CN206422151U - A kind of microbiological fuel cell reactor - Google Patents
A kind of microbiological fuel cell reactor Download PDFInfo
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- CN206422151U CN206422151U CN201720002356.8U CN201720002356U CN206422151U CN 206422151 U CN206422151 U CN 206422151U CN 201720002356 U CN201720002356 U CN 201720002356U CN 206422151 U CN206422151 U CN 206422151U
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Abstract
The utility model discloses a kind of microbiological fuel cell reactor.For single-chamber microbial fuel cell, including sampling adding mouth（1）, silver/silver chloride reference electrode（2）, data acquisition unit（3）, external resistance（4）, PEM（5）, cathode electrode, anode chamber（8）And anode electrode（9）.The microbiological fuel cell structure of reactor is simply compact, the startup time substantially shorten, and electricity production increase, constructions cost, it is stable effectively, power output is high.
Description
Technical field
The utility model is related to microorganism electrolysis cell field, and in particular to a kind of microbiological fuel cell reactor.
Background technology
Microbiological fuel cell（Microbial fuel cell）Be recent years it is emerging study science, be a kind of profit
Chemical energy in organic matter is converted into the new device of electric energy with microorganism.Microbiological fuel cell not only can be by water body
Organic matter and sludge degraded, moreover it is possible to the electronics produced during degradation of organic substances is born by anode, external circuit, circuit
Carry, electronics is finally received by negative electrode, produce electric energy.As a kind of emerging energy conversion device, compared with conventional fuel cell,
Microbiological fuel cell not only degrades organic matter, and obtains electric energy；With operating condition is gentle, clean and effective, fuel
The advantages of wide material sources, recyclable recycling, be a kind of emerging technology of great application prospect, so that by the lasting pass of people
Note.
Currently, microbiological fuel cell still has very low power output.This is primarily due to oxygen of the microorganism to substrate
Change what the reasons such as speed is slow, electron transport rate is small, activation of cathode current potential is low, the internal resistance of cell is big were caused.In order to strengthen microorganism
The power output of fuel cell, has done substantial amounts of research, and very big exert has been done in the research especially in terms of electrode material
The material and structure of power, especially cathode material can directly affect electronics receptance and then influence electricity production power.
Influence of the cathode electrode material to microbial fuel cells system is mainly reflected in：（1）Material and structure, not only shadow
The electric conductivity of electrode is rung, and influences negative electrode to connect nucleophobic speed to directly affect power output；（2）The resistance value of negative electrode
It is also to influence a key factor of cell output, therefore when selecting microorganism battery cathode material, high conductivity is still
It is so the problem of needing to consider；（3）The material of negative electrode is the key factor for determining cathode potential, and general carbon material is loose porous,
With high electric conductivity, it is adaptable to make the material of negative electrode.
The carbon material generally used includes the materials such as graphite, carbon cloth or carbon paper, but directly uses, and effect is not good.To improve
The performance of cathode material, can suitably be used the catalyst of high activity to modify cathode material and be activated with the reaction for reducing negative electrode
Potential, so as to further speed up reaction rate.Carbon composite nano-material is due to very big specific surface area, specific hole knot
Structure, very high heat endurance, extremely strong mechanical strength and toughness and extremely strong electric conductivity, the optimal selection as electrode material,
It is the ideal material for preparing novel nano and high composite, high praise is enjoyed in research fields such as the storages and conversion of energy.
Utility model content
Main purpose of the present utility model is to provide a kind of microbiological fuel cell reactor.
The utility model purpose is achieved through the following technical solutions.
A kind of microbiological fuel cell reactor, is single-chamber microbial fuel cell, including sampling adding mouth, silver/chlorination
Silver-colored reference electrode, data acquisition unit, external resistance, PEM, cathode electrode, anode chamber and anode electrode；
The cathode electrode is embedded on the locular wall of anode chamber side, and has one side directly to be contacted with air, another side and matter
Proton exchange is directly contacted；The PEM has one side and the cathode electrode being embedded on anode locular wall in anode chamber
Directly contact, another side is contacted with the anolyte in anode chamber；The anode electrode is in anode chamber close to the 1/3 of cathode electrode
Place；Top of the sampling adding mouth in anode chamber；In the silver/silver chloride reference electrode insertion anode chamber, and pass through wire
It is connected with external circuit；The cathode electrode and anode electrode are connected by wire with external resistance；The data acquisition unit and dispatch from foreign news agency
Resistance is in parallel；
The cathode electrode is air electrode, mixes back loading with acetylene black by cathode composite and is obtained on carbon cloth；
The cathode electrode by with air contact to contact with PEM while, successively including diffusion layer, carbon based layer,
Carbon cloth and Catalytic Layer.
