CN102324526A - Microbiological fuel cell composite material anode and its manufacturing method - Google Patents
Microbiological fuel cell composite material anode and its manufacturing method Download PDFInfo
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Abstract
The invention provides a microbiological fuel cell composite material anode and a manufacturing method thereof, and relates to a fuel cell composite material anode and a manufacturing method thereof, so that the problems of low electricity generation capacity and low removal rate of organic pollutant in water body or deposit can be solved. The anode is a compressing piece, the anode comprises a first wire mesh layer, a first non-metal sheet layer, a second wire mesh layer, a second non-metal sheet layer and a third wire mesh layer, the second non-metal sheet layer is positioned between the first wire mesh layer and the second wire mesh layer, the second non-metal sheet layer is arranged between the second wire mesh layer and the third wire mesh layer. The main steps for manufacturing the microbiological fuel cell composite material anode comprise: 1) irregularly etching the wire mesh, 2) performing a nitrocementation to liquid phase plasma, 3) compacting the material, 4) performing a carburization to liquid phase plasma, and 5) treating the composite material. The invention is used for power generation of the microbiological fuel cell and the organic pollutant in water body deposit removal.
Description
Technical field
The present invention relates to a kind of fuel cell composite material anode and manufacturing approach.
Background technology
At present; Many in the world countries all are faced with the severe problem of environmental pollution and energy crisis; Along with the research and development of global new forms of energy and sustainable energy, microbiological fuel cell (Microbial Fuel Cells, research MFC); The particularly research of anode of microbial fuel cell and negative electrode and manufacturing becomes the world today and solves one of important channel of environment and this two hang-up of energy crisis.As the MFC technology of handling pollutant and electrogenesis dual-use function; Receive the extensive concern of various countries; The electrogenesis effect of microbiological fuel cell and organic pollutant removal rate are the two big indexs in this field, and research both at home and abroad mostly is in scientific research or experimental stage, does not have substantial breakthrough.
MFC is the various materials that utilize in different carbohydrate and the waste water, carries out power conversion through microbial action, and the electric transmission that produces respiration is to cell membrane; Electronics is transferred to galvanic anode from cell membrane then; Through external circuit, the electronics on the anode arrives negative electrode, produces extrinsic current; Simultaneously the hydrogen ion that produces is delivered to negative electrode through PEM (PEM), at negative electrode proton and electronics, the oxygen generation water that reacts, the transmission of the interior electric charge of realization battery, thus accomplish whole bioelectrochemistry process and energy conversion process.Microbiological fuel cell is a kind of new technology that has combined waste water treatment and biological electrogenesis, can in the microbial degradation debirs, produce electric energy, and not discharge pollutants.
MFC utilizes in the whole process of organic substance electrogenesis, and what play a decisive role is the transmission of electronics in the anode region.In this process; It is the respiratory chain of utilizing in the microbiological oxidation metabolism that endocellular electricity shifts; Make electronics through nadh dehydrogenase, ubiquinone, ubiquinone, cytochromes etc.; Perhaps the hydrogenase on microbial film surface migrates out cell, then extracellular electronics also must through with the film hazardous substance, perhaps the solubility redox mediators is transferred on the electrode.
What of the final electricity generation ability of MFC the speed of transfer rate will influence, and selection of electrode materials has decisive influence to final production capacity efficient in the middle of the factor of transfer rate, and the absorption property of anode material and electric conductivity are leading indicators; Present anode material is a base material with conventional carbon mainly, comprises that the homogenous material of carbon paper, carbon cloth, graphite flake, graphite rod, carbon felt and foamy graphite is made, and to the exploitation dynamics of the modification of existing anode material and anode material not enough.
At present anode is mainly flat and two kinds of material filling types; The former shortcoming is to increase annode area must increase reactor volume; Be unfavorable for the microminiaturization exploitation of battery; Though and the latter can increase the surface area of microbial adhesion, with regard to the per surface microorganism electricity generation, both electricity generation performances do not have significant difference.
Discoveries such as Morozan, CNT and electrogenesis microbe have very high biocompatibility.Liang Peng etc. make anode material with CNT, activated carbon and flexible graphite respectively, measure its surface characteristic, electricity generation performance and power density, the maximum (402mW/m of power density when result's discovery is made anode with CNT
2).Flavine morals etc. are made anode with metals such as copper, aluminium, iron, find these metal electrode superior performances, biological excellent adsorption and with low cost.Yet these materials and method are in the experimental study stage, and the clearance of electrogenesis power and organic pollution is not improved significantly, and whole practical application is restricted.
