CN101485029A

CN101485029A - Materials and configurations for scalable microbial fuel cells

Info

Publication number: CN101485029A
Application number: CNA2007800251900A
Authority: CN
Inventors: B·洛根
Original assignee: Penn State Research Foundation
Current assignee: Penn State Research Foundation
Priority date: 2006-05-02
Filing date: 2007-05-02
Publication date: 2009-07-15

Abstract

Devices for production of electricity and/or hydrogen gas are provided by the present invention. In particular, microbial fuel cells for production of electricity and modified microbial fuel cells for production of hydrogen are detailed. A tube cathode is provided which includes a membrane forming a general tube shape. An anode is provided which has a specific surface area greater than 100 m<2>/m<3>. In addition, the anode is substantially non-toxic to anodophilic bacteria. Combinations of particular anodes and cathodes are included in microbial fuel cells and modified microbial fuel cells.

Description

The material and the configuration that are used for scalable microbiological fuel cell

The reference of related application

The application requires in the priority of the U.S. Provisional Patent Application 60/796,761 of submission on May 2nd, 2006, and the full content of this application mode is by reference included in this specification.

Government-funded

The research relevant with the present invention is subjected to the part support of state natural sciences fund BES-0401885 and the fund 68-3A75-3-150 of United States Department of Agriculture.Therefore, U.S. government can have some right among the present invention.

Invention field

The present invention broadly relates to microbiological fuel cell.Particularly, the present invention relates to the scalable configuration of electrode and microbiological fuel cell.

Background technology

Present progress has made utilizes bacterium to be developed for the fuel-cell device of Catalyst Production useful products.Bacterial oxidation substrate, the electronics of generation are transferred to anode and flow to negative electrode by the conduction connection again, and described conduction connects also can connect a load, and for example an electricity and/or a hydrogen that produces with this fuel cell is the device of power.

Yet the electrode configuration of microbiological fuel cell usually restricts the generation of electric power, and significantly restricts the spatial volume of fuel cell.

Therefore, people have demand to the scalable electrode that is used for microbiological fuel cell and the configuration of scalable electrode assemblie all the time.

Summary of the invention

The invention provides a kind of microbiological fuel cell, comprise a negative electrode, described negative electrode comprises a film, described film forms the cathode wall of surrounding usually and defining an inner space, described cathode wall has an inner surface and the opposed outer surface with described inner space adjacency, and described wall launches between first terminal and second end.In some specific embodiments, this cathode wall surrounds is shaped as common cylindrical shaped.In other specific embodiments, this cathode wall surrounds is shaped as conventional plate shape or brick shape.Anode contained in the microbiological fuel cell is nontoxic substantially to close anode bacterium.Conduction connector connects described anode and described negative electrode.

In the specific embodiments of microbiological fuel cell of the present invention, the contained film of this negative electrode is a kind of NF membrane, a kind of milipore filter or a kind of amberplex.

Contained film is optional to be a kind of conducting film, and this film is electrically connected with described conduction connector.

In other embodiments, electric conducting material exists in inner surface or the contacted mode of outer surface with film, and this electric conducting material is electrically connected with conduction connector.

Electric conducting material is optional to be a kind of carbon-based material.In some configuration, graphite is a kind of and the contacted concrete carbon back electric conducting material of film.

Randomly, described electric conducting material is a carbon-base coating.In specified microorganisms fuel cell configuration of the present invention, this carbon-base coating covers inner surface or the outer surface at least about 50% described film.

In the generating configuration of microbiological fuel cell of the present invention, in order to the accelerating oxidation agent optional inner surface or the outer surface that is present in film of catalyst of the reduction of oxygen particularly.Appropriate catalyst comprises metallic catalyst, Pt for example, and contain nonmetallic catalyst, for example CoTMPP.The also optional bond that comprises catalyst.In addition, in the hydrogen manufacturing configuration of fuel cell of the present invention, comprise in order to the catalytic hydrogen evolution catalyst for reaction.Appropriate catalyst comprises metallic catalyst, for example Pt.

In some specific embodiments, contained anode has greater than 100m ²/ m ³Specific area.In certain embodiments, contained a kind of concrete anode type is a kind of brush shape anode (brushanode).

In the embodiment of microbiological fuel cell of the present invention, comprise more than one anode and/or more than one negative electrode.

Microbiological fuel cell of the present invention be designed to produce hydrogen and/or.When required product was hydrogen, microbiological fuel cell comprised one in order to increase the power supply of electromotive force between anode and negative electrode.Contained power supply can be the power supply of any kind.In the specific embodiments, comprised the power supply of a microbiological fuel cell that is designed to generate electricity as hydrogen manufacturing.

In some specific embodiments, provide a kind of and contain a specific area greater than 100m ²/ m ³The microbiological fuel cell of anode.This anode is nontoxic substantially to close anode bacterium.Also comprise a negative electrode in this microbiological fuel cell, it is connected by conduction connector with described anode.

In an embodiment of microbiological fuel cell of the present invention, contained anode comprises one or more conductive fibers.In a kind of configuration of anode, described one or more conductive fibers are connected on the conductive cores supporter.In some specific embodiments, each single fiber in described one or more conductive fibers all is connected on the described conductive cores supporter.Perhaps, the first of described conductive fiber is connected on the described conductive cores supporter, and the second portion of described conductive fiber is connected in the first of conductive fiber and with it and is electrically connected.

In some specific embodiments, at least a portion conductive fiber is a carbon fiber.

In some specific embodiments, comprise one in order to increase the power supply of electromotive force between anode and negative electrode, from microbiological fuel cell, to produce hydrogen.In other specific embodiments, described power supply is connected with described cathodic electricity with described anode.For example, contained power supply is a secondary microbiological fuel cell, and this secondary microbiological fuel cell is designed to produce electric power.

The invention provides a kind of negative electrode that is used for microbiological fuel cell, comprise a film, described film forms the cathode wall with certain shape, this cathode wall has an outer surface and an inner surface, described wall defined one with the inner space of described abutment and one space outerpace with described abut outer surfaces, described wall launches between first terminal and second end.The film that forms described wall is a NF membrane, a milipore filter or an amberplex.Form the optional conducting film of film of described wall for being connected with the conduction connector conduction.In some specific embodiments, a kind of electric conducting material contacts with the inner surface or the outer surface of described film, and described electric conducting material is connected with described conduction connector conduction.Electric conducting material is optional to be a kind of carbon-based material, and for example, in some specific embodiments, described electric conducting material is a graphite.

When having electric conducting material on the described film, described electric conducting material covers the inner surface or the outer surface of about 50% described film at least.

In some specific embodiments, promote hydrogen reduction or promote the catalyst of proton reduction to contact with described cathodic coating directly or indirectly.Randomly, seal first end of described wall or at least one end of second end.

In the specific embodiments of an improved hydrogen manufacturing microbiological fuel cell, the inner space of described sleeve cathode is at least in part by a kind of liquid filling.

In other embodiments, described cathode wall is common cylindrical shaped or conventional plate shape.

The anode of microbiological fuel cell of the present invention comprises that a kind of specific area is greater than 100m ²/ m ³Electric conducting material, described anode is nontoxic substantially to close anode bacterium.In some specific embodiments, described anode comprises one or more conductive fibers.Randomly, described one or more conductive fibers are connected on the conductive cores supporter.In some specific embodiments, the described conductive fiber of at least a portion directly is connected on this supporter.In other embodiments, each single fiber of described one or more conductive fibers all directly is connected on this conductive cores supporter.Randomly, described specific area is greater than 100m ²/ m ³Electric conducting material comprise a coating.

In a specific embodiments, described one or more fibers contained in anode of the present invention are handled with ammonia.

System of the present invention can be used as, for example, and a kind of method of the waste water treatment that combines with generating, or a kind of method that produces regenerative resource by non-waste product.In addition, system of the present invention also can be used as a method of wastewater treatment that combines with hydrogen manufacturing.Therefore, provide waste water as biodegradable fuel, it is by the bacterium direct oxidation in the microbiological fuel cell, or biodegradable can be to produce by the product of the bacterial oxidation in the microbiological fuel cell.

The invention describes a kind of electricity-generating method, comprising: a kind of microbiological fuel cell is provided, and this battery comprises a sleeve cathode and/or a brush shape anode; With microbionation in this microbiological fuel cell, and supply with a kind of can be by the substrate of bacterial oxidation; Generating whereby.

The invention describes a kind of electricity-generating method, comprising: a kind of microbiological fuel cell is provided, and this battery comprises a sleeve cathode and/or a brush shape anode; With microbionation in this microbiological fuel cell, and supply with a kind of can be by the substrate of bacterial oxidation and apply a voltage in addition to increase electromotive force between described anode and described negative electrode; Hydrogen manufacturing whereby.

The invention describes a kind of hydrogen production process, comprising: a kind of microbiological fuel cell is provided, and this battery comprises a sleeve cathode and/or a brush shape anode; With microbionation in this microbiological fuel cell, and supply with a kind of can be by the substrate of bacterial oxidation and apply a voltage in addition to increase electromotive force between described anode and described negative electrode; Hydrogen manufacturing whereby.

The generating of embodiment of the present invention and/or hydrogen production process comprise provides a kind of microbiological fuel cell in order to generating and/or hydrogen manufacturing, and this battery comprises that a sleeve cathode and/or a specific area are greater than 100m ²/ m ³Anode.In some specific embodiments, method of the present invention comprises provides waste water as can be by the biodegradable substrate of the bacterial oxidation in the microbiological fuel cell, this battery is in order to generating and/or hydrogen manufacturing, and it comprises that a sleeve cathode and/or a specific area are greater than 100m ²/ m ³Anode.