Further, the thickness of the diffusion layer is 0.08 ~ 0.12mm.
Further, the thickness of the Catalytic Layer is 0.04 ~ 0.06mm.
Further, the material of the anode electrode is carbon felt；The electrode gross area of the anode electrode and cathode electrode
Volume ratio with anode chamber is 1:8.7cm2/cm3。
The preparation method of microorganism fuel cell cathode composite in the reactor, comprises the following steps：
（1）After graphite powder is dissolved using the mixed solution of the concentrated sulfuric acid and potassium peroxydisulfate, stir, enter under condition of water bath heating
Row pre-oxidation, obtains pre-oxidizing graphite；
（2）Use the mixed solution of the concentrated sulfuric acid and sodium nitrate to dissolve to keep oxidation environment by graphite is pre-oxidized, add high
Potassium manganate, stirring forms underflow；Add deionized water, heating water bath stirring；
（3）After heating water bath terminates, add after deionized water dilution, be slowly added to hydrogen peroxide and be oxidizing to mixed liquor and go out
Existing bubble is simultaneously changed into yellow, is cleaned successively with hydrochloric acid and deionized water, dries, obtain graphene oxide；
（4）By graphene oxide it is ultrasonically treated in deionized water after, dissolved with the mixed solution of ammonium titanium fluoride and boric acid,
Heating water bath is carried out after stirring, obtained mix products filter membrane, washing, vacuum drying heat calcification, obtain described micro-
Biofuel battery cathode composite.
Further, step（1）In, the graphite powder is agraphitic carbon.The mixing of the concentrated sulfuric acid and potassium peroxydisulfate is molten
Liquid is according to the concentrated sulfuric acid and potassium peroxydisulfate liquid ratio 4.5 ~ 6:1 ml/g is mixed to get.The mixing of the concentrated sulfuric acid and potassium peroxydisulfate is molten
The liquid ratio of liquid and graphite powder is 8 ~ 10:1 ml/g.The temperature of the heating water bath is 80 DEG C, and the time is 6h.
Further, step（2）In, the mixed solution of the concentrated sulfuric acid and sodium nitrate is according to the concentrated sulfuric acid and sodium nitrate liquid material
Than for 46:1ml/g is mixed to get.
Further, step（2）In, the mass ratio of the potassium permanganate and pre-oxidation graphite is 6:1.The potassium permanganate
Divide 10 additions, the time interval added every time is 5min.Step（2）In, the underflow is stirred under 30 ~ 40 DEG C of water bath conditions
50 ~ 70min is mixed to obtain.The ratio of the amount for adding deionized water and the amount of potassium permanganate is 40:3ml/g.The heating water bath
Temperature be 85 ~ 95 DEG C, the time be 30 ~ 40min.
Further, step（3）In, the concentration of the hydrogen peroxide is 30wt%.The addition of the hydrogen peroxide and addition
The volume ratio of deionized water is 3:100.The concentration of the hydrochloric acid is 5wt%.The cleaning is to use hydrochloric acid centrifuge washing 3 times, then is used
Deionized water centrifuge washing 4 ~ 7 times.The drying is that 36 ~ 40h is dried at 60 DEG C.
Further, step（4）In, the ultrasonically treated time is 30 ~ 40min.The ammonium titanium fluoride and boric acid
Mixed solution is by ammonium titanium fluoride and boric acid volume ratio 1:1 is mixed to get, and the concentration of the ammonium titanium fluoride is 0.1mol/L,
The concentration of the boric acid is 0.3mol/L.
Further, step（4）In, the mixed solution of the ammonium titanium fluoride and boric acid and the liquid ratio of graphene be 8 ~
10:1 ml/g.The time of the stirring is 10 ~ 20min.The heating water bath is the water-bath closing heating 2h at 60 DEG C.It is described
Filter membrane was 0.45 μm of filter membrane.The drying is in 50 ~ 70 DEG C of dry 14 ~ 18h.The heating calcification is at 200 DEG C
Heat 1h.