In sum, the anode material structure of MFC and performance directly influence the microbiological fuel cell electricity generation ability and to the raising of the removal efficient of organic pollution: this mainly shows the anode conducting rate variance, electrode surface area is little, biocompatibility is poor, poor chemical stability, the electrogenesis microbial adhesion is few and electronics between microbe and anode, to transmit resistance big; Modification to the MFC anode; Look for the material that has living things catalysis property and biocompatibility concurrently; And with it and typical electrode materials is fixed and the research of MFC high performance anode material; Be to promote the extremely key that shifts of surface of electrons in the microbial cell, effectively improve the key of clearance of electricity generation performance and the organic pollution of MFC especially.
Summary of the invention
The objective of the invention is for solution microbiological fuel cell electricity generation ability is low, and to the low problem of organic pollutant removal rate in water body or the deposit, and then a kind of microbiological fuel cell composite material anode and manufacturing approach are provided.
The present invention addresses the above problem the technical scheme of taking to be:
A kind of microbiological fuel cell composite material anode of the present invention; Described anode is a kind of rolled-up stock; This anode comprises first oven wire mesh blanket, the first nonmetal flaggy, second oven wire mesh blanket, the second nonmetal flaggy and the 3rd oven wire mesh blanket; The second nonmetal flaggy is between first oven wire mesh blanket and second oven wire mesh blanket; The second nonmetal flaggy is arranged between second oven wire mesh blanket and the 3rd oven wire mesh blanket; All have nitriding and carburizing composite bed on the wire of described first oven wire mesh blanket, second oven wire mesh blanket and the 3rd oven wire mesh blanket; The material of the described first nonmetal flaggy and the second nonmetal flaggy is carbon-based material, and the aperture of the woven wire of described second oven wire mesh blanket is less than the aperture of the woven wire of first oven wire mesh blanket, and the aperture of the woven wire of second oven wire mesh blanket is less than the aperture of the woven wire of the 3rd oven wire mesh blanket.
A kind of manufacturing approach of described a kind of microbiological fuel cell composite material anode that realizes of the present invention realizes according to following steps: one, first oven wire mesh blanket, second oven wire mesh blanket and the 3rd oven wire mesh blanket carry out random etching processing respectively: first oven wire mesh blanket that will make, second oven wire mesh blanket and the 3rd oven wire mesh blanket water in advance are cleaned; First oven wire mesh blanket, second oven wire mesh blanket and the 3rd oven wire mesh blanket after cleaning are placed respectively on the anode in bipolar electrode etching reaction pond; In said reaction tank, add etching agent simultaneously; Keeping the anodic-cathodic spacing is 6～14cm; At voltage is 5～9V; Electric current is under 148～288A condition; Reaction 14min～58min, wherein etching agent is that the nitric acid by the hydrochloric acid of 1mol/L and 1mol/L is that 100: 2～100: 4 ratio is made into or mass percent concentration is 10% hydrofluoric acid by volume; Two, first oven wire mesh blanket that will be after step 1 is handled, second oven wire mesh blanket and the 3rd oven wire mesh blanket are after water cleans respectively, and air dry is again through acetone; Three, the two-way carbo-nitriding of liquid phase plasma electrolysis is handled: first oven wire mesh blanket, second oven wire mesh blanket and the 3rd oven wire mesh blanket after step 2 is handled are put into the plasma electrolysis pond respectively; Electrolyte is joined in the said electrolytic cell, is 0.9～1.1A/cm in current density
2, operating voltage is that 222～248V and electrolyte working temperature are under 22 ℃～43 ℃ the condition; Processing time is 3.2～4.8min, and described electrolyte is that 8.5: 0.5: 1 ratio is made into or is that 8.5: 0.5: 1 ratio is made into by urea, sodium chloride and water in mass ratio by urea, potassium chloride and water in mass ratio; Four, first oven wire mesh blanket, second oven wire mesh blanket and the 3rd oven wire mesh blanket water after step 3 is handled are cleaned, use alcohol wash again, air dry; Five, first oven wire mesh blanket, second oven wire mesh blanket and the 3rd oven wire mesh blanket that will be after step 4 is handled and the first nonmetal flaggy of having made and the second nonmetal flaggy formation pre-press that is stacked together in order; The order that stacks is successively: first oven wire mesh blanket, the first nonmetal flaggy, second oven wire mesh blanket, the second nonmetal flaggy and the 3rd oven wire mesh blanket; Through forcing press said pre-press is suppressed, when pressing pressure reaches 0.2～0.8MPa/cm
2The time, stop compacting, and, make semi-finished product the welding of adjacent metal silk screen; Six, the two-way Carburization Treatment of liquid phase plasma electrolysis, the semi-finished product that will make through step 5 are put into the plasma electrolysis pond, electrolyte joined in the said electrolytic cell, be 0.9～1.1A/cm in current density
2, operating voltage is that 222～248V and electrolyte working temperature are under 22 ℃～43 ℃ the condition; Processing time is 3.2～4.8min, and described electrolyte is that 8.5: 0.5: 1 ratio is made into or is that 8.5: 0.5: 1 ratio is made into by formamide, sodium chloride and water in mass ratio by formamide, potassium chloride and water in mass ratio; The composite material water that seven, will after step 6 is handled, obtain cleans, air dry, and excision forming promptly makes a kind of microbiological fuel cell composite material anode.
