CN101447570A - Iron ion circulating electrode and preparation method thereof - Google Patents
Iron ion circulating electrode and preparation method thereof Download PDFInfo
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- CN101447570A CN101447570A CNA2007101954055A CN200710195405A CN101447570A CN 101447570 A CN101447570 A CN 101447570A CN A2007101954055 A CNA2007101954055 A CN A2007101954055A CN 200710195405 A CN200710195405 A CN 200710195405A CN 101447570 A CN101447570 A CN 101447570A
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- Y02E60/30—Hydrogen technology
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Abstract
The invention provides an iron ion circulating electrode which contains ferric sulfate, graphite powder, kaolin and nickelous chloride and has a porous structure. The invention also provides a method for preparing the iron ion circulating electrode, which comprises the steps: the graphite powder, the ferric sulfate, the kaolin, the nickelous chloride and pore creating material are mixed together for ball milling, and then the mixture processed by ball milling is pressed for forming under the pressure intensity of 10-30kgf/cm<2>; after that, the formed mixture is calcined for 8-15 hours at the temperature of 1000-1200 DEG C in shielding gas atmosphere. Compared with the existing iron ion circulating electrode, the iron ion circulating electrode (especially prepared by the method of the invention) can be taken as the cathode of a microbiological fuel cell, so as to remarkably improve the output power density of the microbiological fuel cell.
Description
Technical field
The present invention relates to iron ion circulating electrode and preparation method thereof.
Background technology
The major function of microorganism fuel cell cathode is under the effect of catalyst electron transport to be finished reduction half-reaction, i.e. O to electron acceptor
2+ 4H
++ 4e
-→ 2H
2O.The loss of voltage that negative electrode and cathode chamber cause mainly concentrates on activation loss and mass transport losses two parts, and wherein activation loss is relevant with catalyst, and mass transport losses is relevant with the electron acceptor kind with proton transfer.It is base material that negative electrode adopts carbon cloth or carbon paper usually, spray or adopt screen printing technique attached on the negative electrode catalyst, catalyst can reduce the activation energy of cathode reaction, fast reaction speed, reduce electrochemical activation resistance, at present, mainly to adopt carbon to carry platinum be catalyst to the negative electrode of microbiological fuel cell.Proton is one of reactant that participates in cathode reaction, the speed of its transmission speed directly has influence on cathode reaction, the resistance to mass tranfer that reduces in the negative electrode can reduce the loss of voltage, for example the adhesive that replaces polytetrafluoroethylene (PTFE) to do cathod catalyst with Nafion has reduced the resistance to mass tranfer of proton in negative electrode, reduce the internal resistance of cell, improved battery performance.The kind of electron acceptor also is one of key factor that influences cathode reaction, and the most frequently used electron acceptor is O at present
2, be divided into two kinds of gaseous oxygen and oxygen in water, but dissolved oxygen solubility in water being little and diffusion velocity is slow, in order to improve dissolved oxygen amount, when battery operated, also need blast by corresponding pump, consumed a large amount of electric energy.
Just be based on the relatively little problem of solubility of costliness and oxygen of metal platinum, occurring utilizing the microbiological fuel cell of iron ion circulating electrode now, this battery utilization is exposed to airborne iron ion circulating electrode as cell cathode.As shown in Figure 1, the electronics (representing with e Fig. 1) that comes from the external circuit transmission and transmit the proton that comes from the anode chamber and (use H Fig. 1
+Expression) arrives cathode electrode plate, Fe
3+Be reduced to Fe as electron acceptor
2+, because cathode electrode plate is to be exposed in the air Fe
2+Be Fe by dioxygen oxidation again afterwards
3+, electronics then finally transmits oxygen supply and proton and generates water.Like this, on cathode electrode plate, form the circulation of an iron ion, quickened the transfer rate of electronics, reduced the resistance that causes by mass transfer.For example, DooHyun Park and J.Gregory Zeiku disclose a kind of iron ion cycle battery, this iron ion cycle battery is made up of the ferric sulfate of 3 weight %, the fine graphite powders of 60 weight %, kaolin (particle is less than 400 orders) and the nickel chloride of 1 weight % of 36 weight %, the preparation method is: the mixture that contains said components of 2 weight portions and the distilled water of 1 weight portion are stirred, put into mould then, at 1.0kg/cm
2Pressure under make the thin plate of 20 * 20 * 1cm, with described thin plate at room temperature dry 48 hours, and feeding N
212 hours (Doo Hyun Park of the following 1100 ℃ of calcinings of the anaerobic environment of gas, J.Gregory Zeiku.Improved fuel cell and electrode designs for producing electricity from microbialdegradation.Biotechnology and Bioengineering, 2003,81 (3): 348-355).Yet during as the negative electrode of microbiological fuel cell, the output power density of battery is lower with above-mentioned iron ion circulating electrode.
