sPANI-5>sPANI-5>
SPANI-0, illustrates that the optimal sulfonating reaction time is 3h.
Claims (8)
1. one kind is applied to microbiological fuel cell modified graphite felt electrode, it is characterised in that the modified graphite felt electrode is table
Face uniform load has the graphite felt carrier electrode of sulfonated polyaniline.
2. it is according to claim 1 to be applied to microbiological fuel cell modified graphite felt electrode, it is characterised in that the sulphur
The load capacity for changing polyaniline is 1-10mg/cm2。
3. it is according to claim 1 to be applied to microbiological fuel cell modified graphite felt electrode, it is characterised in that described
Sulfonated polyaniline is supported on graphite felt carrier concrete as under step in the following way：
(1) template-free method prepares polyaniline；
(2) using oleum as sulfonating agent, by polyaniline obtained in step (1), it is at 80 DEG C, to react 1～5h in temperature, obtains
To sulfonated polyaniline；
(3) graphite felt is sequentially placed into into ultrasound 0.5h in second alcohol and water, is repeated 3 times, remove surface impurity；
(4) nitric acid and sulphuric acid mixed acid solution are taken, the graphite felt that step (3) is obtained is immersed in wherein, it is anti-in the case where temperature is for 80 DEG C
Answer 8h；
(5) take PVDF to be dissolved in NMP, then sulfonated polyaniline obtained in taking step (2) is added thereto, and 0.5h is stirred under room temperature；Will
Graphite felt submergence obtained in step (3) wherein, that is, obtains sulfonated polyaniline graphite felt electrode.
4. it is according to claim 1 to be applied to microbiological fuel cell modified graphite felt electrode, it is characterised in that step
(2), in, it is to react 3h at 80 DEG C in temperature.
5. it is according to claim 1 to be applied to microbiological fuel cell modified graphite felt electrode, it is characterised in that step
(5), in, described PVDF and sulfonated polyaniline mass ratio are 5:95.
6. the sulfonated polyaniline modified graphite felt electrode for being applied to microbiological fuel cell according to claim 1, which is special
Levy and be, in step (5), in graphite felt immersion processes, by ultrasonic 0.5h, 24h is dried at 80 DEG C after taking-up so that sulfonation
Polyaniline is uniformly dispersed on electrode.
7. the sulfonated polyaniline modified graphite felt electrode for being applied to microbiological fuel cell according to claim 1, which is special
Levy and be, in step (4), nitric acid and sulphuric acid mixed acid solution volume ratio are 1:3.
8. the sulfonated polyaniline modified graphite felt electrode preparation method of the microbiological fuel cell according to claim 3-7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611209678.6A CN106532076A (en) | 2017-02-06 | 2017-02-06 | Graphite felt electrode for microbial fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611209678.6A CN106532076A (en) | 2017-02-06 | 2017-02-06 | Graphite felt electrode for microbial fuel cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106532076A true CN106532076A (en) | 2017-03-22 |
Family
ID=58337781
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611209678.6A Pending CN106532076A (en) | 2017-02-06 | 2017-02-06 | Graphite felt electrode for microbial fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106532076A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108172841A (en) * | 2017-12-17 | 2018-06-15 | 南京理工大学 | One kind is applied to microbiological fuel cell modified graphite felt electrode and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102496733A (en) * | 2011-12-27 | 2012-06-13 | 中国海洋大学 | Method for accelerating degradation of seabed organic pollutants by microbiological fuel cell catalysis |
| CN103401008A (en) * | 2013-07-31 | 2013-11-20 | 华南理工大学 | Method and device for storing bioelectrical energy by virtue of capacitive anode |
| CN106229535A (en) * | 2016-09-10 | 2016-12-14 | 华南理工大学 | The device utilizing three electrode storage biological powers and the method storing biological power thereof |
-
2017
- 2017-02-06 CN CN201611209678.6A patent/CN106532076A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102496733A (en) * | 2011-12-27 | 2012-06-13 | 中国海洋大学 | Method for accelerating degradation of seabed organic pollutants by microbiological fuel cell catalysis |