A kind of micro- life based on microorganism fuel cell cathode composite made from preparation method described in any of the above-described
Thing fuel cell reactor, is single-chamber microbial fuel cell, including sampling adding mouth, silver/silver chloride reference electrode, data are adopted
Storage, external resistance, PEM, cathode electrode, anode chamber and anode electrode；
The cathode electrode is embedded on the locular wall of anode chamber side, and has one side directly to be contacted with air, another side and matter
Proton exchange is directly contacted；The PEM has one side and the cathode electrode being embedded on anode locular wall in anode chamber
Directly contact, another side is contacted with the anolyte in anode chamber；The anode electrode is in anode chamber close to the 1/3 of cathode electrode
Place；Top of the sampling adding mouth in anode chamber；In the silver/silver chloride reference electrode insertion anode chamber, and pass through wire
It is connected with external circuit；The cathode electrode and anode electrode are connected by wire with external resistance；The data acquisition unit and dispatch from foreign news agency
Resistance is in parallel；
The cathode electrode is air electrode, using the oxygen in air as final electron acceptor；The cathode electrode is by making
Standby cathode composite mixes back loading with acetylene black and obtained on carbon cloth；The cathode electrode is by the one side with air contact
To the one side contacted with PEM, successively including diffusion layer, carbon based layer, carbon cloth and Catalytic Layer.
Further, the anolyte in the anode chamber is the 50mmol/L of sodium acetate phosphate buffer solution, initially
PH value is 6.8 ~ 7.1.
Further, nitrogen treatment is led to before the anolyte is added, to keep anolyte anaerobic state.
Further, the material of the anode electrode is carbon felt.
Further, the volume ratio of the electrode gross area of the anode electrode and cathode electrode and anode chamber is 1:
8.7cm2/cm3。
Further, the PEM before use, respectively concentration be 20wt% hydrogen peroxide, deionized water,
1h is carried out in 0.5mol/L sulfuric acid and deionized water boils processing.
Further, the preparation process of the cathode electrode comprises the following steps：
（1）Acetylene black is added in 40wt% polytetrafluoroethylsolution solution, after vortex 20s, mixed solution uniformly smeared
On carbon cloth, 25min is heated on 370 DEG C of refractory ceramics plates after air-drying, carbon based layer is made on carbon cloth；
（2）60wt% polytetrafluoroethylsolution solution is uniformly applied in obtained carbon based layer, in 370 DEG C of high temperature after air-drying
25min is heated on ceramic wafer；It is repeated 3 times, diffusion layer is made in carbon based layer；
（3）After obtained cathode composite is mixed with acetylene black, sequentially add addition for 0.83ul/mg go from
After the aqueous isopropanol of sub- water, 6.67ul/mg Nafion solution and 3.33ul/mg, vortex 20s, mixed solution is uniformly applied
The another side of carbon cloth is put on, is air-dried, Catalytic Layer is made；Obtain the cathode electrode.
Further, step（1）In, coating weight of the acetylene black on carbon cloth is 1.56mg/cm2。
Further, step（3）In, the mixing quality ratio of the cathode composite and acetylene black is 0.8 ~ 1:
10mg/mg。
Further, step（3）In, the another side of the mixture of the cathode composite and acetylene black in carbon cloth
Coating weight is 0.5mg/cm2。
The electricity generation process of the microbiological fuel cell reactor is：In anaerobic environment, grow on anode electrode
Electricity-producing microorganism is by the oxidation operation of anode chamber into proton, electronics and carbon dioxide, and proton is diffused to by PEM
Negative electrode, electronics is transferred to negative electrode by external circuit；Meanwhile, the oxygen on negative electrode is reduced, and is combined generation water with proton, is produced
Raw electric current.
Compared with prior art, the utility model has the advantages that：
（1）The utility model is simple and compact for structure, reasonable in design., the startup time substantially shortens, and electricity production increase, structure
This is caused, stable effective, power output is high.
（2）It is preferred that scheme in raw material compared with the noble metal electrode catalysis material such as platinum, titanium dioxide and graphite price are low
It is honest and clean, wide material sources；
（2）The startup time of microbiological fuel cell reactor based on preferred cathode material substantially shortens, and electricity production
Amount increase, the cathode electrode catalyst specific surface area of reactor is big, conduct electricity very well, and improves electron transmission efficiency, and common
Fuel cell is compared, and substantially improves electricity production power, reduces cathodic polarization；
（3）As one of preferred scheme, microorganism fuel cell cathode is prepared using titanium dioxide and graphene oxide
Composite, to replace the cathode material of the modifications such as noble metal, obtained cathode composite is applied to microbiological fuel cell
In, the cost of microbiological fuel cell is reduced, the electricity production power of microbiological fuel cell is improved and applies in practice
Feasibility.
Brief description of the drawings
Fig. 1 is the structural representation of the utility model microbiological fuel cell reactor；
Fig. 2 is 20wt%TiO in embodiment 12/RGO、40wt%TiO2/RGO、60wt%TiO2/RGO、80wt%TiO2/RGO、
Pure TiO2With cell voltage figures of the RGO respectively as cathode material；
Fig. 3 is 20wt%TiO in embodiment 12/RGO、40wt%TiO2/RGO、60wt%TiO2/RGO、80wt%TiO2/RGO、
Pure TiO2With polarization curves of the RGO respectively as cathode material；
Fig. 4 is 20wt%TiO in embodiment 12/RGO、40wt%TiO2/RGO、60wt%TiO2/RGO、80wt%TiO2/RGO、
Pure TiO2With power density diagrams of the RGO respectively as cathode material.