Summary of the invention
The objective of the invention is for overcome with existing iron ion circulating electrode as the microbiological fuel cell of negative electrode the lower defective of output power density, provide a kind of and can make iron ion circulating electrode that microbiological fuel cell has higher output power density and preparation method thereof.
Iron ion circulating electrode provided by the invention contains ferric sulfate, graphite powder, kaolin and nickel chloride, and this electrode is a loose structure.
The method of the described iron ion circulating electrode of preparation provided by the invention comprises: graphite powder, ferric sulfate, kaolin, nickel chloride and pore creating material are mixed the back ball milling, then with the mixture behind the ball milling at 10-30kgf/cm
2Pressure under compression moulding; In protective atmosphere, calcined 8-15 hour under 1000-1200 ℃ then.
With respect to existing iron ion circulating electrode, utilize the negative electrode of (method preparation especially provided by the invention) provided by the invention iron ion circulating electrode as microbiological fuel cell, significantly improved the output power density of microbiological fuel cell.
Description of drawings
Fig. 1 is the operation principle schematic diagram of iron ion circulating electrode;
Fig. 2 is a kind of method flow diagram for preparing iron ion circulating electrode of the present invention;
Fig. 3 is the schematic diagram of a kind of microbiological fuel cell provided by the invention.
Embodiment
The invention provides a kind of iron ion circulating electrode, this electrode contains ferric sulfate, graphite powder, kaolin and nickel chloride, and this electrode is a loose structure, and the cumulative volume of hole can be the 10-15% of described electrode cumulative volume.
Wherein, the average pore diameter of described hole can be the 50-100 micron.
Wherein, be benchmark with the graphite powder of 100 weight portions, the content of ferric sulfate can be the 3-8 weight portion, and kaolinic content can be the 50-70 weight portion, and the content of nickel chloride can be the 1-3 weight portion.
The present invention also provides a kind of method of making described iron ion circulating electrode, and this method comprises: graphite powder, ferric sulfate, kaolin, nickel chloride and pore creating material are mixed the back ball milling, then with the mixture behind the ball milling at 10-30kgf/cm
2Pressure under compression moulding; In protective atmosphere, calcined 8-15 hour under 1000-1200 ℃ then.
Wherein, be benchmark with the graphite powder of 100 weight portions, the consumption of ferric sulfate can be the 3-8 weight portion, and kaolinic consumption can be the 50-70 weight portion, and the consumption of nickel chloride can be the 1-3 weight portion, and the consumption of pore creating material can be the 1-3 weight portion.
Wherein, this method can also be included in the mixture behind the ball milling and add organic solvent, is benchmark with the graphite powder of 100 weight portions, and the consumption of organic solvent can be the 1-10 weight portion.Described organic solvent can be the organic solvent of routine, for example can be for being selected from white oil, silicone oil, atoleine, propyl alcohol, polyethylene glycol and the chloroform one or more.
Wherein, described pore creating material can be the volatilization temperature of the routine pore creating material less than 1000 ℃, for example can be for being selected from polyvinyl alcohol, Tissuemat E, polyvinyl chloride and the polyethylene one or more.