| CN103401008A (en) * | 2013-07-31 | 2013-11-20 | 华南理工大学 | Method and device for storing bioelectrical energy by virtue of capacitive anode |
| CN106229535A (en) * | 2016-09-10 | 2016-12-14 | 华南理工大学 | The device utilizing three electrode storage biological powers and the method storing biological power thereof |
Non-Patent Citations (2)
| Title |
|---|
| Y. HINDATU等: "Mini-review: Anode modification for improved performance of microbial fuel cell", 《RENEWABLE AND SUSTAINABLE ENERGY REVIEWS》 * |
| 于黄中 等: "磺化聚苯胺性能的研究", 《华南师范大学学报(自然科学版)》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108172841A (en) * | 2017-12-17 | 2018-06-15 | 南京理工大学 | One kind is applied to microbiological fuel cell modified graphite felt electrode and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bai et al. | All-solid state asymmetric supercapacitor based on NiCoAl layered double hydroxide nanopetals on robust 3D graphene and modified mesoporous carbon | |
| Li et al. | A multi-interface CoNi-SP/C heterostructure for quasi-solid-state hybrid supercapacitors with a graphene oxide-containing hydrogel electrolyte | |
| Shi et al. | MOF-derived M-OOH with rich oxygen defects by in situ electro-oxidation reconstitution for a highly efficient oxygen evolution reaction | |
| CN107694581B (en) | Application of heteroatom-doped porous carbon-coated cuprous phosphide composite catalyst | |
| CN111403696B (en) | Flaky manganese dioxide hollow frame structure material and preparation method and application thereof | |
| CN105742074A (en) | Poly-dopamine based porous carbon fiber/MoSe2 composite material and preparation method thereof | |
| Zhu et al. | One-step hydrothermal synthesis of flower-like CoS hierarchitectures for application in supercapacitors | |
| CN111569855B (en) | ZIF-8/C 60 Preparation method of compound derived nonmetal electrocatalyst | |
| Fan et al. | Carbon-covered hollow nitrogen-doped carbon nanoparticles and nitrogen-doped carbon-covered hollow carbon nanoparticles for oxygen reduction | |
| CN110504456B (en) | Oxygen reduction electrode based on nitrogen-oxygen doped ball/sheet porous carbon material and preparation method and application thereof | |
| CN113816437B (en) | Preparation method of oxygen reduction catalyst of dimethyl imidazole cobalt combined nickel-aluminum layered double hydroxide/graphene oxide | |
| CN106532068A (en) | Modified graphite felt electrode used for microbial fuel cell | |
| CN106159239A (en) | The preparation method of a kind of Manganese monosulfide ./graphene nanocomposite material, lithium ion battery negative, lithium ion battery | |
| Zhao et al. | Doping engineering on carbons as electrocatalysts for oxygen reduction reaction | |
| CN104600249A (en) | Preparation methods of nanometer porous metal and nanometer porous metal and lithium-sulfur battery positive pole material | |
| Zhang et al. | Design of co-continuous structure of cellulose/PAA-based alkaline solid polyelectrolyte for flexible zinc-air battery | |
| CN108172841B (en) | Modified graphite felt electrode applied to microbial fuel cell and preparation method thereof | |
| Cui et al. | Bamboo derived N-doped carbon as a bifunctional electrode for high-performance zinc–air batteries | |
| Yao et al. | Flexible carbon film with local enlarged interlayer spacing for ultrafast and highly durable potassium storage | |
| CN113223869A (en) | Three-dimensional porous nanoflower-like NiS2Preparation and application of/carbon cloth composite material | |
| CN106532076A (en) | Graphite felt electrode for microbial fuel cell | |
| CN116845254A (en) | Oxygen reduction catalyst of polyaniline conductive polymer coupled with carbon nano tube/covalent organic framework compound, and preparation method and application thereof | |
| CN110265644A (en) | A kind of preparation method of antimony pentoxide/polyacrylic acid of reticulated porous structures/carbon cloth flexibility anode material of lithium-ion battery | |
| CN109256561A (en) | Hard carbon cathode material and preparation method thereof and the method for making battery using it | |
| CN106960953A (en) | A kind of preparation method of nitrogen-doped carbon fibrous material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170322 |