The invention has the beneficial effects as follows:
(1) have nitriding and carburizing composite bed on the wire of the woven wire of composite material anode of the present invention, the wire surface structure changed, help metal and carbon mutually, biophasic compatible; Help anode microbe electron transfer and reduce oxidizing potential; Increase the anode conducting rate, improve the oxidation reaction speed of microbe, non-metal carbon sill and woven wire mechanical compound at anode surface; Carbo-nitriding; Make metal the firm crimping of mechanicalness promptly arranged mutually, also have the plasma nanometer conduit micro-structural that common carburizing produces, greatly reduce the internal resistance of microbiological fuel cell with carbon-based material; Improve anode electron transport speed, improved the effect and the performance of integral composite.
(2) selection in inner layer metal silk screen aperture of the present invention and outer layer metal silk screen aperture; Guaranteed that integral material can give play to better microbial adhesion area and adhere to quantity; Increase electron transport speed, also make microbial bacterial can obtain more to mate the hole, inner layer metal silk screen aperture is smaller; Make carbon-based material layer and inner layer metal silk screen that more alternate the connection arranged, increase electron transport speed; Outer layer metal silk screen aperture is bigger, guarantees the firm of carbon-based material layer, also makes the carbon-based material layer have more surface area to contact with microbe simultaneously, guarantees the bond area of microbe at anode, has increased the adhesion amount of microbe on anode.
(3) woven wire of the present invention has been strengthened structure between austenite crystal through random etching processing, and the wire surface structure is changed, and has increased surface area, microstructure demonstrates the sharpening characteristic; Woven wire of the present invention is through two-way carbo-nitriding, and woven wire and compound, the two-way carburizing of non-metal carbon sill machinery are because the carburizing of oven wire mesh blanket and carbon-based material layer; The outer layer metal silk screen along with moving of plasma source, distributes because the inner layer metal silk screen has the gap proterties in carburizing process; The discharge source that makes diverse location can form different discharge angles, therefore corresponding to the same point wire; The infiltration of carbon source is that the multi-angle alternating expression takes place, and the conduction electrons that promptly has macroscopic view transmits directionality, has staggered, the tridimensional structure in microcosmic carbon nanochannel and hole again; The CNT of these microcosmic and hole are the bases of microbial adhesion; Also be that the basic condition that swift electron transmits takes place microbe, make metal the firm crimping of mechanicalness promptly arranged mutually, therefore with carbon back; Greatly reduce the anode internal resistance of microbiological fuel cell; The electronics that effectively raises microorganisms improves the oxidizing reaction rate of microbe at anode surface in carbon-based material and metal transfer rate mutually, has improved the effect and the performance of integral composite.
(4) performance of MFC has been optimized in the improvement of the formation of anode of the present invention and structure greatly, and the resistivity of composite material anode of the present invention is＜0.5 Ω mm, the specific area＞1.8m of composite material anode
2/ g applies to microbiological fuel cell (MFC) with composite material anode of the present invention, and power density reaches 4402mW/m
3, compare existing power density 402mW/m
2, power density is greatly improved; Be 72 hours the start-up time of MFC, compares 100～300 hours start-up times of existing MFC, improved 28%～76% start-up time, helps the quick performance of electrogenesis usefulness; Voltage peak is 8.32V, and the ability long-time steady operation, compares existing voltage peak 7V, and voltage peak has improved 18.9%; Electricity generation ability reaches 4009.6mW/m
3The BOD clearance is 90.5%, compares existing BOD clearance 82.5%, and clearance has improved 9.7%; Composite material anode of the present invention is applicable to the processing of organic pollution in the water body deposit of organic pollution in the large tracts of land water or sealing water body and different depth, and applicability is good, is fit to industrial applications.