Description of drawings

Fig. 1 is the schematic diagram of a brush shape anode;

Fig. 2 is the schematic diagram of a brush shape anode;

Fig. 3 is the schematic diagram of a brush shape anode;

Fig. 4 is the schematic diagram of a hollow common cylindrical shaped film negative electrode;

Fig. 5 is the schematic diagram of the conventional plate shape of hollow film negative electrode;

Fig. 6 is the schematic diagram of an electrode of microbial fuel cell assembly, and it comprises a brush shape anode that is arranged in sleeve cathode;

Fig. 7 is the schematic diagram of an electrode of microbial fuel cell assembly, and it comprises a plurality of brush shape anodes that are connected with a plurality of sleeve cathodes;

Fig. 8 is the schematic diagram of an electrode of microbial fuel cell assembly, and it comprises two brush shape anodes that are connected with a sleeve cathode;

Fig. 9 is the schematic diagram of an electrode of microbial fuel cell assembly, and it comprises a plurality of brush shape anodes that are connected with a plurality of sleeve cathodes;

Figure 10 is the schematic diagram of an electrode of microbial fuel cell assembly, and it comprises a brush shape anode and a hollow cylindrical negative electrode;

Figure 11 is the schematic diagram of an electrode of microbial fuel cell assembly, and it comprises a brush shape anode and a hollow sheeting shape negative electrode;

Figure 12 is the schematic diagram of the electrode assemblie of a microbiological fuel cell, and it comprises an electricity generation module, and described electricity generation module comprises a brush shape anode and a sleeve cathode; And this electricity generation module provides power for a hydrogen manufacturing module, and described hydrogen manufacturing module comprises a brush shape anode and a sleeve cathode;

Figure 13 is the schematic diagram of a hydrogen manufacturing electrode of microbial fuel cell assembly, and it comprises a plurality of brush shape anodes that are connected with a plurality of cylindrical cathodes;

Figure 14 is the schematic diagram of the electrode assemblie of a hydrogen manufacturing microbiological fuel cell, and it comprises a plurality of brush shape anodes that are connected with a plurality of plate shape negative electrodes;

Figure 15 is a chart, and it illustrates 4 initial production capacity cycles of microbiological fuel cell of containing a brush shape anode;

Figure 16 A is a chart, and it illustrates the power density and the cell voltage potential of the microbiological fuel cell that contains a brush shape anode;

Figure 16 B is a chart, and it illustrates the coulombic efficiency of the microbiological fuel cell that contains a brush shape anode;

Figure 17 is a chart, and the corresponding Nyquist diagram of microbiological fuel cell impedance spectrum (Nyquist Plot) that it illustrates and records between negative electrode and anode, described microbiological fuel cell comprise a cloth shape or brush shape anode;

Figure 18 A is a chart, and it illustrates the power density curve of the microbiological fuel cell that contains various types of anodes in 200mM PBS;

Figure 18 B is a chart, and it illustrates the power density curve of the microbiological fuel cell that contains various types of anodes in 50mM PBS;

Figure 19 A is a chart, the power density of its 10 micron diameter graphite fibres that random distribution of using different amounts are shown during as anode material;

Figure 19 B is a chart, the power density of its 6 micron diameter graphite fibres that random distribution of using different amounts are shown during as anode material;

Figure 20 A is one and illustrates as the power density (open symbols) of the function that is normalized to the long-pending current density of overall reactor, the chart of voltage (filled symbols) that this chart obtains by the external resistance (40-3000 Ω) that changes carbon paper anode microbiological fuel cell.

Figure 20 B is a chart that illustrates as the electrode potential (negative electrode open symbols, anode filled symbols) of the function that is normalized to the long-pending current density of overall reactor, and this chart obtains by the external resistance (40-3000 Ω) that changes carbon paper anode microbiological fuel cell.

Figure 21 A is one and conduct is shown based on the power density (open symbols) of the function of the current density of reactor volume and the chart of voltage (filled symbols) that this chart obtains by the external resistance (40-3000 Ω) that changes brush shape anode microbiological fuel cell.

Figure 21 B is an electrode potential (negative electrode open symbols that conduct is shown based on the function of the current density of reactor volume, the anode filled symbols) chart, this chart obtains by the external circuit resistance (40-3000 Ω) that changes brush shape anode microbiological fuel cell.

Figure 22 A is a chart that illustrates as the power of the function with sleeve cathode microorganism fuel cell cathode surface area of brushing the shape anode;

Figure 22 B is a chart that illustrates as the volumetric power density of the function with sleeve cathode microorganism fuel cell cathode surface area of brushing the shape anode;

Figure 23 A is a chart that ripple (Figures) voltage is shown as the function of time, wherein brushes shape anode microbiological fuel cell and moves with continuous or batch mode under 1000 Ω fixed resistances;

Figure 23 B is a chart of volumetric power density that illustrates as the function of the electric current that is normalized to volume, and this chart obtains by changing with external resistance (40-3000 Ω) continuous or the brush shape anode microbiological fuel cell that batch mode is moved.

Figure 24 is a form, its illustrate the type of employed electrode among the embodiment 2 and surface area and electrode area and volume ratio, volume, internal resistance, be normalized to the maximum power density of anode surface area or reactor total measurement (volume) and the coulombic efficiency of carbon paper anode and brush shape anode MFC batch run.

Embodiment

The invention provides the microbiological fuel cell that comprises the scalable electrode that is used for microbiological fuel cell and scalable electrode assemblie.Terminology used here " microbiological fuel cell " is meant a kind of device that uses bacterium to be transferred to the electronics of anode with oxygenated fuel and generation as catalyst.Microbiological fuel cell produces electric power usually.Terminology used here " microbiological fuel cell " also refers to the improved microbiological fuel cell in order to hydrogen manufacturing.The microbiological fuel cell that is modified to hydrogen manufacturing comprises a power supply that increases voltage, and is different from water electrolyser.Also the known microorganisms fuel cell can be used as the auxiliary microbial reaction heap of bioelectrochemistry (BEAMR).The main aspect of hydrogen manufacturing microbiological fuel cell (BEAMR) is described in the U.S. Patent application 11/180,454.

Microbiological fuel cell can be used for various uses, for example the manufacturing of the processing of waste water or regenerative resource.Microbiological fuel cell of the present invention can be used for providing power for device, for example portable electron device.Microbiological fuel cell of the present invention can advantageously be applied to remote equipment, for example sea sensor.

Generally speaking, microbiological fuel cell comprises the bacterium as catalyst, is used to generate electricity and/or the electronics of hydrogen manufacturing with generation.Microbiological fuel cell generally includes an anode, a negative electrode and an electronic conductor that connects described anode and described negative electrode.Microbiological fuel cell comprises can oxidation substrates and produce the bacterium of electronics.In the concrete configuration of some microbiological fuel cells, also optional cation-exchange membrane, anion-exchange membrane or the neutral film of comprising.

The operation of the microbiological fuel cell that is used to generate electricity can roughly be described as, and the oxidable substrate that is provided is produced electronics and proton by bacterial oxidation.When being organic substrates, substrate also produces carbon dioxide.Electronics is transferred to anode, and by a load transfer such as device to be driven to negative electrode.Proton and electronics react and generation water at negative electrode place and oxygen.

The operation that is used for the microbiological fuel cell of hydrogen manufacturing can roughly be described as, and the oxidable substrate that is provided is produced electronics and proton by bacterial oxidation.When being organic substrates, substrate also produces carbon dioxide.A power supply is connected with this microbiological fuel cell and imposes an auxiliary voltage.The electron transfer that bacterium produced is to anode, and is transferred to negative electrode by a conduction connector.Oxygen is excluded substantially outside this cathode zone, thereby makes proton and electronics generate hydrogen in the combination of negative electrode place.

In microbiological fuel cell of the present invention, contained electrode is conductive.Exemplary conductive electrode material includes, but not limited to carbon paper, carbon cloth, carbon felt, carbon suede, carbon foam, graphite, porous graphite, graphite powder, graphite granule, graphite fibre, conducting polymer, conducting metal, reaches the bond of any above-mentioned substance.

Typically, anode for close anode bacterium adhere to and growth provides a surface, thereby anode is made by being suitable for bacterial growth and the material kept.Growth of bacterium and the compatibility kept can be used the standard technique assessment in material and the microbiological fuel cell, for example, use the check of survival ability label, described survival ability label is rhodamine 123, propidium iodide, SYTO9, and the bond of above-mentioned or other bacteria live ability label for example.

In the embodiment of microbiological fuel cell of the present invention, contained anode comprises the fiber of being made by a kind of conductive anode material, and described fiber provides the big surface area that can contact with the bacterium in the microbiological fuel cell.

In the embodiment of fuel cell of the present invention, the specific area of contained anode is greater than 100m ²/ m ³Here specific area is meant total anode surface area of per unit anode volume.In the microbiological fuel cell of embodiment of the present invention, specific area is greater than 100m ²/ m ³The time help to produce electric power.In other embodiments, fuel cell of the present invention comprises that one has greater than 1000m ²/ m ³The anode of specific area.In other embodiment, fuel cell of the present invention comprises that has greater than 5 a 000m ²/ m ³The anode of specific area.In other embodiment of the present invention, described fuel cell comprises that has greater than 10 a 000m ²/ m ³The anode of specific area.According to the present invention, the anode with bigger serface makes it possible to amplify microbiological fuel cell.

A kind of brush shape anode is provided in some specific embodiments, and it has greater than 100m ²/ m ³Specific area.Brush shape anode comprises one or more conductive fibers.In some specific embodiments, described one or more fibers are connected on the supporter.

In some particular, many fibers are connected on the above support, and described fiber is radial extension from this supporter usually.Brush shape anode is chosen wantonly and is comprised a supporter that is positioned at the center with longitudinal axis.

Brush shape anode can comprise multiple configuration, exemplarily comprises various twisted wire brush configurations and bar brush configuration.For example, concrete twisted wire brush configuration comprises that described fiber is connected between the described lead by two or more multiple conducting wires and fibroplastic supporter.In another example, bar brush configuration comprises the fiber that is connected on the conduction back of the body bar (backing strip), and described back of the body bar is connected on the above support.

The fiber of brush shape anode conducts electricity, and is connected with a cathodic electricity with above support.In some specific embodiments, the fiber and/or the supporter of brush shape anode provide a carrier for trooping of close anode bacterium, thereby described brush shape anode is preferably nontoxic substantially to close anode bacterium.

In some specific embodiments, the fiber of brush shape anode comprises a kind of metal and/or non-metallic conducting material, and this material is nontoxic substantially to close anode bacterium.In a particular instance, described fiber comprises carbon fiber.Carbon fiber is optional to be made up of graphite substantially.In another was selected, material with carbon element mixed with a kind of conducting polymer to form fiber.In other embodiment, polymer fiber applies with a kind of material with carbon element of conduction.

In a kind of configuration, the graphite fibre 112 of brush shape anode 100 is basically perpendicular to two or more anti-corrosion leads of conduction and between it, described lead forms a supporter 110, thus make carbon fiber 112 from this supporter 110 substantially with radial extension, as shown in Figure 1.A lead is chosen twisting around described brush wantonly so that itself and this lead keeps good electrical contact, thereby forms anode.Conduction connector is connected on the supporter 110 usually so that this anode is connected to negative electrode.

The graphite fibre that comprises in brush shape anode can cut off as shown in Figure 1 endways, thereby has many discontinuous fibres 112 in brush shape anode.In other embodiments, as shown in Figure 2, anode 200 is chosen wantonly and is comprised one or more fiber with continuous orderly configuration, thereby for example helps to keep fiber to stretch in the aqueous culture medium of microbiological fuel cell.In described configuration, at least one continuous fiber is coiling around central shaft, to form circular fiber expansion position 212.Optional supporter 210 has been shown among Fig. 2.When not comprising supporter, conduction connector is connected on described one or more fiber so that this anode is connected to negative electrode.When comprising supporter, conduction connector is connected on the supporter usually so that this anode is connected with negative electrode.

In another configuration, brush shape anode 300 comprises the graphite fibre 312 of random orientation and does not have supporter, thus the continuous cushion structure that formation is connected with connector 310 conductions, as shown in Figure 3.

Brush shape anode can comprise different coating arbitrarily.In some specific embodiments, coating is included on the brush shape anode to improve the bacterium generating efficiency on this anode.For example, brush shape anode can apply a kind of conductive material of electronics from bacterium to the surface that strengthen.The example that can strengthen the conductive material of electronics from bacterium to the surface includes, but not limited to dimethyl diaminophenazine chloride, Mn ⁴⁺, Fe ₃O ₄, Ni ²⁺, fluoridize polyaniline for example poly-(2-fluoroaniline) and poly-(2,3,5, the 6-tetrafluoroaniline), anthraquinone-1,6-disulfonic acid (AQDS), 1, reaches the bond of any above-mentioned substance at 4-naphthoquinones (NQ).