Wherein, the average grain diameter of described pore creating material can be 50-100 μ m, is the hole of 50-100 μ m so that form average diameter, and kaolin can be the 300-600 order, and graphite powder can be the 300-500 order.
Wherein, described protective atmosphere can be the inert gas of routine, for example can be nitrogen and/or argon gas; Described calciner plant can be the calciner of routine, for example can be Muffle furnace.
The following examples are used for that the present invention will be further described.
This embodiment is used to illustrate the preparation method of iron ion circulating electrode provided by the invention.
The operating process of this embodiment as shown in Figure 2.With 15 gram ferric sulfate, 300 grams, 400 purpose graphite powders, 175 grams, 500 purpose kaolin, 5 gram nickel chlorides and 5 gram diameters is that the polyethenol pellets of 80 μ m mixes after ball mill ball milling two angel's powder mix, then dry powder directly being put into a diameter of section is 8cm, high for the cylindrical die of 9cm, at 20kgf/cm
2It is 8cm that (kilogram/square centimeter) pressure depresses to diameter, thickness is the circular sheet of 5mm, the thin plate that is pressed into is placed Muffle furnace, feed nitrogen, in temperature is 1100 ℃ of following constant temperature calcination 12 hours, make iron ion circulating electrode, be cut into the cuboid electrode at last, be of a size of 50mm * 50mm * 5mm.
Measure the cumulative volume of sample (iron ion circulating electrode) hole and the ratio (%) of described sample cumulative volume according to following method:
1) sample is placed electrically heated drying cabinet under 70 ℃, dry, take out then and place drier to constant weight.
2) dry sample is accurately weighed on balance, be accurate to 0.01 gram.Obtain G1.
3) make the sample hole fully by water saturation with vacuumizing method.
Sample is put into clean beaker and placed vacuum desiccator, be evacuated to residual pressure less than 10 millimetress of mercury, kept 30 minutes, move the liquid funnel and put into distilled water by suitable for reading dress of vacuum desiccator then, flood fully up to sample, be pumped to again when no bubble occurs on the sample and can stop.
Above-mentioned saturated sample is put into the copper wire basket, be suspended in the container of topping-up of carry potential overflow pipe, the weight of weighing saturated sample in water is accurate to 0.01 gram.Obtain G3.
Take out saturated sample from water, the multilayer gauze with being full of water dabs off the specimen surface superfluous water (not answering the water in the sucking-off sample hole), and the aerial weight of weighing saturated sample is accurate to 0.01 gram rapidly.Obtain G2.
And calculate porosity according to the following equation:
q＝(G2-G1/G2-G3)×100
The apparent porosity of q sample (%)
The dry weight of G1 sample (gram)
The aerial weight of G2 saturated sample (gram)
The weight (gram) of G3 saturated sample in water
The cumulative volume that records hole according to the method described above is 12% of a described electrode cumulative volume.
This embodiment is used to illustrate the preparation method of iron ion circulating electrode provided by the invention.
Different with example 1 is, with 5 gram diameters is that to replace with 8 gram diameters be the polyethylene bead of 60 μ m for the polyethenol pellets of 80 μ m, and add 15 gram chloroforms behind the ball milling in mixture, put into mould after mixing again, other operating condition is identical with embodiment 1 with step.15% of the electrode cumulative volume that the cumulative volume that records hole according to embodiment 1 described method makes for this embodiment.
Comparative Examples 1
This Comparative Examples is used to illustrate the preparation method of existing iron ion circulating electrode.
Different with example 1 is, does not add polyethenol pellets, adds 15 gram distilled water behind the ball milling in mixture, puts into mould after mixing again, and other operating condition is identical with embodiment 1 with step.0.2% of the electrode cumulative volume that the cumulative volume that records hole according to embodiment 1 described method makes for this Comparative Examples.
This embodiment is used to illustrate that the iron ion circulating electrode that makes with embodiment 1 prepares the method for microbiological fuel cell as negative electrode.