Embodiment
The utility model is further described with specific embodiment below in conjunction with the accompanying drawings, its object is to preferably reason
Content of the present utility model is solved, rather than to limitation of the present utility model.
The structural representation of the utility model microbiological fuel cell reactor is as shown in figure 1, be single-chamber microbial fuel
Battery, including sampling adding mouth 1, silver/silver chloride reference electrode 2, data acquisition unit 3, external resistance 4, PEM 5, negative electrode
Electrode, anode chamber 8 and anode electrode 9；
Cathode electrode is embedded on the locular wall of the side of anode chamber 8, and has one side directly to be contacted with air, and another side is handed over proton
Change the directly contact of film 5；PEM 5 has cathode electrode of the one side with being embedded on anode locular wall directly to connect in anode chamber
Touch, another side is contacted with the anolyte in anode chamber 8；Anode electrode 9 is in anode chamber 8 at the 1/3 of cathode electrode；Sampling
Top of the adding mouth 1 in anode chamber 8；In the silver/insertion of silver chloride reference electrode 2 anode chamber 8, and connected by wire and external circuit
Connect；Cathode electrode and anode electrode 9 are connected by wire with external resistance 4；Data acquisition unit 3 is in parallel with external resistance 4；
Cathode electrode is air electrode, and back loading is mixed with acetylene black by the cathode composite prepared obtains on carbon cloth
Arrive；Cathode electrode by with air contact to contact with PEM 5 while, successively including diffusion layer 7, carbon based layer
10th, carbon cloth 11 and Catalytic Layer 6；The thickness of diffusion layer 7 is 0.08 ~ 0.12mm；The thickness of Catalytic Layer 6 is 0.04 ~ 0.06mm.
Embodiment 1
1st, the preparation of cathode composite
（1）The pre-oxidation of graphite：Under the conditions of ice-water bath, the 30mL concentrated sulfuric acids, 6g potassium peroxydisulfates and 4g graphite are separately added into
Powder, is well mixed and after dissolving, in 80 DEG C of stirred in water bath reaction 6h, and adds the dilution of 2000ml pure water, micro- using 0.45 afterwards
After rice filter membrane suction filtration, freezing 6h, it is positioned in freeze drying box and dries 36h, that is, obtains pre-oxidizing graphite；
（2）The preparation of graphene oxide：
Under the conditions of ice-water bath, concentrated sulfuric acid 23ml, sodium nitrate 0.5g and obtained pre-oxidation graphite 0.5g are added, magnetic force is stirred
Mix and 20min is dissolved on device；
0.3g potassium permanganate is slowly added to every 5min, is added altogether after 3g, mixed solution is under the conditions of 35 DEG C, and water-bath is stirred
Mix 60min formation underflows；
40ml deionized waters, 90 DEG C of stirred in water bath 35min are added in underflow；100ml deionized waters are added, stirring is equal
After even, 3ml 30wt% hydrogen peroxide is slowly added to, mixed liquor bubble occurs and is changed into yellow；
By mixed liquor with after 5wt% hydrochloric acid centrifuge washing 3 times, then with deionized water centrifuge washing 4 times, in 60 DEG C of drying boxes
After middle dry 40h, graphene oxide is obtained；
（3）The preparation of cathode composite：
0.64g, 0.24g, 0.107g and 0.04g is taken to be added in 250ml deionized waters respectively graphene oxide, ultrasound
30min is handled, solution is obtained；
Take respectively again after the 20ml 0.1mol/L boric acid mixing of ammonium titanium fluoride and 20ml 0.3mol/L, add solution
In, after stirring 15min, solution closes heating 2h in 60 DEG C of water-baths, obtains solidliquid mixture；
Obtained solidliquid mixture is washed with sediment is obtained after 0.45 micron of membrane filtration, in 50 DEG C of vacuum drying
18h is dried in case, dried solid heats 1h at 200 DEG C, obtains cathode composite, respectively 20wt%TiO2/RGO、
40wt%TiO2/RGO、60wt%TiO2/ RGO and 80wt%TiO2/RGO；
（4）The preparation of cathode electrode：
By 1.56mg/cm2Ratio, acetylene black is added in 40wt% PTFE solution, after vortex 20s, small brushes are used
Mixed liquor is uniformly applied on carbon cloth, after being air-dried in fume hood, in being heated on 370 DEG C of refractory ceramics plates after 25min, is made
Carbon based layer；
60wt% PTFE solution is uniformly applied in carbon based layer with small brushes, after being air-dried in fume hood, in 370 DEG C
25min is heated on refractory ceramics plate；Repeat above step 3 times, form 4 layers of PTFE coatings, diffusion layer, the thickness of diffusion layer is made
For 0.10mm；
Obtained cathode composite is added in acetylene black, relative solid is sequentially added and mixes amount of substance 0.83ul/mg
Deionized water, 6.67ul/mg Nafion solution and 3.33ul/mg aqueous isopropanol, it is compound by negative electrode after vortex 20s
The coating weight 0.5mg/cm of material and acetylene black on carbon cloth2Ratio, the one of diffusion layer phase pair is uniformly applied to small brushes
Side, standby after dry 24h in fume hood, the thickness of gained Catalytic Layer is 0.04mm；Obtained cathode electrode be respectively containing
20wt%TiO2/RGO、40wt%TiO2/RGO、60wt%TiO2/ RGO and 80wt%TiO2/ RGO cathode electrode.