In a specific embodiments, anode is handled with the generation that increases electric power with ammonia technology and is reduced this reactor and inoculated the back and produce the required time of a large amount of electric power.For example, brush shape anode can be with the Ammonia gas of heating NH for example ₃Gas is handled.In a specific embodiments, brush shape anode is heated to 700 ℃ and use NH ₃Air culture was supported about 1 hour.

In brush shape anode, thereby optionally comprise that extra material for example reinforces or support described graphite fibre, perhaps under described brush can move around or rotate with the situation of sweeping neighbouring surface, negative electrode or other material, remove biomembrane, with the help cleaning systems.

In system of the present invention, can make contained negative electrode be dipped in the liquid or be used as and have a gaseous cathode (gas cathod) that is exposed to the surface in the gas.Negative electrode preferably includes a kind of electrically conductive material.Include, but not limited to the examples of materials that the negative electrode that is comprised in the system of the present invention comprises carbon paper, carbon cloth, carbon felt, carbon suede, carbon foam, graphite, porous graphite, graphite powder, conducting polymer, conducting metal, and the bond of any above-mentioned material.

In some specific embodiments, microbiological fuel cell of the present invention comprises a negative electrode, and wherein said negative electrode comprises a film, and described film forms a cathode wall.Described cathode wall has an outer surface and an inner surface, and described wall defined with the inner space of abutment and with the space outerpace of abut outer surfaces.In some specific embodiments, described cathode wall forms is shaped as common cylindrical shaped.In other specific embodiments, plate shape that is shaped as conventional inner hollow or brick shape that described cathode wall forms.Other hollow shape also is possible, exemplarily comprises the hollow dish type.

The film that forms cathode wall is a perforated membrane.Described film be abundant porous so that material requested can diffuse through described film.For example, in some specific embodiments of microbiological fuel cell of the present invention, contained film is a porous for oxygen, proton and/or hydrogen.In some particular of microbiological fuel cell generating configuration, contained film is a porous for oxygen and proton.In some particular of improved hydrogen manufacturing microbiological fuel cell, when having catalyst on the inner surface of contained film or near the inner surface, this film is a porous for proton.In other particular of improved hydrogen manufacturing microbiological fuel cell, when having catalyst on the outer surface of contained film or near the outer surface, this film is a porous for proton and hydrogen.In some preferred embodiments, effective hole of contained film is about 1000 nanometers less than the size of conventional bacterium.Therefore, water and/or bacterium are limited through described film and any included the mobile of membrane coat.

The film that in negative electrode of the present invention, contains in film aspect the contained material without limits.The composition of micro-filtration membrane, NF membrane and amberplex is known in this area, and the various films arbitrarily that can get rid of bacterium and allow desired gas to diffuse through film all can use.The illustrative examples of micro-filtration membrane, NF membrane and/or ion-exchange film composition comprises, but be not limited to, halogenated compound, for example tetrafluoroethene, TFE copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, poly-inclined to one side 1,1-difluoroethylene, poly-inclined to one side vinylidene fluoride copolymer, polyvinyl chloride, polyvinyl chloride copolymer; TPO, for example polyethylene, polypropylene and polybutene; Polyamide-based, nylon for example; Sulfone class, for example polysulfones and polyether sulfone; Based on the polymer of nitrile, for example acrylonitrile; And the polymer of styrene-based, for example polystyrene.

An optional structural support layers, for example the porous plastics backing layer of comprising of film.For example, the film optional stays is on a polyester layer.In preferred embodiments, supporting layer is flexible.

The example of suitable membrane material is for removing the milipore filter and the NF membrane of degerming simultaneously in order to filtered water usually in water treatment industry.For example, suitable film is the milipore filter B0125 that Dutch X-Flow produces.Other example comprises CMI and the AMI amberplex that the Membranes Internation Co., Ltd of N.J. produces.

Contained film comprises a kind of electric conducting material in negative electrode of the present invention, so that described film can conduct electricity and/or a kind of electric conducting material is coated on a side of described film.

In some concrete configurations, to the described film conduction that imposes one or more coatings so that this material becomes.For example, an optional part that the coating of containing metal or carbon is applied at least a side of described film.In a specific embodiments, used an equadag coating.The exemplary formulations of equadag coating comprises the product of Superior Graphite: preparation ELC E34 and Surecoat1530.

Randomly, make a kind of membrane material, so that contain a kind of electric conducting material in the film, this electric conducting material makes by its film of making and conducts electricity.For example, carbon fiber can mix with the polymer phase that uses in milipore filter, NF membrane and/or amberplex usually.

Randomly, in negative electrode of the present invention, containing a kind of promotion negative electrode place needs catalyst for reaction.Therefore, in the generating configuration of microbiological fuel cell, contain a kind of catalyst that promotes hydrogen reduction.In addition, in the hydrogen manufacturing configuration of microbiological fuel cell, contain a kind of proton that promotes and be reduced to hydrogen, promptly promote the catalyst of evolving hydrogen reaction.Contained catalyst can increase reaction power usually, for example, increases the speed of oxygen and/or proton reduction.In addition, catalyst has reduced the applying electrical potential of the reduction that is used to cause oxygen and/or hydrogen and the demand of overpotential.

Catalyst is chosen wantonly and is applied to conducting film.In another was selected, catalyst mixed with electric conducting material and forms the mixture that is applied to film.In another selection, catalyst was applied to film before or after using electric conducting material.

In some specific embodiments, catalyst is optional to be mixed mutually with a kind of polymer and a kind of electric conducting material, forms the catalyst material of whole conduction so that film comprises a kind of and this film.For example, catalyst is mixed mutually with the equadag coating material and this mixture is applied to cathodic coating.

Appropriate catalyst is known in this area, comprises metallic catalyst, for example noble metal.Comprise to the appropriate catalyst examples of metals platinum, nickel, copper, tin, iron, palladium, cobalt, tungsten, and the alloy of these metals.When the negative electrode in the embodiment of system of the present invention contains a kind of catalyst metals for example during platinum, the content of platinum can reduce, and for example can be reduced to 0.1mg/cm ², and the unlikely generation that influences energy.In other embodiments, contained catalyst comprises a kind of non-noble metal catalyst, for example CoTMPP of containing.

Can the coating that one or more are other be coated on one or more electrode surfaces.For example, the coating of this other adding can be served as diffusion layer.For example, can add a cathodic protection layer and prevent that bacterium or other material from contacting with this cathode surface, and allow oxygen to diffuse to catalyst and conducting base simultaneously.In other embodiments, comprise the carrier of a cathodic protection layer, thereby make bacterium remove near the oxygen the described negative electrode and directly do not contact with this negative electrode as clusters of bacteria.

Fig. 4 shows according to common cylindrical shaped of the present invention " tubulose " negative electrode 400, and it has a cathode wall, described cathode wall has an outer surface 414 and an inner surface 416, and described wall has defined an inner space 418 with described inner surface 416 adjacency.

Fig. 5 shows according to conventional plate shape of the present invention " tubulose " negative electrode 500, and it has a cathode wall, described cathode wall has an outer surface 514 and an inner surface 516, and described wall has defined an inner space 518 with described inner surface 516 adjacency.

With in the microbiological fuel cell, contained sleeve cathode is opened to containing the oxygen culture medium in the one or both ends of its length in generating.In some specific embodiments, with in the microbiological fuel cell, the one or both ends of contained sleeve cathode air towards periphery are open in generating.

Use in the microbiological fuel cell in the hydrogen manufacturing of embodiment of the present invention, contained sleeve cathode is collected or is carried the container or the pipeline of the hydrogen that is produced at an end of its length to one and opens.

As mentioned above, sleeve cathode of the present invention has an inner space.In a kind of selection scheme, to use in the microbiological fuel cell in the hydrogen manufacturing of embodiment of the present invention, a kind of scheme is that the inner space of sleeve cathode is filled with gas.Therefore, for example, surrounding air can be contained at first in the inner space of described sleeve cathode during startup, and along with the carrying out of hydrogen manufacturing microbiological fuel cell run duration hydrogen manufacturing and contain increasing hydrogen.The hydrogen that makes is from the inner space of this described sleeve cathode flow direction for example gas collection unit or device.In another embodiment, this inner space is by liquid filling or partially filled.Apply little back-pressure by the liquid in described inner space, can make the hydrogen that makes at hydrogen manufacturing microbiological fuel cell run duration for example move to a gas collection unit or device effectively from the described inner space of containing liquid.In sleeve cathode, contain liquid and help separating out of hydrogen,, and reduce the anti-phase diffusion of anode chamber because it causes being separated of hydrogen and liquid.By using the liquid in the described negative electrode inner space, recyclable relatively large hydrogen.Contained liquid can be any in the multiple liquid compatible with hydrogen with cathode material in the described inner space.Suitable liquid comprises waterborne liquid, water for example, and it can contain one or more salt, buffer or other additive.

In some embodiments, thus negative electrode operation makes water be attracted porous film material by described negative electrode, and water is contacted with the conductive coating or the conductive matrices of described film.Described membrane material can contain a large amount of carbon blacks so that its conduction, or can be made by graphite fibre, or so that water is applied by the mode of described equipment.

Randomly, and in some embodiments for preferably, described negative electrode is a gaseous cathode.In some specific embodiments, contained negative electrode has a plane configuration, for example when using jointly with a brush shape anode.In this configuration, described negative electrode is preferably a gas-diffusion electrode.

Randomly, contained negative electrode is arranged in aqueous culture medium, contains the oxygen in order to the dissolving of reacting at the negative electrode place in this culture medium.

In one embodiment of the invention, cathodic coating almost can not permeate water.

In some specific embodiments, described negative electrode contains one or more cathode screen materials.This shielding material can preferably include a shielding material layer that is positioned at the arbitrary cathode surface, described cathode surface comprises inner cathode surface and outer surface, described inner cathode surface promptly is present in the cathode surface in the reative cell internal volume, and described outer surface is promptly at the cathode surface of reative cell outside.Cathode surface in the reative cell outside may exist when using a gaseous cathode, and this moment, this external cathode surface contacted with gas.Therefore, in one embodiment, cathode outer surface partly or preferably uses one deck cathode diffusion layer (CDL) to cover fully.This CDL can directly be exposed in the gas phase, and preferred combination is oozed out to prevent water autoreaction chamber interior from seeing through described negative electrode on described negative electrode.In addition, in the hydrogen manufacturing configuration, described CDL can see through hydrogen, can make hydrogen freely the catalyst in negative electrode diffuse to other assembly of gas collection chamber, gas pipeline or gas gathering system.CDL also can be described negative electrode and provides support, and can form a part of reaction chamber wall.CDL also can help to reduce bacterium and diffuse to negative electrode and pollute cathode surface.CDL comprises a kind of hydrophobic polymer material that sees through hydrogen, for example polytetrafluoroethylene (PTFE) or materials similar.The thickness that can change this material as required maybe can impose multilayer material to reduce seepage.