Description of drawings
Fig. 1 is the overall structure front view of composite material anode of the present invention; Fig. 2 is the left view of Fig. 1; Fig. 3 is the vertical view of Fig. 1; Fig. 4 is the carbon carpet veneer surface electronic microphotograph figure of the composite material anode that makes of embodiment 16; Fig. 5 is the titanium silk screen layer electron micrograph figure of the composite material anode that makes of embodiment 16, and Fig. 6 is the carbon carpet veneer and the titanium silk screen layer interface electron micrograph figure of the composite material anode that makes of embodiment 16, and Fig. 7 is the carbon carpet veneer transmission electron microscope photo figure of the composite material anode that makes of embodiment 16.
Embodiment
Embodiment one: combine Fig. 1～Fig. 3 that this execution mode is described; A kind of microbiological fuel cell composite material anode of this execution mode is a kind of rolled-up stock; This anode comprises the nonmetal flaggy of first oven wire mesh blanket 1, first 2, second oven wire mesh blanket, 3, the second nonmetal flaggy 4 and the 3rd oven wire mesh blanket 5; The second nonmetal flaggy 2 is between first oven wire mesh blanket 1 and second oven wire mesh blanket 3; The second nonmetal flaggy 4 is arranged between second oven wire mesh blanket 3 and the 3rd oven wire mesh blanket 5; All have nitriding and carburizing composite bed on the wire of described first oven wire mesh blanket 1, second oven wire mesh blanket 3 and the 3rd oven wire mesh blanket 5; The material of the described first nonmetal flaggy 4 and the second nonmetal flaggy 5 is carbon-based material, and the aperture of the woven wire of described second oven wire mesh blanket 3 is less than the aperture of the woven wire of first oven wire mesh blanket 1, and the aperture of the woven wire of second oven wire mesh blanket 3 is less than the aperture of the woven wire of the 3rd oven wire mesh blanket 5.
The aperture of the woven wire of first oven wire mesh blanket 1 of this execution mode equates with the aperture of the woven wire of the 3rd oven wire mesh blanket 5 or is unequal.
Embodiment two: combine Fig. 2 and Fig. 3 that this execution mode is described, described second oven wire mesh blanket 3 of this execution mode is wherein a kind of in titanium silk screen layer, nickel oven wire mesh blanket, 316 stainless steel wire stratum reticulares or the 316L stainless steel wire stratum reticulare.So be provided with, can effectively improve the antiseptic power of product, be fit to the water body in different waters.Other is identical with embodiment one.
Embodiment three: combine Fig. 2 and Fig. 3 that this execution mode is described; The woven wire of described second oven wire mesh blanket 3 of this execution mode is the square hole net; The silk wiry footpath of second oven wire mesh blanket 3 is 0.5～5.0mm, and the aperture of the woven wire of second oven wire mesh blanket 3 is 3～30mm.So be provided with, meet design requirement.Other is identical with embodiment one or two.
Embodiment four: combine Fig. 2 and Fig. 3 that this execution mode is described, described first oven wire mesh blanket 1 of this execution mode is wherein a kind of in titanium silk screen layer, nickel oven wire mesh blanket, 316 stainless steel wire stratum reticulares or the 316L stainless steel wire stratum reticulare.So be provided with, can effectively improve the antiseptic power of product, be fit to the water body in different waters.Other is identical with embodiment one.
Embodiment five: combine Fig. 1～Fig. 3 that this execution mode is described, described the 3rd oven wire mesh blanket 5 of this execution mode is wherein a kind of in titanium silk screen layer, nickel oven wire mesh blanket, 316 stainless steel wire stratum reticulares or the 316L stainless steel wire stratum reticulare.So be provided with, can effectively improve the antiseptic power of product, be fit to the water body in different waters.Other is identical with embodiment one.
Embodiment six: combine Fig. 1～Fig. 3 that this execution mode is described; The woven wire of described first oven wire mesh blanket 1 of this execution mode and the 3rd oven wire mesh blanket 5 is the square hole net; The silk wiry footpath of first oven wire mesh blanket 1 and the 3rd oven wire mesh blanket 5 is 0.5～5.0mm, and the aperture of the woven wire of first oven wire mesh blanket 1 and the 3rd oven wire mesh blanket 5 is 10.5～105mm.So be provided with; Make the aperture of inner layer metal silk screen and the aperture of outer layer metal silk screen have certain matching ratio; The aperture of inner layer metal silk screen is 1 with the ratio in the aperture of outer layer metal silk screen: (3-15); Help increasing the microbial adhesion area and adhere to quantity, increase electron transport speed, improve the electrogenesis energy.Other is identical with embodiment one, two, four or five.