2nd, the assembling and startup of microbiological fuel cell
By Fig. 1 structural representations, the cathode electrode of preparation is embedded in the locular wall of anode chamber side, anode electrode has been placed in
Machine glass reactor（Dischargeable capacity is 343ml）At the 1/3 of cathode electrode, added in the middle of cathode electrode and anode electrode
PEM；Respectively through hydrogen peroxide before PEM addition（20wt%）, deionized water, sulfuric acid（0.5mol/L）With go
Ionized water 1h boils processing；Total electrode effective area of anode electrode and cathode electrode is 25cm2；Silver/silver chloride reference electrode
Insert in anode chamber；
Anode electrode and cathode electrode are passed through into wire and external 0 ~ 1000 ohm of change resistant series, data acquisition unit
（The types of Keithley 2007）It is in parallel with external resistance, and silver/silver chloride reference electrode is accessed into external circuit；
In start-up course, the 50mmol/L of sodium acetate phosphate buffer solution is added in anode chamber（pH=7.0）Anode
Liquid；0.31g ammonium chlorides, 2.452g hypophosphite monohydrates sodium dihydrogen, 4.576g disodium hydrogen phosphates and 0.13g chlorine are added in every liter of buffer solution
Change potassium.By anolyte and cultured sludge, in mass ratio 3.5:1 is added in anode chamber, and oxygen is caught up with by high pure nitrogen
30min, keeps anaerobic state；Sludge is derived from Guangzhou LiKau sewage treatment plants Aerobic Pond and anaerobic pond mixing sludge.
Intermittent duty is carried out at ambient temperature, and cell voltage passes through data acquisition unit（The types of Keithley 2007）Automatically
It recorded in computer；When the voltage of microbiological fuel cell reactor is less than 50mV, new anolyte is used instead, when voltage reaches
To when stablizing, start successfully.
3rd, the electricity generation performance test of microbiological fuel cell
Microbiological fuel cell monitors the output voltage of battery in real time after startup（Fig. 2）, voltage output maximum
It is containing 20%TiO2/ RGO battery, voltage reaches 298mV.