In another embodiment, use a cathodic protection layer (CPL) with protection inner cathode surface.The function of this CPL is the biological pollution that the protection negative electrode is avoided catalyst.In addition, CPL also can reduce the diffusion of carbon dioxide to negative electrode, thereby restriction is by abiotic source and biogenic or form methane by bacterial action at the negative electrode place.CPL also is used near the clusters of bacteria the negative electrode that carrier is provided, and allows it to remove oxygen and not target generation biological pollution at cathode zone.

In one embodiment, design CPL makes it contact with cathode inner surface.Therefore, for example, can be by such as mode on the negative electrode that CPL is bonded to CPL partly or entirely being covered or around described cathode inner surface.

In another embodiment, CPL is present in the inside of reative cell but does not contact with negative electrode.Contain this CPL and defined two or more zones based on the reactor of this CPL.Described CPL can be the barrier of proton, liquid and/or gas permeable, for example a filter.For example, prevent large particulate matter be introduced into reactor filter can between anode and the negative electrode so that material when flowing through reative cell between anode and negative electrode by this filter.As alternative or additional, the particle that filter can be positioned on the negative electrode with the restricting bacterial size arrives negative electrode and catalyst.In addition, filter also can be positioned at admission passage and/or discharge the inside of people having a common goal and reative cell, or between its part.Suitable filter can be in order to for example to get rid of the particle greater than 0.01 micron-1 micron.CPL also can contain the material of helpful bacterial adhesion, so that bacterium can be removed the oxygen of the dissolving that can infiltrate described system.

In one embodiment, CPL comprises that one optionally makes material by arriving near negative electrode " diffusion of protons layer ".In one embodiment, diffusion layer contains a kind of ion exchange material.But the suitable ion conductive substance of any proton conducting all can be included in the proton exchange membrane.For example, can use fluoridized sulfonic acid polymer film.Particularly, but can be used for described purpose such as the proton exchange membrane of the proton conducting of NAFION.

In one embodiment, diffusion layer comprises a kind of anion exchange material.In a preferred embodiment, described diffusion layer comprises a kind of anion exchange material that anion and the bacteriogenic proton of close anode can be conducted to together negative electrode, for example a kind of quaternary amine SDEB styrene diethylenebenzene copolymer.Contained diffusion layer also can be used for suppressing gas to the negative electrode diffusion or from the diffusion of negative electrode to relevant anode chamber.Be not limited to any theory, we think with electronegative anionic ion-exchange group for example the proton that combines of phosphate allow especially and contain positively charged proton but the electronegative anion of whole band net negative charge passes through, and do not allow that positively charged ion passes through, and reduce the diffusion of hydrogen anode chamber.This diffusion layer can be realized the effective conduction of proton through described barrier, suppresses the reverse conduction of hydrogen simultaneously.An example of this diffusion layer material is for purchasing the International in Membranes, Glen Rock, the anion-exchange membrane AMI-7001 of New Jersey.Except the form of film, described diffusion layer also can comprise a kind of anionic conduction material that directly is applied to negative electrode as pastel.In a preferred embodiment, anion-exchange material can contain the catalyst that is applied to negative electrode.

The fuel cell configuration

Generally speaking, microbiological fuel cell comprises an electrode assemblie, and it comprises an anode, negative electrode and a conduction connector that is connected described anode and described negative electrode.Other assemblies of microbiological fuel cell also can comprise a reative cell, and anode and negative electrode are placed in one at least in part.Reative cell can have one or more locellus, for example, and an anode locellus and a negative electrode locellus of separating by for example a kind of cation-exchange membrane.Perhaps, reative cell can be a kind of single chamber configuration.In reative cell, can comprise one or more passage to add and to remove various materials, for example the substrate of bacterial metabolism and product hydrogen for example.

Electrode in the electrode assemblie can be arranged as various not isomorphism types relative to each other according to required application.

Usually, anode and negative electrode disposed adjacent.In some specific embodiments, anode can contact with negative electrode, and for example, one or more fiber of brush shape anode contacts with the inboard sleeve cathode with catalyst of pipe.

In a kind of configuration, described " brush shape " anode electrode is positioned at the inside of " tubulose " negative electrode, and continuous water flows through the inside of described pipe and flows through brush shape anode top, and wherein said cathod catalyst is applied to the outside of described pipe.

In the example of a this layout, one or more brush shape anodes are positioned at the inside of sleeve cathode, as shown in Figure 6.Fig. 6 shows the embodiment of the electrode assemblie 600 of a microbiological fuel cell that has a brush shape anode 620 in sleeve cathode 630 inside.Described sleeve cathode 630 has one by film formed wall, and described film has an outer surface 614 and an inner surface 616.Outer surface 614 is coated with a kind of catalyst material (CSM) of conduction.Described sleeve cathode have one define by described film and with the inner space of inner surface 616 adjacency, this space is open to allow entering and/or directly flowing of aqueous culture medium.For example, thus fluid directly flows through described pipe stream above the high conductivity carbon fiber of the anode 620 of close anode bacterial adhesion and on every side.The oxidable organic substance of described bacterium, the anode fiber discharges electronics.These electronics pass the circuit 650 of load 660 belows so that electric current acting, or are transferred as power supply and use at a distance.The proton that the organic substance oxidation produces moves towards described cathode direction in water, diffuses to the electric conducting material place on the described sleeve cathode outer surface 614 at the negative electrode place, and if have a catalyst, they can form water with combining from the oxygen in the circuit and electronics.In the embodiment of this example, electronics reaches CSM place on the surface 614 through connector 650 and negative electrode connector 670.

In second kind of configuration, one or more brush electrodes are positioned at outside the sleeve cathode.Randomly, aqueous culture medium stream can directly flow through the reative cell that contains one or more brush electrodes, and flows on the surface of cathode tube.Sleeve cathode in this configuration can comprise a catalyst layer at the outer surface or the inner surface of described pipe.

An example of this configuration of the electrode assemblie of microbiological fuel cell as Fig. 7 700 shown in, wherein said brush shape anode is arranged in the culture medium of described cathode external.Fig. 7 shows a plurality of anodes 720 with two sleeve cathode 730 series arrangement, the catalyst material that described negative electrode has a kind of conduction in the outside of pipe 714.Medium flow directly flows through described brush electrode and flow to then on the negative electrode, flows through so that proton is transferred to described cathode surface well from negative electrode.Described anode and negative electrode use an electric connector 750 by a load 760 to be electrically connected.Described electric connector also can comprise a negative electrode connector 770 that contacts with the CSM of surface on 714.

Contain in a kind of embodiment of electric conducting material in the sleeve cathode outside, described conductive cathode surface contacts well with aqueous culture medium, as shown in Figure 7.

In another embodiment, electric conducting material and catalyst are positioned at the inner surface of described sleeve cathode.This configuration have make electric conducting material away from bacterium and in this aqueous culture medium, may exist make described catalysqt deactivation or reduce the advantage of the chemical substance of its effect, as shown in Figure 8.Fig. 8 illustrates an electrode assemblie 800 of microbiological fuel cell, and it comprises a plurality of anodes 820 near a sleeve cathode 830, described sleeve cathode has a kind of conduction in the inside of cathode tube on the inwall 816 that film limits catalyst material.Fig. 8 also shows the outer surface 814 of described sleeve cathode and the connector 850 that links to each other with described anode, described negative electrode and load 860 with electrically conducting manner.

Perhaps in this configuration, described cathode tube is made by a kind of conductive catalyst material, and the outside of described pipe is non-conductive, for example realizes by applying a kind of non-conducting material.Cathode conductive layer can apply the above-mentioned protective layer of one deck.If described sleeve cathode is the coated with conductive catalyst material on inwall, then this cathodic protection layer must can see through oxygen.If described sleeve cathode is the coated with conductive catalyst material on outer wall, then this cathodic protection layer must be able to make proton reach cathode surface from water; In this layout, preferably can suppress oxygen and diffuse to coating in the water.

In another configuration, brush shape anode is positioned at the outside of sleeve cathode chamber, and water moves to the inside of this negative electrode periosteum by the mode of for example suction.Randomly, described conductive catalyst material can be positioned at the outside, inboard of membrane material or integrate with membrane material.In this layout, the water that drew this negative electrode can filter through a milipore filter or NF membrane.

Fig. 9 shows the electrode assemblie 900 of microbiological fuel cell, and it comprises a plurality of anodes 920 and negative electrode 930.Shown in Fig. 94 anode-cathode modules as shown in Figure 8.

In the embodiment shown in Fig. 9, this electrode assemblie 900 is present in the aqueous culture medium 904 of microbiological fuel cell reative cell 902 to produce electric power.Passage 922 and 924 also are shown, and it can be used for introducing and removing in the autoreaction chamber 902 one or more materials.Sleeve cathode 930 passes reative cell so that the inside of this sleeve cathode 930 is opened and/or opened to the oriented stream by described pipe 903 to ambient air 926.Randomly, an end of cathode tube 903 is sealing or reversible end socket.Anode and negative electrode contained in the electrode assemblie 900 are electrically connected by electric connector 950.The electricity that produces can be used for driving a device, illustrates as load 960.The anode-cathode module of electrode assemblie can be connected in series to increase voltage or to be connected in parallel to increase electric current.When the anode-cathode module was connected in series, each module was isolated substantially by a dividing plate shown among Fig. 9 928, so that each anode basic insulation.The dividing plate 928 that illustrates comprises a hole, thereby links with the reactor other parts that contain other anode-cathode module.Can use the series connection and the combination in parallel of anode-cathode assembly to increase voltage and current.

When electricity was the principal product of system of the present invention, the negative electrode place existed oxygen to generate the reaction of water to promote proton, electronics and oxygen.Microbiological fuel cell of the present invention also can improve to produce hydrogen.In a hydrogen manufacturing embodiment of microbiological fuel cell of the present invention, oxygen is got rid of from cathode zone substantially, and comprise a power supply that increases electromotive force between described anode and described negative electrode in the system, it does not contain additional power supply by applying a voltage outside the voltage that produces at microbiological fuel cell again and realizing.

Oxygen by removing cathode zone and apply a small voltage that is enough to produce hydrogen at cathode surface, system of the present invention is applicable to making hydrogen, and according to employed system configuration, the hydrogen of making can be collected in described pipe or on the outside of pipe.The main aspect of hydrogen manufacturing microbiological fuel cell is described in the U.S. Patent application 11/180,454.

In a hydrogen manufacturing embodiment, anode can be as above-mentioned structure and layout.Yet negative electrode does not need oxygen, so should avoid its existence.When oxygen is removed, the material that produces is applied a small voltage on anode.Generally speaking, the voltage range that applies is between about 10-1000 millivolt.The mode that the hydrogen that the negative electrode place produces can be collected the gas outside this cathode tube when placing in the described sleeve cathode when anode or collect the gas in this cathode tube outside anode places described sleeve cathode the time is caught.

Brush shape negative electrode or planar cathode also can be used in combination to produce hydrogen with brush shape anode.Similarly, brush shape anode or dull and stereotyped anode can use to produce hydrogen with sheath.In addition, in some embodiments of electrode of microbial fuel cell assembly of the present invention, the combination of one or more brush shape anodes and/or dull and stereotyped anode can be used with one or more brush shape negative electrodes, planar cathode and/or sleeve cathode.