Embodiment seven: combine Fig. 2 and Fig. 3 that this execution mode is described; The thickness of this execution mode described first nonmetal flaggy 2 and the second nonmetal flaggy 4 is 2～16mm; The first nonmetal flaggy 2 is identical with the material of the second nonmetal flaggy 4, and material is wherein a kind of in carbon felt, flexible graphite or the foamy graphite.So be provided with, material property is good, with the compound and common carburizing of woven wire machinery; To produce numerous microscopic CNT passage; Make metal the firm crimping of mechanicalness promptly arranged mutually, also have the plasma nanometer conduit micro-structural that common carburizing produces, therefore with carbon-based material; Greatly reduce the internal resistance of microbiological fuel cell, improved integral material microbial adhesion amount and electron transport speed.Meet design requirement.Other is identical with embodiment one, two, four or five.
Embodiment eight: combine Fig. 2 and Fig. 3 that this execution mode is described; The material of this execution mode described first nonmetal flaggy 2 and the second nonmetal flaggy 4 is the carbon felt, all has the flexible graphite coating on the first nonmetal flaggy 2 and the second nonmetal flaggy 4 and the end face that second oven wire mesh blanket 3 reclines mutually.So be provided with, more help producing numerous microscopic CNT passage, improved the effect and the performance of composite material, meet design requirement.Other is identical with embodiment seven.
Embodiment nine: a kind of manufacturing approach of embodiment one described a kind of microbiological fuel cell composite material anode that realizes realizes according to following steps: one, first oven wire mesh blanket, second oven wire mesh blanket and the 3rd oven wire mesh blanket carry out random etching processing respectively: first oven wire mesh blanket that will make, second oven wire mesh blanket and the 3rd oven wire mesh blanket water in advance are cleaned; First oven wire mesh blanket, second oven wire mesh blanket and the 3rd oven wire mesh blanket after cleaning are placed respectively on the anode in bipolar electrode etching reaction pond; In said reaction tank, add etching agent simultaneously; Keeping the anodic-cathodic spacing is 6～14cm; At voltage is 5～9V; Electric current is under 148～288A condition; Reaction 14min～58min, wherein etching agent is that the nitric acid by the hydrochloric acid of 1mol/L and 1mol/L is that 100: 2～100: 4 ratio is made into or mass percent concentration is 10% hydrofluoric acid by volume; Two, first oven wire mesh blanket that will be after step 1 is handled, second oven wire mesh blanket and the 3rd oven wire mesh blanket are after water cleans respectively, and air dry is again through acetone; Three, the two-way carbo-nitriding of liquid phase plasma electrolysis is handled: first oven wire mesh blanket, second oven wire mesh blanket and the 3rd oven wire mesh blanket after step 2 is handled are put into the plasma electrolysis pond respectively; Electrolyte is joined in the said electrolytic cell, is 0.9～1.1A/cm in current density
2, operating voltage is that 222～248V and electrolyte working temperature are under 22 ℃～43 ℃ the condition; Processing time is 3.2～4.8min, and described electrolyte is that 8.5: 0.5: 1 ratio is made into or is that 8.5: 0.5: 1 ratio is made into by urea, sodium chloride and water in mass ratio by urea, potassium chloride and water in mass ratio; Four, first oven wire mesh blanket, second oven wire mesh blanket and the 3rd oven wire mesh blanket water after step 3 is handled are cleaned, use alcohol wash again, air dry; Five, first oven wire mesh blanket, second oven wire mesh blanket and the 3rd oven wire mesh blanket that will be after step 4 is handled and the first nonmetal flaggy of having made and the second nonmetal flaggy formation pre-press that is stacked together in order; The order that stacks is successively: first oven wire mesh blanket, the first nonmetal flaggy, second oven wire mesh blanket, the second nonmetal flaggy and the 3rd oven wire mesh blanket; Through forcing press said pre-press is suppressed, when pressing pressure reaches 0.2～0.8MPa/cm
2The time, stop compacting, and, make semi-finished product the welding of adjacent metal silk screen; Six, the two-way Carburization Treatment of liquid phase plasma electrolysis, the semi-finished product that will make through step 5 are put into the plasma electrolysis pond, electrolyte joined in the said electrolytic cell, be 0.9～1.1A/cm in current density
2, operating voltage is that 222～248V and electrolyte working temperature are under 22 ℃～43 ℃ the condition; Processing time is 3.2～4.8min, and described electrolyte is that 8.5: 0.5: 1 ratio is made into or is that 8.5: 0.5: 1 ratio is made into by formamide, sodium chloride and water in mass ratio by formamide, potassium chloride and water in mass ratio; The composite material water that seven, will after step 6 is handled, obtain cleans, air dry, and excision forming promptly makes a kind of microbiological fuel cell composite material anode.