It is sufficient in organic matter, when electricity generation ability is maximum, by changing the size of external resistance, 10 Ω are reduced to from 9999 Ω,
The change of monitoring cell output voltage, obtains the polarization curve and power density curve of battery respectively such as Fig. 3 and Fig. 4 institutes in real time
Show, from Fig. 3 and Fig. 4, the maximum open circuit voltage and maximum power density of microbiological fuel cell be respectively 422.3mV and
1226.9mW/m2。
Embodiment 2
1st, the preparation of cathode composite
（1）The pre-oxidation of graphite：Under the conditions of ice-water bath, be separately added into the 30mL concentrated sulfuric acids, 6.67g potassium peroxydisulfates and
3.67g graphite powders, are well mixed and after dissolving, in 80 DEG C of stirred in water bath reaction 6h, and add the dilution of 2000ml pure water, make afterwards
With 0.45 micron membrane filter suction filtration, freeze after 6h, be positioned in freeze drying box and dry 36h, that is, obtain pre-oxidizing graphite；
（2）The preparation of graphene oxide：
Under the conditions of ice-water bath, concentrated sulfuric acid 23ml, sodium nitrate 0.5g and obtained pre-oxidation graphite 0.5g are added, magnetic force is stirred
Mix and 20min is dissolved on device；
0.3g potassium permanganate is slowly added to every 5min, is added altogether after 3g, mixed solution is under the conditions of 30 DEG C, and water-bath is stirred
Mix 70min formation underflows；
40ml deionized waters, 95 DEG C of stirred in water bath 30min are added in underflow；100ml deionized waters are added, stirring is equal
After even, 3ml 30wt% hydrogen peroxide is slowly added to, mixed liquor bubble occurs and is changed into yellow；
By mixed liquor with after 5wt% hydrochloric acid centrifuge washing 3 times, then with deionized water centrifuge washing 7 times, in 60 DEG C of drying boxes
After middle dry 40h, graphene oxide is obtained；
（3）The preparation of cathode composite：
0.64g, 0.24g, 0.107g and 0.04g is taken to be added in 250ml deionized waters respectively graphene oxide, ultrasound
40min is handled, solution is obtained；
Take respectively again after the 20ml 0.1mol/L boric acid mixing of ammonium titanium fluoride and 20ml 0.3mol/L, add solution
In, after stirring 10min, solution closes heating 2h in 60 DEG C of water-baths, obtains solidliquid mixture；
Obtained solidliquid mixture is washed with sediment is obtained after 0.45 micron of membrane filtration, in 60 DEG C of vacuum drying
16h is dried in case, dried solid heats 1h at 200 DEG C, obtains cathode composite, respectively 20wt%TiO2/RGO、
40wt%TiO2/RGO、60wt%TiO2/ RGO and 80wt%TiO2/RGO；
（4）The preparation of cathode electrode：
By 1.56mg/cm2Ratio, acetylene black is added in 40wt% PTFE solution, after vortex 20s, small brushes are used
Mixed liquor is uniformly applied on carbon cloth, after being air-dried in fume hood, in being heated on 370 DEG C of refractory ceramics plates after 25min, is made
Carbon based layer；
60wt% PTFE solution is uniformly applied in carbon based layer with small brushes, after being air-dried in fume hood, in 370 DEG C
25min is heated on refractory ceramics plate；Repeat above step 3 times, form 4 layers of PTFE coatings, diffusion layer, the thickness of diffusion layer is made
For 0.12mm；
Obtained cathode composite is added in acetylene black, relative solid is sequentially added and mixes amount of substance 0.83ul/mg
Deionized water, 6.67ul/mg Nafion solution and 3.33ul/mg aqueous isopropanol, it is compound by negative electrode after vortex 20s
The coating weight 0.5mg/cm of material and acetylene black on carbon cloth2Ratio, the one of diffusion layer phase pair is uniformly applied to small brushes
Side, standby after dry 24h in fume hood, the thickness of gained Catalytic Layer is 0.05mm；Obtained cathode electrode be respectively containing
20wt%TiO2/RGO、40wt%TiO2/RGO、60wt%TiO2/ RGO and 80wt%TiO2/ RGO cathode electrode.
2nd, the assembling and startup of microbiological fuel cell
By Fig. 1 structural representations, the cathode electrode of preparation is embedded in the locular wall of anode chamber side, anode electrode has been placed in
Machine glass reactor（Dischargeable capacity is 343ml）At the 1/3 of cathode electrode, added in the middle of cathode electrode and anode electrode
PEM；Respectively through hydrogen peroxide before PEM addition（20wt%）, deionized water, sulfuric acid（0.5mol/L）With go
Ionized water 1h boils processing；Total electrode effective area of anode electrode and cathode electrode is 25cm2；Silver/silver chloride reference electrode
Insert in anode chamber；
Anode electrode and cathode electrode are passed through into wire and external 0 ~ 1000 ohm of change resistant series, data acquisition unit
（The types of Keithley 2007）It is in parallel with external resistance, and silver/silver chloride reference electrode is accessed into external circuit；
In start-up course, the 50mmol/L of sodium acetate phosphate buffer solution is added in anode chamber（pH=7.0）Anode
Liquid；0.31g ammonium chlorides, 2.452g hypophosphite monohydrates sodium dihydrogen, 4.576g disodium hydrogen phosphates and 0.13g chlorine are added in every liter of buffer solution
Change potassium.By anolyte and cultured sludge, in mass ratio 3.5:1 is added in anode chamber, and oxygen is caught up with by high pure nitrogen
30min, keeps anaerobic state；Sludge is derived from Guangzhou LiKau sewage treatment plants Aerobic Pond and anaerobic pond mixing sludge.
Intermittent duty is carried out at ambient temperature, and cell voltage passes through data acquisition unit（The types of Keithley 2007）Automatically
It recorded in computer；When the voltage of microbiological fuel cell reactor is less than 50mV, new anolyte is used instead, when voltage reaches
To when stablizing, start successfully.