An instantiation of the hydrogen manufacturing anode-cathode assembly 1000 of microbiological fuel cell as shown in figure 10, it shows a brush shape anode 1020 and cylindrical tubular negative electrode 1030 that is electrically connected by a connector that passes load 1,090 1050.Optional resistor 1090 illustrates as load in the figure.Comprise a power supply in the hydrogen-generating fuel cell, not shown in this figure.Described sleeve cathode 1030 comprises an outer surface 1014 and an inner surface 1016.

An instantiation of the hydrogen manufacturing anode-cathode assembly 1110 of microbiological fuel cell as shown in figure 11, it shows brush shape anode 1120 being electrically connected by a connector that passes load 1,190 1150 and one and has block-shaped sleeve cathode 1130.Power supply contained in the hydrogen-generating fuel cell links to each other with electrode assemblie, and is not shown in this figure.Described sleeve cathode 1130 comprises an outer surface 1114 and an inner surface 1116.

Figure 12 shows the schematic diagram of an electrode assemblie 1200 of microbiological fuel cell, and first electrode assemblie that wherein is used to generate electricity links to each other with second electrode assemblie that is used for hydrogen manufacturing.In such embodiment, brush shape anode 1220 is chosen wantonly and is electrically connected with sleeve cathode 1230 through a load 1290.The second brush shape anode 1222 is electrically connected with second sleeve cathode 1232 by connector 1252.Described first electrode assemblie is connected with described second electrode assemblie by electric connector 1254, so that can increase electromotive force between described anode 1222 and the described negative electrode 1232 by applying a voltage by the electric power of first electrode assemblie generation.

Figure 13 shows the schematic diagram of the microbiological fuel cell 1300 of hydrogen manufacturing, and it comprises an electrode assemblie with a series of electrode modules.Described electrode assemblie is present in the aqueous culture medium 1304 in single groove reative cell 1302.Can choose wantonly and comprise that passage 1322 and 1324 so that material enters or discharges, for example makes aqueous culture medium flow to and flows out reative cell.Can choose wantonly and comprise that passage 1327 and 1329 so that material enters or discharges, for example makes sweep gas or hydrogen enter and discharge reative cell and/or hydrogen collecting apparatus.Also show a plurality of anodes 1320 and sleeve cathode 1330, they are electrically connected by connector 1350.Power supply contained in the hydrogen-generating fuel cell is connected with described electrode assemblie, and is not shown in this figure.Collected hydrogen stream is entered the room in 1380 in the described sleeve cathode 1330.Described gas is passable, for example, collects in described chamber, or leads to gatherer or directly introduce hydrogen power set from described chamber 1380.Sleeve cathode 1330 has an inner space 1325, and the one end is opened to described chamber 1380.In a selection scheme, but inner space 1325 gassies.Therefore, for example, surrounding air can be contained in the inner space 1325 of sleeve cathode when initial the startup, and contains the hydrogen of recruitment along with the carrying out of hydrogen manufacturing at the run duration of hydrogen manufacturing microbiological fuel cell 1300.In another embodiment, inner space 1325 is filled by liquid or is partly filled.The inner space 1325 that hydrogen applies little back pressure by the liquid in described inner space 1325 and oneself contains liquid effectively that is produced at these hydrogen manufacturing microbiological fuel cell 1300 run durations moves in the chamber 1328.

Figure 14 shows the schematic diagram of a series of electrode assemblies 1400 of hydrogen manufacturing microbiological fuel cell.Described electrode is present in the aqueous culture medium 1404 in single groove reative cell 1402.Can choose wantonly and comprise that

passage

1422 and 1424 so that material enters or discharges, for example makes aqueous culture medium flow to and flows out reative cell.Can choose wantonly and comprise that

passage

1427 and 1429 so that material enters or discharges, for example makes sweep gas or hydrogen enter and discharge reative cell and/or hydrogen collecting apparatus.Also show a plurality of anodes 1420 and sleeve cathode 1430, they are electrically connected by connector 1450.Power supply contained in the hydrogen-generating fuel cell links to each other with described electrode assemblie, and is not shown in this figure.Collected hydrogen stream is entered the room in 1480 in the described sleeve cathode 1430.Described gas can for example be collected in described chamber, or 1480 leads to gatherer or directly introduce hydrogen power set from the chamber.Shown piece shape sleeve cathode occupies the degree of depth of whole reactor.

Anode can have different shape and size arbitrarily with negative electrode, and can have various position relation each other.In one embodiment, described anode and described negative electrode all have a dimension the longest, and this anode and this negative electrode are arranged as and make the longest dimension of anode be parallel to the longest dimension of negative electrode.In another selection scheme, described anode and described negative electrode all have a dimension the longest, and this anode and this negative electrode are arranged as and make the longest dimension of anode perpendicular to the longest dimension of negative electrode.In addition randomly, described anode and described negative electrode all have a dimension the longest, and this anode and this negative electrode are arranged as and make the longest dimension of anode perpendicular to the longest dimension of negative electrode.In addition, this anode and this negative electrode can be arranged as and make the longest dimension of the longest dimension of anode and negative electrode be angle between 0 to 180 degree.

The electrode that in system of the present invention, can comprise various different sizes and shape.Generally speaking, anode has a surf zone and is present in surface in the reative cell, and negative electrode has the surface of surf zone in reative cell.In one embodiment, the ratio of the anode total surface area of system of the present invention and negative electrode total surface area is about 1: 1.In one embodiment, the anode surface area in the reative cell is greater than the cathodic surface area in the reative cell.This layout has many benefits, for example, when cathode material is expensive, can reduce cost when for example comprising platinum catalyst.In addition, the bigger anode surface surface that generally helps providing a growth for close anode bacterium with electron transfer to this anode.In another preferred selection scheme, the ratio of the cathodic surface area in the anode surface area in the reative cell and this reative cell is in the 1.5:1-1000:1 scope, more preferably in the 2:1-10:1 scope.

Electrode can various mode be arranged to reach space required between electrode.For example, first electrode can be arranged as and make its longest dimension be basically parallel to second the longest dimension of electrode.In another embodiment, first electrode can be arranged as and make its longest dimension be basically perpendicular to second the longest dimension of electrode.In addition, first electrode also can be arranged as and make its longest dimension and second dimension that electrode is the longest be angle between 0 to 90 degree.

In the embodiment of microbiological fuel cell of the present invention, cation-exchange membrane can be chosen wantonly between anode and negative electrode.Cation-exchange membrane can see through one or more selected cations.Especially preferably can see through the cation-exchange membrane of proton, promptly a kind of proton exchange membrane.Suitable proton exchange membrane material comprises for example copolymer of tetrafluoroethene and perfluorovinyl sulfide ether sulfonic acid of perfluorinated sulfonic acid polymer, and derivative.Particular instance comprises NAFION, and for example NAFION 117, and by E.I.DuPont de Nemours﹠amp; Co., Wilmington, the derivative that DE produces.

In some specific embodiments, microbiological fuel cell of the present invention can be designed to self-supporting fuel cell.Therefore, for example, in this fuel cell, comprise a large amount of biodegradable substrates and no longer add extra substrate.In other selection, add extra substrate off and on or continuously so that this fuel cell turns round as a batch process device or as a continuous-flow system.

Randomly, the system of the present invention that provides comprises more than one anode and/or more than one negative electrode.For example, can provide 1-100 extra anode and/or negative electrode.The quantity of one or more anodes and/or one or more electrodes and layout can be paid attention to according to the condition of concrete application.For example, in reactor, there is the substrate of large volume can provide the larger area anode surface by in the specific embodiments of microbial organisms metabolism.Similarly, the larger area cathode surface is suitable.In one embodiment, electrode surface area makes it comprise that one or more electrodes that stretch in the reative cell provide by reactor design.In another embodiment, electrode surface area provides as the part of reactor wall or reactor wall by making negative electrode.In some specific embodiments, the ratio range of the inner cumulative volume of the total surface area of one or more anodes and this reative cell is about 10000:1-1:1 (comprising end points, metre squared per cubic).In other embodiment, the scope of this ratio is about 5000:1-100:1.

Bacterium in the microbiological fuel cell comprises at least a or multiple close anode bacterium.Terminology used here " close anode " and " close anode bacterium " be meant directly or the amboceptor by endogenous generation with the bacterium of electron transfer to electrode.Generally speaking, close anode bacterium is obligate anaerobe or facultative anaerobe.Term " external electrogen (exoelectrogen) " is also in order to explain suitable bacterium.The example of parent anode bacterium comprise be selected from Aeromonas section (Aeromonadaceae), alternately unit cell Cordycepps (Alteromonadaceae), Clostridiaceae (Clostridiaceae), comamonas section (Comamonadaceae), desulfurization unit cell Cordycepps (Desulfuromonaceae), enterobacteriaceae (Enterobacteriaceae), Bacteriaceae (Geobacteraceae), Pasturellaceae, and the bacterium of pseudomonadaceae (Pseudomonadaceae).These and other case description that is applicable to the bacterium in the system of the present invention is in Bond, D.R., and et al., Science 295,483-485,2002; Bond, D.R., et al., Appl.Environ.Microbiol.69,1548-1555,2003; Rabaey, K., et al., Biotechnol.Lett.25,1531-1535,2003; United States Patent (USP) 5976719; Kim, H.J., et al., Enzyme Microbiol.Tech.30,145-152,2002; Park, H.S., et al., Anaerobe 7,297-306,2001; Chauduri, S.K., et al., Nat.Biotechnol., 21:1229-1232,2003; Park, D.H., et al., Appl.Microbiol.Biotechnol., 59:58-61,2002; Kim, N.et al., Biotechnol.Bioeng., 70:109-114,2000; Park, D.H.et al., Appl.Environ.Microbiol., 66,1292-1297,2000; Pham, C.A.et al., Enzyme Microb.Technol., 30:145-152,2003; And Logan, B.E., et al., Trends Microbiol., 14 (12): among the 512-518.

Parent anode bacterium preferably contacts with anode, with directly with electron transfer to anode.Yet for for the close anode bacterium of amboceptor metastatic electron, described bacterium can be present in other position in the reactor and still can play the effect that produces useful electronics in process of the present invention.

Randomly, in fuel cell, can comprise a kind of electron transfer amboceptor.The example of this amboceptoid comprises iron oxide, dimethyl diaminophenazine chloride, anthraquinone-1,6-disulfonic acid (ADQS) and 1,4-naphthoquinones (NQ).Each amboceptor is optional to be combined by chemical mode with anode, thereby or anode is for example applied via various processing and improves and contain one or more amboceptors.

As needs, close anode bacterium can be used as the pure culture that is rich in close anode bacterium even is rich in the bacterium of a particular types and provides.At Bond, D.R., et al., Appl.Environ.Microbiol.69,1548-1555, the coulombic efficiency of the pure culture of having reported in 2003 test is up to 98.6%.Therefore, use selected bacterial strain can increase total electronics rate of recovery and hydrogen manufacturing amount, particularly like this when this system uses under aseptic condition.Can be to the electromotive force that bacterium selects or genetic modification produces with increase coulombic efficiency and anode place.

In addition, also can provide a kind of mixed cell population that comprises close anode anaerobic bacteria and other bacterium.