Embodiment ten: this execution mode with embodiment nine differences is: the anodic-cathodic spacing in the step 1 is 8～12cm; At voltage is 6～8V; Electric current is under 150～286A condition; Reaction 16min～56min, wherein etching agent is that the nitric acid by the hydrochloric acid of 1mol/L and 1mol/L is that 100: 2.5～100: 3.5 ratio is made into by volume.Other is identical with embodiment nine.
Embodiment 11: this execution mode with embodiment nine or ten differences is: the anodic-cathodic spacing in the step 1 is 10cm; At voltage is 7V; Electric current is under the 220A condition; Reaction 36min, wherein etching agent is that the nitric acid by the hydrochloric acid of 1mol/L and 1mol/L is that 100: 3 ratio is made into by volume.Other is identical with embodiment nine or ten.
Embodiment 12: this execution mode with embodiment nine to 11 differences is: the current density in the step 3 is 1A/cm
2, operating voltage is that 225V and electrolyte working temperature are that the processing time is 4.5min under 28 ℃ the condition.Other is identical with embodiment nine to 11.
Embodiment 13: this execution mode with embodiment nine to 12 differences is: the pressing pressure in the step 5 reaches 0.4～0.6MPa/cm
2The time, stop compacting.Other is identical with embodiment nine to 12.
Embodiment 14: this execution mode with embodiment nine to 13 differences is: the pressing pressure in the step 5 reaches 0.5MPa/cm
2The time, stop compacting.Other is identical with embodiment nine to 13.
Embodiment 15: this execution mode with embodiment nine to 14 differences is: the current density in the step 6 is 1A/cm
2, operating voltage is that 230V and electrolyte working temperature are that the processing time is 4min under 25 ℃ the condition.Other is identical with embodiment nine to 14.
Embodiment 16: the manufacturing approach of a kind of microbiological fuel cell composite material anode of this execution mode realizes according to following steps: one, first oven wire mesh blanket, second oven wire mesh blanket and the 3rd oven wire mesh blanket carry out random etching processing respectively: first oven wire mesh blanket that will make, second oven wire mesh blanket and the 3rd oven wire mesh blanket water in advance are cleaned; First oven wire mesh blanket, second oven wire mesh blanket and the 3rd oven wire mesh blanket after cleaning are placed respectively on the anode in bipolar electrode etching reaction pond; In said reaction tank, add etching agent simultaneously; Keeping the anodic-cathodic spacing is 12cm; At voltage is 7V; Electric current is under the 220A condition; Reaction 40min, wherein etching agent is that the nitric acid by the hydrochloric acid of 1mol/L and 1mol/L is that 100: 3 ratio is made into or mass percent concentration is 10% hydrofluoric acid by volume; Two, first oven wire mesh blanket that will be after step 1 is handled, second oven wire mesh blanket and the 3rd oven wire mesh blanket are after water cleans respectively, and air dry is again through acetone; Three, the two-way carbo-nitriding of liquid phase plasma electrolysis is handled: first oven wire mesh blanket, second oven wire mesh blanket and the 3rd oven wire mesh blanket after step 2 is handled are put into the plasma electrolysis pond respectively; Electrolyte is joined in the said electrolytic cell, is 1A/cm in current density
2, operating voltage is that 235V and electrolyte working temperature are under 28 ℃ the condition; Processing time is 3.5min, and described electrolyte is that 8.5: 0.5: 1 ratio is made into or is that 8.5: 0.5: 1 ratio is made into by urea, sodium chloride and water in mass ratio by urea, potassium chloride and water in mass ratio; Four, first oven wire mesh blanket, second oven wire mesh blanket and the 3rd oven wire mesh blanket water after step 3 is handled are cleaned, use alcohol wash again, air dry; Five, first oven wire mesh blanket, second oven wire mesh blanket and the 3rd oven wire mesh blanket that will be after step 4 is handled and the first nonmetal flaggy of having made and the second nonmetal flaggy formation pre-press that is stacked together in order; The order that stacks is successively: first oven wire mesh blanket, the first nonmetal flaggy, second oven wire mesh blanket, the second nonmetal flaggy and the 3rd oven wire mesh blanket; Through forcing press said pre-press is suppressed, when pressing pressure reaches 0.5MPa/cm
2The time, stop compacting, and, make semi-finished product the welding of adjacent metal silk screen; Six, the two-way Carburization Treatment of liquid phase plasma electrolysis, the semi-finished product that will make through step 5 are put into the plasma electrolysis pond, electrolyte joined in the said electrolytic cell, be 1A/cm in current density
2, operating voltage is that 230V and electrolyte working temperature are under 25 ℃ the condition; Processing time is 4min, and described electrolyte is that 8.5: 0.5: 1 ratio is made into or is that 8.5: 0.5: 1 ratio is made into by formamide, sodium chloride and water in mass ratio by formamide, potassium chloride and water in mass ratio; The composite material water that seven, will after step 6 is handled, obtain cleans, air dry, and excision forming promptly makes a kind of microbiological fuel cell composite material anode.