3rd, the electricity generation performance test of microbiological fuel cell
Microbiological fuel cell after startup, is monitoring the output voltage of battery in real time, and voltage output maximum is to contain
There is 20%TiO2/ RGO battery, voltage reaches 286mV.
It is sufficient in organic matter, when electricity generation ability is maximum, by changing the size of external resistance, 10 Ω are reduced to from 9999 Ω,
The change of monitoring cell output voltage in real time, obtains the maximum open circuit voltage and maximum power density difference of microbiological fuel cell
For 410.5mV and 1173.7mW/m2。
Embodiment 3
1st, the preparation of cathode composite
（1）The pre-oxidation of graphite：Under the conditions of ice-water bath, the 30mL concentrated sulfuric acids, 5g potassium peroxydisulfates and 4.58g stones are separately added into
Ink powder, is well mixed and after dissolving, in 80 DEG C of stirred in water bath reaction 6h, and adds the dilution of 2000ml pure water, afterwards using 0.45
After micron membrane filter suction filtration, freezing 6h, it is positioned in freeze drying box and dries 36h, that is, obtains pre-oxidizing graphite；
（2）The preparation of graphene oxide：
Under the conditions of ice-water bath, concentrated sulfuric acid 23ml, sodium nitrate 0.5g and obtained pre-oxidation graphite 0.5g are added, magnetic force is stirred
Mix and 20min is dissolved on device；
0.3g potassium permanganate is slowly added to every 5min, is added altogether after 3g, mixed solution is under the conditions of 40 DEG C, and water-bath is stirred
Mix 50min formation underflows；
40ml deionized waters, 85 DEG C of stirred in water bath 40min are added in underflow；100ml deionized waters are added, stirring is equal
After even, 3ml 30wt% hydrogen peroxide is slowly added to, mixed liquor bubble occurs and is changed into yellow；
By mixed liquor with after 5wt% hydrochloric acid centrifuge washing 3 times, then with deionized water centrifuge washing 6 times, in 60 DEG C of drying boxes
After middle dry 40h, graphene oxide is obtained；
（3）The preparation of cathode composite：
0.64g, 0.24g, 0.107g and 0.04g is taken to be added in 250ml deionized waters respectively graphene oxide, ultrasound
35min is handled, solution is obtained；
Take respectively again after the 20ml 0.1mol/L boric acid mixing of ammonium titanium fluoride and 20ml 0.3mol/L, add solution
In, after stirring 20min, solution closes heating 2h in 60 DEG C of water-baths, obtains solidliquid mixture；
Obtained solidliquid mixture is washed with sediment is obtained after 0.45 micron of membrane filtration, in 70 DEG C of vacuum drying
14h is dried in case, dried solid heats 1h at 200 DEG C, obtains cathode composite, respectively 20wt%TiO2/RGO、
40wt%TiO2/RGO、60wt%TiO2/ RGO and 80wt%TiO2/RGO；
（4）The preparation of cathode electrode：
By 1.56mg/cm2Ratio, acetylene black is added in 40wt% PTFE solution, after vortex 20s, small brushes are used
Mixed liquor is uniformly applied on carbon cloth, after being air-dried in fume hood, in being heated on 370 DEG C of refractory ceramics plates after 25min, is made
Carbon based layer；
60wt% PTFE solution is uniformly applied in carbon based layer with small brushes, after being air-dried in fume hood, in 370 DEG C
25min is heated on refractory ceramics plate；Repeat above step 3 times, form 4 layers of PTFE coatings, diffusion layer, the thickness of diffusion layer is made
For 0.08mm；
Obtained cathode composite is added in acetylene black, relative solid is sequentially added and mixes amount of substance 0.83ul/mg
Deionized water, 6.67ul/mg Nafion solution and 3.33ul/mg aqueous isopropanol, it is compound by negative electrode after vortex 20s
The coating weight 0.5mg/cm of material and acetylene black on carbon cloth2Ratio, the one of diffusion layer phase pair is uniformly applied to small brushes
Side, standby after dry 24h in fume hood, the thickness of gained Catalytic Layer is 0.06mm；Obtained cathode electrode be respectively containing
20wt%TiO2/RGO、40wt%TiO2/RGO、60wt%TiO2/ RGO and 80wt%TiO2/ RGO cathode electrode.