Contained biodegradable substrate can be by close anode bacterial oxidation in the microbiological fuel cell of embodiment of the present invention, or biodegradable and generate can be by the material of close anode bacterial oxidation.In preferred embodiments, biodegradable substrate is a kind of biodegradable and generate can be by the organic material of the organic substrates of close anode thin rice seedling oxidation.The biodegradable organic matter of any kind all can be used as " fuel " of bacterium among the MFC, comprises carbohydrate, amino acids, fats, lipid and protein-based, and animal, the mankind, city, agricultural and industrial wastewater.Naturally occurring and/or synthetic polymer exemplarily comprises carbohydrate, for example chitin and cellulose; And biodegradable plastics, for example biodegradable aliphatic polyester, biodegradable aliphatic-aromatic polyester, biodegradable polyurethane and biodegradable polyvinyl alcohol.The particular instance of biodegradable plastics comprises polyhydroxy-alkanoate, poly butyric ester, poly-hydroxycaproic ester, poly-hydroxyl valerate, poly-ethanedioic acid, PLA, polycaprolactone, polybutylene succinate, the own diester of polybutylene succinate, polyethylene succinate, aliphatic-aromatic copolyester, polyethylene terephthalate, polybutene adipate ester/terephthalate, reaches polymethylene adipate ester/terephthalate.

Can be well known in the art by the organic substrates of close anode bacterial oxidation.Can be included, but not limited to the C of monose, disaccharides, amino acid, straight or branched by the illustrative examples of the organic substrates of close anode bacterial oxidation ₁-C ₇Compound, the C of described straight or branched ₁-C ₇Compound includes, but not limited to alcohols and volatile fat acids.In addition, can be comprised aromatic compound by the organic substrates of close anode bacterial oxidation, for example toluene, phenol, cresols, benzoic acid, phenmethylol and benzaldehyde.Other can be described in Lovely by the organic substrates of close anode bacterial oxidation, D.R., and et al., Applied and Environmental Microbiology56:1858-1864 is in 1990.In addition, the substrate that provides can or biodegradablely can be provided by the form of the organic substrates of close anode bacterial oxidation to generate by close anode bacterial oxidation.

Can be comprised glycerol, glucose, acetic acid esters, butyrate, ethanol, cysteine, and the bond of above-mentioned arbitrarily or other oxidable organic substance by the specific example of the organic substrates of close anode bacterial oxidation.

Terminology used here " biodegradable " is meant the organic substance that decomposes by biological mechanism, and described biological mechanism exemplarily comprises microbial action, heating and decomposition.Microbial action comprises for example hydrolysis.

In some specific embodiments, microbiological fuel cell of the present invention can be in order to produce electricity and/or hydrogen.

An embodiment of system of the present invention be one by a little auxiliary voltage is provided in circuit the system in the complete anaerobism of negative electrode hydrogen manufacturing.The method of the auxiliary hydrogen manufacturing of this electrochemistry is based on two electrodes are divided into half-cell reaction.The electromotive force of anode is by the oxidation decision of substrate.Therefore, the operation of anode one side of system of the present invention embodiment is similar to the operation in microbiological fuel cell (MFC): bacterium is CO with the organic compound complete oxidation ₂, and with electron transfer to anode.The half-cell reaction electromotive force that in an embodiment of system of the present invention, records at the anode place for-480mV (Ag/AgCl) or-285mV (NHE) (reduction).

On the contrary, in an embodiment of anaerobism hydrogen generating system of the present invention, the operation of negative electrode obviously is different from the operation in standard MFC.By the cathode potential in the electrochemical means raising MFC circuit, can be directly by proton and hydrogen manufacturing by bacteriogenic electronics.This method greatly reduces the directly required energy of hydrogen manufacturing in organic material with comparing by electrolysis hydrogen manufacturing in water institute energy requirement.In the MFC of routine, the open circuit potential of anode is about-300mV.When producing hydrogen at the negative electrode place, the half-cell reaction with the acetic acid esters oxidation of anode place that takes place at anode and negative electrode place is:

Anode: C ₂H ₄O ₂+ 2H ₂O → 2CO ₂+ 8e ^-+ 8H ⁺

Negative electrode: 8H ⁺+ 8e ^-→ 4H ₂

Can comprise that a power supply is to increase the electromotive force between anode and negative electrode.Exemplarily include, but not limited to electric supply (grid power), sun-generated electric power, wind-force power supply in order to the power supply that increases electromotive force between anode and negative electrode.The example that is suitable for power supply in system of the present invention also comprises dc power supply and electrochemical cell for example battery or capacitor.

In a specific embodiments, the power supply that is used for the hydrogen manufacturing microbiological fuel cell is a generating microbiological fuel cell.

In another embodiment, described reaction chamber wall comprises two or more parts, for example a structure division and an electrode part.Structure division is for forming and keeping the shape of this reative cell that support structure is provided, and this is similar to conventional reaction chamber wall.The electrode part of reaction chamber wall is divided into reative cell provides support structure, also plays functional effect in the running of system of the present invention.In this embodiment, this structure division and electrode part branch combine and form a wall that defines the reative cell inner space.In a particular, the electrode part branch of described wall comprises negative electrode.In addition, the electrode of described wall partly also can comprise the supporting construction of a supporting anodes or negative electrode.This supporting construction may further be formation and keeps the reative cell shape that support structure is provided.

Comprise a hydrogen collection in that hydrogen manufacturing of the present invention is optional in microbiological fuel cell, to collect the hydrogen that produces and can store for future use; Or hydrogen introduced make use, for example a hydrogen fuel device driven.

For example, a hydrogen collector unit can comprise one or more Hydrogen Lines, makes use so that hydrogen stream is introduced reservoir vessel or directly caused from described negative electrode.Hydrogen Line is optional to link to each other with source purge gas.For example along with hydrogen begins to produce, sweep gas can be introduced Hydrogen Line, towards reservoir vessel or hydrogen the direction of use is flowed.For example, hydrogen collection can comprise that a collection is derived from the container of the hydrogen of negative electrode.Gathering system also can comprise a hydrogen delivery tube road.This pipeline and/or container can with the passage airflow connection that is used to make hydrogen autoreaction chamber to flow out.Typically, described pipeline and/or container and negative electrode, particularly airflow connection when this negative electrode is a gaseous cathode.

Aqueous culture medium in the microbiological fuel cell reative cell be mixed with to this fuel cell in the contacted bacterium of aqueous culture medium nontoxic.In addition, also can adjust culture medium or solvent so that the metabolic fit of itself and bacterium, for example, by regulating pH to about pH3-9 (comprising 3 and 9), preferably in the scope of about 5-8.5 (comprising 5 and 8.5), in culture medium or solvent, add buffer if desired, and by dilution or add the osmotic pressure activating substance and regulate the gram molecule osmotic concentration of culture medium or solvent and realize.Can regulate ionic strength by for example diluting or adding a kind of salt.In addition, if desired, also can comprise nutrients, co-factor, vitamin and the bacterial population of other similar additive to keep fit.Referring to being described in Lovley andPhillips, Appl.Environ.Microbiol., 54 (6): the example of this class additive among the 1472-1480.Randomly, with the contacted aqueous culture medium of close anode bacterium contain dissolving can be by the substrate of bacterial oxidation.

Be in operation, reaction condition comprises the variable such as the pH of culture medium in the reactor, temperature, osmolality and ionic strength.Generally speaking, the pH of culture medium is between the 3-9 (comprising 3 and 9) in the reactor, between the preferred 5-8.5 (comprising 5 and 8.5).

Though by being included in the suitable bacteria of growing under the selected temperature device can be used under the arbitrary temp in the 0-100 degree centigrade of scope, for nonrefractory bacterium, reaction temperature is usually in about 10-40 ℃ scope.Yet, keeping reaction temperature to be higher than ambient temperature and may need the energy input, the preferred temperature of reactor that keeps is about 15-25 ℃ under the situation of noenergy input.A surprising discovery of the present invention is, reaction temperature is in 16-25 ℃ (comprising 16 and 25 ℃) or more preferably 18-24 ℃ (comprising 18 and 24 ℃) and further when preferred 19-22 ℃ (comprising 19 and 22 ℃), the reacting phase that carries out under hydrogen manufacturing amount, electrode potential, coulombic efficiency and energy recovery rate and 32 ℃ is worked as, and 32 ℃ of be considered to anaerobic growth and metabolism usually optimum temperatures of---comprising the oxidation of organic substance---.

The ionic strength of culture medium preferably in 50-500 mM scope, more preferably (comprises 75 and 450) in the reactor in 75-450 mM scope, and further preferably (comprises 100 and 400) in 100-400 mM scope.

In some specific embodiments, comprise a passage that defines from the reative cell outside to the reative cell internal path.The passage that can comprise one or more is to allow and/or instrumentality flows to and flows out this reative cell.For example, can comprise a passage so that the gas that the negative electrode place produces flows out.In addition, also can comprise a passage so that the gas that the anode place produces flows out.

In the specific embodiments of a Continuous Flow configuration, can comprise a passage so that logistics enters reative cell, and can use an independent passage so that the material in the reative cell flows out.Can comprise more than one passage to be used for any inflow or the outflow of material.

Can comprise an adjusting device, for example a valve flows out into described reactor with further instrumentality.In addition, optional cap or the seal of using is with closed channel.For example, when fuel cell remotely move or as one separately use equipment operation and do not have additional material add fashionable, optional cap or the seal closed channel of using.

Can provide a pump to strengthen flowing into and/or flowing out the liquid or the gas stream of reative cell.

Following examples will describe the embodiment of combination of the present invention and method.Provide these embodiment only for the purpose of illustration, and be not considered to restriction combination of the present invention and method scope.

Embodiment

Embodiment 1

Electrode material.

Brush the shape anode in the present embodiment by the carbon fiber (PANEX that is cut into regular length

33160K ZOLTEK), and uses the industrial brush manufacturing system to twine into a sth. made by twisting core of being made up of two titanium wires and makes.Two kinds of brushes that present embodiment uses are of a size of: little brush external diameter is 2.5cm, long 2.5cm; Big brush diameter is 5cm, long 7cm.According to the fiber diameter of using quality of fiber and 7.2 microns in the single brush, estimate that little brush anode has 0.22m ²Or 18,200m ²/ m ³The surface area (95% porosity) that brush body is long-pending is brushed anode greatly and is had 1.06m ²Or 7170m ²/ m ³The surface area (98% porosity) that brush body is long-pending.

Unless note is arranged in addition, brushes the shape anode according to Cheng, S.; Logan, B.E.Ammoniatreatment of carbon cloth anodes to enhance power generationof microbial fuel cells.Electrochem.Commun.2007,9, use ammonia to handle described in the 492-496..In brief, use thermogravimetric analyzer to realize the ammonia processing of anode in the present embodiment.The stove of any controllable temperature all can be used for the ammonia of anode to be handled.Down this furnace temperature is warming up to 700 ℃ gradually with the speed of 50 ℃/min at nitrogen (70mL/min), then feed gas is transferred to 5% NH in helium ₃This anode is kept 60min down at 700 ℃, in nitrogen (70mL/min), be cooled to room temperature then through 120min.