The silk footpath of first oven wire mesh blanket and the 3rd oven wire mesh blanket is 1.0-4.0mm in this execution mode, and the aperture of woven wire is 60-90mm, and described first oven wire mesh blanket and the 3rd oven wire mesh blanket are 316 stainless steel metal silk screen layers; The silk footpath of second oven wire mesh blanket is 1.0-4.0mm, and the aperture is 10-25mm, and described second oven wire mesh blanket is the titanium silk screen layer, and the thickness of the first nonmetal flaggy and the second nonmetal flaggy is 6-12mm, and material is the carbon felt.
The carbon carpet veneer surface electronic microphotograph of the composite material anode that this execution mode makes is as shown in Figure 4; As can be seen from Figure 4; Carbon carpet veneer surface has the CNT passage, and the titanium silk screen layer electron micrograph of the composite material anode that this execution mode makes is as shown in Figure 5, as can be seen from Figure 5; The titanium silk screen layer has carbon nano tube structure; Fig. 6 is the carbon carpet veneer and the titanium silk screen layer interface electron micrograph of the composite material anode that makes of this execution mode, and as can be seen from Figure 6, the composite material anode has CNT passage and void structure; CNT, metal ion bridge joint are in titanium silk screen layer and carbon carpet veneer tissue; Fig. 7 is that the carbon carpet veneer electron micrograph of the composite material anode that makes of this execution mode is as shown in Figure 7, and as can be seen from Figure 7, the carbon carpet veneer has the multi-wall carbon nano-tube tubular construction.
Claims (10)
1. microbiological fuel cell composite material anode; It is characterized in that: described anode is a kind of rolled-up stock; This anode comprises first oven wire mesh blanket (1), the first nonmetal flaggy (2), second oven wire mesh blanket (3), the second nonmetal flaggy (4) and the 3rd oven wire mesh blanket (5); The second nonmetal flaggy (2) is positioned between first oven wire mesh blanket (1) and second oven wire mesh blanket (3); The second nonmetal flaggy (4) is arranged between second oven wire mesh blanket (3) and the 3rd oven wire mesh blanket (5); All have nitriding and carburizing composite bed on the wire of described first oven wire mesh blanket (1), second oven wire mesh blanket (3) and the 3rd oven wire mesh blanket (5); The material of the described first nonmetal flaggy (4) and the second nonmetal flaggy (5) is carbon-based material; The aperture of the woven wire of described second oven wire mesh blanket (3) is less than the aperture of the woven wire of first oven wire mesh blanket (1), and the aperture of the woven wire of second oven wire mesh blanket (3) is less than the aperture of the woven wire of the 3rd oven wire mesh blanket (5).
2. a kind of microbiological fuel cell composite material anode according to claim 1 is characterized in that: described second oven wire mesh blanket (3) is wherein a kind of in titanium silk screen layer, nickel oven wire mesh blanket, 316 stainless steel wire stratum reticulares or the 316L stainless steel wire stratum reticulare.
3. a kind of microbiological fuel cell composite material anode according to claim 1 and 2; It is characterized in that: the woven wire of described second oven wire mesh blanket (3) is the square hole net; The silk wiry footpath of second oven wire mesh blanket (3) is 0.5～5.0mm, and the aperture of the woven wire of second oven wire mesh blanket (3) is 3～30mm.
4. a kind of microbiological fuel cell composite material anode according to claim 1 is characterized in that: described first oven wire mesh blanket (1) is wherein a kind of in titanium silk screen layer, nickel oven wire mesh blanket, 316 stainless steel wire stratum reticulares or the 316L stainless steel wire stratum reticulare.
5. a kind of microbiological fuel cell composite material anode according to claim 1 is characterized in that: described the 3rd oven wire mesh blanket (5) is wherein a kind of in titanium silk screen layer, nickel oven wire mesh blanket, 316 stainless steel wire stratum reticulares or the 316L stainless steel wire stratum reticulare.
6. according to claim 1,2,4 or 5 described a kind of microbiological fuel cell composite material anodes; It is characterized in that: the woven wire of described first oven wire mesh blanket (1) and the 3rd oven wire mesh blanket (5) is the square hole net; The silk wiry footpath of first oven wire mesh blanket (1) and the 3rd oven wire mesh blanket (5) is 0.5～5.0mm, and the aperture of the woven wire of first oven wire mesh blanket (1) and the 3rd oven wire mesh blanket (5) is 10.5～105mm.