2nd, the assembling and startup of microbiological fuel cell
By Fig. 1 structural representations, the cathode electrode of preparation is embedded in the locular wall of anode chamber side, anode electrode has been placed in
Machine glass reactor（Dischargeable capacity is 343ml）At the 1/3 of cathode electrode, added in the middle of cathode electrode and anode electrode
PEM；Respectively through hydrogen peroxide before PEM addition（20wt%）, deionized water, sulfuric acid（0.5mol/L）With go
Ionized water 1h boils processing；Total electrode effective area of anode electrode and cathode electrode is 25cm2；Silver/silver chloride reference electrode
Insert in anode chamber；
Anode electrode and cathode electrode are passed through into wire and external 0 ~ 1000 ohm of change resistant series, data acquisition unit
（The types of Keithley 2007）It is in parallel with external resistance, and silver/silver chloride reference electrode is accessed into external circuit；
In start-up course, the 50mmol/L of sodium acetate phosphate buffer solution is added in anode chamber（pH=7.0）Anode
Liquid；0.31g ammonium chlorides, 2.452g hypophosphite monohydrates sodium dihydrogen, 4.576g disodium hydrogen phosphates and 0.13g chlorine are added in every liter of buffer solution
Change potassium.By anolyte and cultured sludge, in mass ratio 3.5:1 is added in anode chamber, and oxygen is caught up with by high pure nitrogen
30min, keeps anaerobic state；Sludge is derived from Guangzhou LiKau sewage treatment plants Aerobic Pond and anaerobic pond mixing sludge.
Intermittent duty is carried out at ambient temperature, and cell voltage passes through data acquisition unit（The types of Keithley 2007）Automatically
It recorded in computer；When the voltage of microbiological fuel cell reactor is less than 50mV, new anolyte is used instead, when voltage reaches
To when stablizing, start successfully.
3rd, the electricity generation performance test of microbiological fuel cell
Microbiological fuel cell after startup, is monitoring the output voltage of battery in real time, and voltage output maximum is to contain
There is 20%TiO2/ RGO battery, voltage reaches 294mV.
It is sufficient in organic matter, when electricity generation ability is maximum, by changing the size of external resistance, 10 Ω are reduced to from 9999 Ω,
The change of monitoring cell output voltage in real time, obtains the maximum open circuit voltage and maximum power density difference of microbiological fuel cell
For 417.2mV and 1257.6mW/m2。
Claims (4)
1. a kind of microbiological fuel cell reactor, it is characterised in that be single-chamber microbial fuel cell, including sample adding mouth
（1）, silver/silver chloride reference electrode（2）, data acquisition unit（3）, external resistance（4）, PEM（5）, cathode electrode, anode
Room（8）And anode electrode（9）；
The cathode electrode is embedded in anode chamber（8）On the locular wall of side, and there is one side directly to be contacted with air, another side and proton
Exchange membrane（5）Directly contact；The PEM（5）In anode chamber, and there are one side and the negative electrode being embedded on anode locular wall
Electrode is directly contacted, another side and anode chamber（8）Interior anolyte contact；The anode electrode（9）In anode chamber（8）It is interior close
At the 1/3 of cathode electrode；The sampling adding mouth（1）In anode chamber（8）Top；The silver/silver chloride reference electrode（2）Insert
Enter anode chamber（8）It is interior, and be connected by wire with external circuit；The cathode electrode and anode electrode（9）Pass through wire and dispatch from foreign news agency
Resistance（4）Series connection；The data acquisition unit（3）With external resistance（4）It is in parallel；
The cathode electrode is air electrode, mixes back loading with acetylene black by cathode composite and is obtained on carbon cloth；It is described
Cathode electrode by the one side with air contact to and PEM（5）The one side of contact, successively including diffusion layer（7）, it is carbon-based
Layer（10）, carbon cloth（11）And Catalytic Layer（6）.
2. a kind of microbiological fuel cell reactor according to claim 1, it is characterised in that the diffusion layer（7）'s
Thickness is 0.08 ~ 0.12mm.
3. a kind of microbiological fuel cell reactor according to claim 1, it is characterised in that the Catalytic Layer（6）'s
Thickness is 0.04 ~ 0.06mm.
4. a kind of microbiological fuel cell reactor according to claim 1, it is characterised in that the anode electrode（9）
Material be carbon felt；The anode electrode（9）With the electrode gross area of cathode electrode and anode chamber（8）Volume ratio be 1:
8.7cm2/cm3。
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| CN108808015A (en) * | 2018-05-21 | 2018-11-13 | 南昌航空大学 | A kind of polyaniline/reduced graphene/TiO2The synthetic method of material and its application |
| CN114524493A (en) * | 2022-01-25 | 2022-05-24 | 中南大学 | Ammonia recovery device and method for electrochemically treating nitrate wastewater |
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| CN114524493A (en) * | 2022-01-25 | 2022-05-24 | 中南大学 | Ammonia recovery device and method for electrochemically treating nitrate wastewater |
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