Use in some tests and be untreated and non-water-tight general T oray carbon paper anode and the contrast of brush shape anode, this carbon paper anode is made by ETEK, and the two sides all has 23cm ²Effective area (projected area).

Also used the random distribution graphite fibre bundle of ammonia treatment in some tests, every bundle is made up of 1 to 4 fibre bundle, and is cut into the regular length of 10cm separately.The quality of each fibre bundle is about 0.1g, and the effective area that wherein calculates the fibre bundle (Granoc-Nippon) of each 10 micron diameter fiber is 0.020m ², the effective area of the fibre bundle of each 6 micron diameter fiber (#292 carbon fiber bundle, Fibre Glast, Ohio) is 0.035m ²

Described negative electrode is according to Cheng.S.et al., Electrochem.Commun.2006, and 8, described in the 489-494., by (model B-1B uses platinum (0.5mg/cm on E-TEK) at 30 weight % waterproof carbon cloths ²Pt) and 4 layers of diffusion layer and making.In some experiments, described negative electrode uses identical method manufacturing and contains 40% tetramethylphenyl Cobalt Porphyrin (CoTMPP, 1.2mg/cm in addition ²) replace Pt as catalyst.

The MFC reactor

In the present embodiment, use two kinds of single chamber MFG to detect the generating situation of using brush electrode: a kind ofly be cube MFG (C-MFC), it is designed to make the energy output maximization; Another kind of for containing the bottle type MFC (B-MFC) of single face port, it is used for detecting the generating situation of pure culture and mixed culture in the system of a kind of easy system, cheapness.C-MFG is according to Liu, H.; Logan, B.E.Electricity generation using an air-cathode singlechamber microbial fuel cell in the presence and absence of aproton exchange membrane.Environ.Sci.Technol.2004,38,4040-4046. described in make, different is, usually place the anode of this reactor blind end to be replaced by a little brush electrode, this electrode is positioned at the axle center of cylindrical anode cell in concentric mode.The end of described brush is fixed in reative cell (4cm length * 3cm diameter; Liquid volume is 26ml) in so that its terminal (diameter is 3.8cm, and total exposed surface area is 7cm with described negative electrode ²) at a distance of 1cm.The metal end of described brush is stretched out by the hole that gets out on the reactor, and with epoxy sealing (Quick Set ^TMEpoxy, LOCTITE).All C-MFC test of present embodiment all with CoTMPP as catalyst.

B-MFC is made by the laboratory cultures base bottle (capacity is 320mL, Corning Co., Ltd, New York) of routine, even after assembling fully, but also high temperature high voltage resistant.A big brush electrode hangs on the bottle middle part that contains the 300mL culture medium, and the top of brush is apart from the about 6cm of bottle cap.The lead that brushes is drawn from bottle cap hole, and use epoxy sealing.Using carbon paper anode (2.5cm * 4.5cm, 22.5cm altogether ²) test in, the about 6cm of described electrode spacing bottle cap, and link to each other with the titanium silk (purity 99.8%) that passes with the bottle cap hole of epoxy sealing.The side pipe that described 4cm grows is apart from reactor bottom 5cm, and the negative electrode of a 3.8cm diameter is fixed between this pipe and another the single pipe that independently 4cm grows by a clip of its end, and negative electrode total projection surface area is 4.9cm ²(side of described negative electrode).In the test of using random distribution fiber Shu Zuowei anode, described fiber uses the spring clip that is connected with a lead to fix, and described lead passes in the bottle cap hole and uses epoxy sealing.

The reactor inoculation

C-MFC uses and is derived from another has moved the MFC (using primary clarifier overflow substance (primary clarifier overflow) inoculation at first) that surpasses 6 months in the batch charging mode pre-adaptation microbionation.According to Lovley, D.R.; Phillips, E.J.P.Novelmode of microbial energy metabolism:organic carbon oxidationcoupled to dissimilatory reduction of iron or manganese.Appl.Environ.Microbiol.1988,54, described in the 1472-1480, add culture medium in this reactor, described culture medium contains the 50mM phosphate buffer (PBS of 1g/L acetate; Na ₂HPO ₄, 4.09g/L and NaH ₂PO ₄H ₂O, 2.93g/L) or the PBS of 200mM, NH ₄Cl (0.31g/L), KCl (0.13g/L), and slaine (12.5mL/L) and vitamin (5mL) solution.When voltage is brought down below 20mV, upgrade feed liquid, form the once complete operation cycle.C-MFC is in the indoor operation of 30 ℃ controlled temperature.

The fresh primary clarifier overflow substance (except as otherwise noted) that B-MFC is used in the 1g/L dextrose culture-medium is inoculated, and this dextrose culture-medium uses 50 or 200mM PBS preparation as mentioned above.In independent battery of tests, described reactor uses the used identical pre-adaptation bacterial solution inoculation with C-MFC.All B-MFC are moving under 23 ± 3 ℃ ambient temperature on the testing stand.

Analyze

(1000 Ω, voltage except as otherwise noted) (V) use the universal instrument (Keithley Instruments, Ohio) that links to each other with computer to monitor once every 30min to external resistance in the MFC circuit.Electric current (I), power (P=IV) and coulombic efficiency (CE) are according to Kim, J.R.etal., Appl.Microbiol.Biotechnol.2005,68, method is calculated described in the 23-30, wherein power density is carried out normalization by the effective area of negative electrode one side, and the volume of volumetric power density by fluid nutrient medium carries out normalization.The electrochemical impedance spectroscopy (EIS) that internal resistance Rint uses potentiostat (PC 4/750, Gamry Instrument Inc., Pennsylvania) to measure records, and wherein the anode chamber is filled by PBS and substrate.According to Cheng, S.etal., Environ.Sci.Technol.2006,40, described in the 2426-2432, impedance measurement under the sinusoidal perturbation of 10mV amplitude 10 ⁵To the inherent open circuit voltage of 0.005Hz frequency range (0CV), carry out.Polarization curve obtains by measure the burning voltage that produces under different extrernal resistances, then according to Logan, and B.E.et al., Environ.Sci.Technol.2006,40, the method described in the 5181-5192 is used this polarization curve estimated maximum power density.Described C-MFC all moves two operation cycles at least under each extrernal resistance, the phase is about 2 days weekly.Described B-MFC needs longer cycle time (about 21 days), so under each extrernal resistance, polarization data is measured after the single operation cycle brings into operation 15min.According to He, Z.et al, Environ.Sci.Technol.2006,40,5212-5217; Cai, M.et al., Environ.Sci.Technol.2004,38,3195-3202; Raz, S.et al., Solid State Ionics2002,149,335-341; And Cooper, K.R.et al., J.Power Sources 2006,160, described in the 1088-1095., the internal resistance of C-MFC and B-MFC all uses the Nyquist mapping (Nyquist plot) of impedance spectrum by itself and X-axis (void value impedance Z _ImReal-valued impedance Z when=0) intersecting _ReDetermine that described internal resistance is defined as the summation of all Ohmic resistances, comprises bath resistance and contact resistance.

Use the generating situation of C-MFC

The voltage cycle that produces that contains the C-MFC of brush shape anode is reproducible behind 4 feed cycles that use fresh culture, and the maximum voltage that produces under the condition that connects 1000 Ω resistors is 0.57V and coulombic efficiency=41%.Figure 15 shows initial 4 generating cycles of the C-MFC that contains brush shape anode, and described C-MFC comprises the resistor of 50mM PBS and one 1000 Ω; Arrow represents to add the time of fresh culture among the figure in reactor.

According to polarization data, when current density is 0.82mA/cm ²(R _Ext=50 Ω) time, the maximum power that this fuel cell produces is 2400mW/m ², or power carried out normalization by this liquid reactor volume, be 73W/m ³, shown in Figure 16 A.Coulombic efficiency changes in the 40-60% scope according to described current density, as shown in figure 16.

The internal resistance of described brush shape C-MFC (200mM PBS) is R _Int=8 Ω, and the internal resistance of carbon cloth C-MFC (200mM PBS, 4cm electrode spacing) is R _Int=31 Ω are shown in Figure 17 and table 1.Figure 17 illustrates and the mapping of the corresponding Nyquist of the impedance spectrum of described C-MFC, this anti-resistance spectrum in 200mM PBS negative electrode and anode (bipolar electrode pattern) between record.Described MFC is discharged to 0.57V under 1000 Ω and external circuit has disconnected 2 hours.Internal resistance is the x values of intercept.

Use the generating situation of B-MFC

With the 600mW/m that uses the carbon paper electrode generation in 200mM PBS solution ²(0.98W/m ³) compare, the power that the brush electrode that uses in B-MFC produces is up to 1430mW/m ²(2.3W/m ³), as shown in figure 18.The power reduction that produces when using a kind of solution than low ionic strength to use brush shape anode is to 570mW/m ²(0.93W/m ³), the power reduction when using the carbon paper anode is to 300mW/m ²(0.50W/m ³).This influence of electrical conductivity of solution shows that Ohmic resistance reduces makes power increase with the increase (being up to the limit of restraining oneself of bacterium) of ionic strength.The internal resistance of described brush shape B-MFC is 50 Ω, and the value of other reactor condition is summarized in the table 1.

^aElectrode spacing is 4cm.

^bUse the inoculum of the MFC of pre-adaptation.

In order to confirm that using ammonia to handle brush electrode is a kind of effective ways that reduce adaptation time and increase power, uses untreated brush shape anode to carry out additional testing.The maximum of using the generated output when being untreated anode to reach is 750mW/m ², lower by 37% than the generated output of the anode of handling through ammonia, as shown in figure 18.The electrode that is untreated reaches the peak value generated output in first cycle and has spent 330 hours, and treated electrode has then only been spent 136 hours, and this explanation ammonia is handled and can be reduced adaptation time.Generated output when using treated brush electrode also is higher than the generated output when using the untreatment carbon paper electrode substantially, and the maximum generation power of generation is 600mW/m ²

Use the generating situation of random distribution fiber bundle

Present embodiment uses the B-MFC reactor that the application of graphite fibre random distribution or the non-structure configuration is tested.When using 0.11g 6 micron diameter fibers, use the maximum generation power of B-MFC random distribution or non-structure graphite fibre anode configuration to be 1100mW/m ², as shown in figure 19.When using 10 micron diameter fibers, the power bracket when mass loading is 0.09g to 0.35g is 690mW/m ²To 850mW/m ²The generated output scope of using 6 micron diameter fibers is 770 to 1100mW/m ², as shown in figure 19.

Embodiment 2

The preparation of negative electrode

Use an internal diameter 14.4mm (B0125, X-FLOW), the hydrophilic tubular milipore filter (polysulfone membrane on the complex polyester carrier) of wall thickness 0.6mm is as sleeve cathode.With this pipe be cut into 3,6 or the length of 12cm (be equivalent to 13.5,27 and 54cm ²Surface area), the commercially available graphite paint (ELC E34 Semi-Colloidal, SuperiorGraphite Co., Ltd) of applied in two coats then.Except as otherwise noted, cathod catalyst is tetramethylphenyl Cobalt Porphyrin (CoTMPP).CoTMPP/ carbon mix (20%CoTMPP) is according to Cheng, S.et al., Environ.Sci.Technol.2006,40, the preparation of method described in the 364-369, and mixes the formation slurry with 5% Nafion solution, every milligram of CoTMPP/C catalyst uses 7 microlitre Nafion.Then this slurry is applied to all sleeve cathodes towards the surface of air to reach about 0.5mg/cm ²The CoTMPP load capacity.In some tests, contain Pt, 0.35mg/cm ²Pt catalyst, waterproof paper, and the commercially available carbon paper negative electrode (A of E-Tek _Cat=7cm ²) can use catalyst towards water-soluble liquid level.Prepare one only the 3cm sleeve cathode of graphitiferous coating as the catalyst-free tester.