As shown in Figure 3, to be of a size of the anode chamber of the cuboid polymethyl methacrylate container of 15cm (length) * 12cm (wide) * 8cm (height) as battery, the container top is dismountable cover plate, have 8 apertures on the cover plate, wherein 3 is electrode cable outlets (6 wire outlets), the 1st, gas feed, the 2nd, gas vent.Open the square window 6 of a step in a side of container, its outer dimension is 5cm, nexine is of a size of 4cm, 4 screws are set around window, utilize described screw, the iron ion circulating electrode that embodiment 1 is made is fixed on the window 6 as negative electrode, uses proton exchange membrane 5 (Nafion-117 between cathode electrode plate 4 and the anode chamber 8, Dupont) be separated by, keep sealing with vacuum pad between proton exchange membrane 5 and the cathode electrode plate 4.Wherein, proton exchange membrane is used before successively at 30%H
2O
2, deionized water, 0.5mol/L H
2SO
4And respectively boiled 1 hour in the deionized water, be kept in the deionized water.Anode electrode is installed in the position shown in 7, wherein, anode electrode is unpolished high purity graphite electrode, graphite electrode is of a size of 50mm * 50mm * 5mm, anode electrode soaks with 1mol/L HCl before use removes foreign ion, soaks to remove the bacterium of its surface adsorption with 1mol/L NaOH after the use again.1 liter of culture medium (as shown in table 1) is injected the anode chamber, load onto behind the cover plate N
2-CO
2(volume ratio is 80:20) gaseous mixture is the feeding anode chamber, mixed cellulose ester microporous membrane filtration back of 0.45 μ m by the aperture, to eliminate the oxygen in the culture medium, use syringe then, inject 10 milliliters of Rhodoferaxferrireducens (metal alienation reduction bacterium) bacterium liquid (10 by 2 mouthfuls
8Individual/milliliter), continue the anode chamber and slowly feed described gaseous mixture, and slowly stir the anode chamber.
Table 1
| Culture medium is formed | The content of each part in 1 liter of culture medium (solvent is a distilled water) |
| The basic inorganic salt part | KCl?0.1g，NH 4Cl?0.2g，NaH 2PO 4?0.6g，NaHCO 3?2.5g |
| Electron donor | Glucose 1.8 grams |
| Wolfe vitamin | Biotin ... ... ... ... ..2.0mg folic acid ... ... ... .2.0mg puridoxine hydrochloride ... .10.0mg thiamine hydrochloride ... ... ... 5.0mg riboflavin ... ... ... the .5.0mg niacinamide ... ... ... 5.0mg D-(+)-calcium pantothenate ... 5.0mg cobalamin ... ... ... the 0.1mg aminobenzoic acid ... ... the .5.0mg lipoic acid ... ... ... .5.0mg |
| The Wolfe mineral matter | Na
2SeO
3.................................10.0mg NiCl
2·6H
2O............................10.0mg complexon I ... ..1.5g MgSO
4·7H
2O.................3.0g MnSO
4.H
2O..................0.5g NaCl.........................1.0g FeSO
4·7H
2O.................0.1g CoCl
2·6H
2O.................0.1g CaCl
2........................0.1g ZnSO
4·7H
2O.................0.1g CuSO
4·5H
2O.................0.01g AlK(SO4)
2·12H
2O.............0.01g H
3BO
3........................0.01g Na
2 |
This embodiment is used to illustrate that the iron ion circulating electrode that makes with embodiment 2 prepares the method for microbiological fuel cell as negative electrode.
The iron ion circulating electrode that makes with embodiment 2 is as negative electrode as different from Example 3, and other step is identical with embodiment 3.
Comparative Examples 2
This embodiment is used to illustrate that the iron ion circulating electrode that makes with Comparative Examples 1 prepares the method for microbiological fuel cell as negative electrode.
The iron ion circulating electrode that makes with Comparative Examples 1 is as negative electrode as different from Example 3, and other step is identical with embodiment 3.