7. according to claim 1,2,4 or 5 described a kind of microbiological fuel cell composite material anodes; It is characterized in that: the thickness of the described first nonmetal flaggy (2) and the second nonmetal flaggy (4) is 2～16mm; The first nonmetal flaggy (2) is identical with the material of the second nonmetal flaggy (4), and material is wherein a kind of in carbon felt, flexible graphite or the foamy graphite.
8. a kind of microbiological fuel cell composite material anode according to claim 7; It is characterized in that: the material of the described first nonmetal flaggy (2) and the second nonmetal flaggy (4) is the carbon felt, all has the flexible graphite coating on the first nonmetal flaggy (2) and the second nonmetal flaggy (4) and the end face that second oven wire mesh blanket (3) reclines mutually.
9. manufacturing approach that realizes the described a kind of microbiological fuel cell composite material anode of claim 1; It is characterized in that: this method realizes according to following steps: one, first oven wire mesh blanket, second oven wire mesh blanket and the 3rd oven wire mesh blanket carry out random etching processing respectively: first oven wire mesh blanket that will make, second oven wire mesh blanket and the 3rd oven wire mesh blanket water in advance are cleaned; First oven wire mesh blanket, second oven wire mesh blanket and the 3rd oven wire mesh blanket after cleaning are placed respectively on the anode in bipolar electrode etching reaction pond; In said reaction tank, add etching agent simultaneously; Keeping the anodic-cathodic spacing is 6～14cm; At voltage is 5～9V; Electric current is under 148～288A condition, reaction 14min～58min, and wherein etching agent is that the nitric acid by the hydrochloric acid of 1mol/L and 1mol/L is that 100: 2～100: 4 ratio is made into or mass percent concentration is 10% hydrofluoric acid by volume; Two, first oven wire mesh blanket that will be after step 1 is handled, second oven wire mesh blanket and the 3rd oven wire mesh blanket are after water cleans respectively, and air dry is again through acetone; Three, the two-way carbo-nitriding of liquid phase plasma electrolysis is handled: first oven wire mesh blanket, second oven wire mesh blanket and the 3rd oven wire mesh blanket after step 2 is handled are put into the plasma electrolysis pond respectively; Electrolyte is joined in the said electrolytic cell, is 0.9～1.1A/cm in current density
2, operating voltage is that 222～248V and electrolyte working temperature are under 22 ℃～43 ℃ the condition; Processing time is 3.2～4.8min, and described electrolyte is that 8.5: 0.5: 1 ratio is made into or is that 8.5: 0.5: 1 ratio is made into by urea, sodium chloride and water in mass ratio by urea, potassium chloride and water in mass ratio; Four, first oven wire mesh blanket, second oven wire mesh blanket and the 3rd oven wire mesh blanket water after step 3 is handled are cleaned, use alcohol wash again, air dry; Five, first oven wire mesh blanket, second oven wire mesh blanket and the 3rd oven wire mesh blanket that will be after step 4 is handled and the first nonmetal flaggy of having made and the second nonmetal flaggy formation pre-press that is stacked together in order; The order that stacks is successively: first oven wire mesh blanket, the first nonmetal flaggy, second oven wire mesh blanket, the second nonmetal flaggy and the 3rd oven wire mesh blanket; Through forcing press said pre-press is suppressed, when pressing pressure reaches 0.2～0.8MPa/cm
2The time, stop compacting, and, make semi-finished product the welding of adjacent metal silk screen; Six, the two-way Carburization Treatment of liquid phase plasma electrolysis, the semi-finished product that will make through step 5 are put into the plasma electrolysis pond, electrolyte joined in the said electrolytic cell, be 0.9～1.1A/cm in current density
2, operating voltage is that 222～248V and electrolyte working temperature are under 22 ℃～43 ℃ the condition; Processing time is 3.2～4.8min, and described electrolyte is that 8.5: 0.5: 1 ratio is made into or is that 8.5: 0.5: 1 ratio is made into by formamide, sodium chloride and water in mass ratio by formamide, potassium chloride and water in mass ratio; The composite material water that seven, will after step 6 is handled, obtain cleans, air dry, and excision forming promptly makes a kind of microbiological fuel cell composite material anode.
10. the manufacturing approach of a kind of microbiological fuel cell composite material anode according to claim 9 is characterized in that: the current density in the step 6 is 1A/cm
2, operating voltage is that 230V and electrolyte working temperature are that the processing time is 4min under 25 ℃ the condition.
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