As shown in Figure 3, the battery that embodiment 3, embodiment 4 and Comparative Examples 2 are made records external resistance two ends ceiling voltage with voltage data collecting card 10 in being connected with 510 ohm the circuit of external resistance 9 respectively, and data are listed in the table below 2.
Table 2
| The negative electrode source | The battery source | Voltage (mv) |
| |
|
513.5 |
| |
|
365 |
| Comparative Examples 1 | Comparative Examples 2 | 203 |
More than the specification of all iron ion circulating electrode and battery all identical, external circuit is also identical, so the voltage that records is high more, the output power density that just shows battery is high more, therefore the magnitude of voltage from table 2 can be judged, with respect to existing iron ion circulating electrode, iron ion circulating electrode provided by the invention has improved the output power density of battery significantly as the negative electrode of microbiological fuel cell.
Claims (10)
1, a kind of iron ion circulating electrode, this electrode contains ferric sulfate, graphite powder, kaolin and nickel chloride, it is characterized in that: this electrode is a loose structure.
2, electrode according to claim 1, wherein, the cumulative volume of hole is the 10-15% of described electrode cumulative volume.
3, electrode according to claim 1 and 2, wherein, the average pore diameter of hole is the 50-100 micron.
4, electrode according to claim 1 wherein, is a benchmark with the graphite powder of 100 weight portions, and the content of ferric sulfate is the 3-8 weight portion, and kaolinic content is the 50-70 weight portion, and the content of nickel chloride is the 1-3 weight portion.
5, the preparation method of the described electrode of claim 1, this method comprises: graphite powder, ferric sulfate, kaolin, nickel chloride and pore creating material are mixed the back ball milling, then with the mixture behind the ball milling at 10-30kgf/cm
2Pressure under compression moulding; In protective atmosphere, calcined 8-15 hour under 1000-1200 ℃ then.
6, method according to claim 5 wherein, is a benchmark with the graphite powder of 100 weight portions, and the consumption of ferric sulfate is the 3-8 weight portion, and kaolinic consumption is the 50-70 weight portion, and the consumption of nickel chloride is the 1-3 weight portion, and the consumption of pore creating material is the 1-3 weight portion.
7, according to claim 5 or 6 described methods, wherein, described pore creating material is selected from one or more in polyvinyl alcohol, Tissuemat E, polyvinyl chloride and the polyethylene; The average grain diameter of pore creating material is the 50-100 micron.
8, method according to claim 5, wherein, this method also is included in the mixture behind the ball milling and adds organic solvent, is benchmark with the graphite powder of 100 weight portions, and the consumption of organic solvent is the 1-10 weight portion; Described organic solvent is selected from one or more in white oil, silicone oil, atoleine, propyl alcohol, polyethylene glycol and the chloroform.
9, according to claim 5 or 6 described methods, wherein said kaolin is the 300-600 order, and graphite powder is the 300-500 order.
10, method according to claim 5, wherein, described protective atmosphere is nitrogen and/or argon gas.
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|---|---|---|---|
| CNA2007101954055A CN101447570A (en) | 2007-11-27 | 2007-11-27 | Iron ion circulating electrode and preparation method thereof |
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|---|---|---|---|
| CNA2007101954055A CN101447570A (en) | 2007-11-27 | 2007-11-27 | Iron ion circulating electrode and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105776502A (en) * | 2016-01-06 | 2016-07-20 | 浙江工商大学 | Method for reducing CO2 by virtue of metal oxide modified biofilm electrode |
-
2007
- 2007-11-27 CN CNA2007101954055A patent/CN101447570A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105776502A (en) * | 2016-01-06 | 2016-07-20 | 浙江工商大学 | Method for reducing CO2 by virtue of metal oxide modified biofilm electrode |
| CN105776502B (en) * | 2016-01-06 | 2019-04-16 | 浙江工商大学 | A kind of metal oxide modified electrode biomembrane reduction CO2Method |
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Open date: 20090603 |