The preparation of anode

Described anode can be the common non-water-tight Toray carbon paper of a slice; E-Tek; A _An=7cm ², the long routine of or 25mm diameter * 25mm the graphite fibre brush; Fiber model: PANEX

33160K, ZOLTEK has 2235cm ²Estimating table area (95% porosity).

Sleeve cathode reactor with carbon paper anode

Each reactor configuration of present embodiment is all used the labelling method of X-YZ-J, wherein: X=anode material (C=carbon paper, B=black lead brush); Y=cathode material (C=carbon paper, T _n=length is the quantity of the sleeve cathode of 3cm, wherein n=1 to 4); Z=catalyst (Pt=platinum; Co=CoTMPP; The carbon of C=catalyst-free); With J=negative electrode configuration (I=is within reactor, and O=is outside reactor).

Three single chamber carbon paper anodes (C) MFC all is configured to sleeve cathode and is positioned at cylindrical chamber reactor (I), and described sleeve cathode is of a size of 4 or 6cm length * 3cm diameter, as shown in table 2, Figure 24.Table 2 illustrates electrode type and the electrode surface area that present embodiment uses; And electrode surface area and volume, volume, internal resistance, be normalized to the ratio of the maximum power density of anode surface area or total reactor volume; And the coulombic efficiency of all carbon paper anode MFC and brush shape anode MFC batch run in the present embodiment.

Two reactors all are configured to be coated with the sleeve cathode (TCo) of CoTMPP.One of them has an independent 3cm pipe (C-T ₁Co-I, the 4cm chamber), its total cathodic surface area is A _Cat=13.5cm ², the surface area that is normalized to reactor volume is A _{Cat, s}=59m ²/ m ³, another has two 3cm pipe (C-T that connect by lead ₂Co-I; The 6cm chamber; A _Cat=27cm ², A _{Cat, s}=84m ²/ m ³).

The 3rd reactor assembly is constructed to comprise: an independent 3cm sleeve cathode that does not contain any catalyst, C-T ₁C-I; The 4cm chamber; A _Cat=13.5cm ², A _{Cat, s}=59m ²/ m ³

Each cathode tube is inserted the center of a 2cm sliver of described chamber, and the carbon paper anode is positioned at the offside of another 2cm sliver.Described CoTMPP catalyst layer is coated on the inboard (side of film) of these pipes and towards air.

With Liu, H.et al., Environ.Sci.Technol.2004,38, the single chamber cube MFC of same type described in the 4040-4046 also uses the carbon paper anode and contains Pt catalyst (C-CPt-I; A _Cat=7cm ², A _{Cat, s}=25m ²/ m ³) the carbon paper negative electrode test, described electrode is positioned at the offside (4cm length * 3cm diameter) of described chamber.

Sleeve cathode reactor with brush shape anode

Use contains the sleeve cathode of CoTMPP catalyst (TCo) two different brush shape anode (B) MFC configurations is tested: one in reactor (I) have cylindrical chamber MFC (6cm length * 3cm the diameter) (B-T of sleeve cathode ₂Co-I); And the identical but sleeve cathode of type reactor (4cm length * 3cm diameter) (B-T of (0) outside reactor ₂Co-O), as shown in table 2.

For indoor sleeve cathode reactor, black lead brush shape anode vertically is arranged on the long reactor slide of 2cm, and two are respectively made the long reactor (B-T of 6-cm for long the inserting by adjacent 2cm thin slice through the continuous sleeve cathode of lead of 3cm ₂Co-I; A _Cat=27cm ², A _{Cat, s}=93m ²/ m ³).Described catalyst-coated is in the inboard of cathode tube (side of film) and towards air.Cathode tube is placed on the outer MFC of cube reactor and is constructed to the brush shape anode that uses one to be arranged in parallel at the long reative cell of 4cm center, and one of them independent 6cm grows, and (2 * 3cm) cathode tube is stretched (B-T from a side of reative cell ₂Co-O; A _Cat=27cm ², A _{Cat, s}=75m ²/ m ³).In this case, described catalyst-coated is in the outside of this cathode tube (support-side of film) and towards air.

The influence that brings for further research cathodic surface area adds the inside of this MFC with other 3cm sleeve cathode, connects sleeve cathode (B-T by outer lead ₃Co-I and B-T ₄Co-I).For the reactor with reactor outer cathode pipe, this length of tube increases to 12 (4 * 3) cm (B-T ₄Co-O), form 54cm ²Cathodic surface area.

Start and operation

All MFC are all according to Liu in the present embodiment, H.et al., and Environ.Sci.Technol.2004,38, method described in the 4040-4046 is used phosphate buffer (PBS, the 50mM in the nutrient medium; PH=7.0) mixture of the 50:50 of glucose in the nutrient medium (0.8g/L) and sanitary sewage (about 300mg-COD/L) is inoculated.

Behind 2-3 feed cycle that repeats, only add culture medium (no waste water).When the maximum voltage that produces can reappear, can think that reactor adapts at least 3 cycles.After these tests, will brush the shape anode reactor and transfer 200mM PBS to, because the increase of electrical conductivity of solution can increase generated output.When voltage reduce to about 20mV (40 to 500 Ω resistance) or about 40mV (1000 to 3000 Ω resistance) when following in reactor supplemented medium again.

Have and be arranged in inside reactor or outside brush shape anode and the reactor of sleeve cathode and also move under continuous flow mode, hydraulic detention time (HRT) is 24 hours (a total reactor volume).(AVI trace 210A infusion pump 3M) enters from anode one side, and discharges from negative electrode one side liquid stream by using microinfusion pump.These experiments are all implemented down at 30 ℃.

Calculate and measure

The output voltage of all reactors (V) is measured in fixing extrernal resistance (1000 Ω are unless there is note in addition) two ends Usage data collection system (2700, Keithly, the U.S.).Electrode potential uses universal instrument (83 III, Fluke, the U.S.) and reference electrode (Ag/AgCl; RE-5B, bio-analysis system, the U.S.) measure.Electric current (I=V/R), power (P=IV), and coulombic efficiency (based on the glucose of input) according to Zuo, Y.et al., Energy ﹠amp; Fuels.2006,20 (4), the method described in the 1716-1721 is calculated.Power density and current density are normalized to the effective area (m of carbon paper anode ²) or total reactor volume (m ³).

For obtaining polarization curve and power density curve, make external resistance be changed to 3000 Ω from 40 Ω as the function of electric current.For batch run, a resistor is used for a complete cycle (at least 24 hours), and independently uses in the cycle at least two, and for the Continuous Flow test, each resistor all used 24 hours at least.

For the brush shape anode reactor of carbon paper anode MFC that fills with the nutrient medium that contains 50mM PBS and use 200mM PBS, internal resistance R _IntBy 10 ⁵The electrochemical impedance spectroscopy with 10mV sinusoidal perturbation amplitude (EIS) to the 0.005Hz frequency range records, and this electrochemical impedance spectroscopy uses potentiostat (PC 4/750 potentiostat, Gamry Instr Ltd.) to measure.As Cheng, S.et al., Environ.Sci.Technol.2006.40, described in the 2426-2432 with anode as work electrode, negative electrode is as counterelectrode and reference electrode.

The oxygen transmission determines by the oxygen accumulation of measuring in the nonvaccinated carbon paper anode MFC reactor that by the maximum rate of sleeve cathode described carbon paper anode MFC reactor contains a clean 3cm pipe-shaped membrane (not containing any graphite/catalyst) and deoxidation deionized water.The effective mass tranfer coefficient k of oxygen is according to Cheng, S.etal., and Electrochem Commun.2006,8, the method described in the 489-494 is used the dissolved oxygen probe of the reactor center that is positioned at stirring, and (Foxy-21G, Ocean Optics Co., Ltd F1) measures.Proton conduction resistance by the pipe-shaped membrane negative electrode is according to Kim, J.et al., Environ.Sci.Technol.2007.41 (3), the added value of internal resistance was measured when the method described in the 1004-1009 added this membrane material by measuring between two carbon electrodes of two chambers cube reactor.The film pipe is scratched, be cut into annular to form 7cm ²Flat surfaces, be arranged in the middle of the reactor then, and make each carbon electrode and described film at a distance of 2cm.Contain film (R _{Int, m+}) and do not contain any film (R _{Int, m-}) the internal resistance of reactor can use potentiostat to measure by EIS.Proton conduction resistivity (the Ω cm of pipe-shaped membrane ²) according to (R _{Int, m+}-R _{Int, m-}) * A _MemCalculate.

The COD concentration of reactor effluent is according to for example American Public HealthAssociation; American Water works association; Water PollutionControl Federation, Standard Methods for the Examination ofWater and Wastewater, the 19th edition; Washington D.C., the standard method described in 1995 is measured.

The generating situation of the tubular reactor of carbon paper anode

After 4 whole carbon paper anode MFC reactors adapted to, formation was repeatably generated electricity the cycle rapidly.Figure 20 A shows, and as power density (open symbols), the voltage (filled symbols) of the function of the current density that is normalized to total reactor volume, they obtain by the external resistance (40 to 3000 Ω) that changes carbon paper anode MFC.According at two or more mean value of the output of the firm power in batch experiment period detecting independently, error range is ± S.D..

By external resistance is shown to have two sleeve cathode MFC (C-T that scribble the pipe of CoTMPP from power density curve and the polarization curve that 40 Ω change to 3000 Ω acquisition ₂Co-I; A _Cat=27cm ²) power that produces is only a little less than the carbon paper negative electrode (C-CPt-I with Pt catalyst; A _Cat=7cm ²), and the R that coexists _ExtUnder=250 Ω, the sleeve cathode system has 8.8 ± 1.0W/m ³(403 ± 33mW/m ², anode surface area) maximum power density, the carbon paper cathod system then is 9.9 ± 0.1W/m ³(394 ± 3mW/m ²), shown in Figure 20 A.The sleeve cathode area reduces by 50% (C-T ₁Co-I, A _Cat=13.5cm ²) only since reducing of cathode volume and affects volumetric power density (9.3 ± 0.3W/m ³R _Ext=250 Ω), but based on anode surface area (306 ± 8mW/m ²) power reduction 24%.Under the situation that catalyst-free exists, tubular reactor (C-T ₁C-I, A _Cat=13.5cm ²) produce much less or be 3.1 ± 0.1W/m ³(R _Ext=250 Ω) power is shown in Figure 20 A.The internal resistance scope of these 4 MFC is 84 to 131 Ω (table 2).

Figure 20 B illustrates electrode potential---negative electrode open symbols, the anode filled symbols as the function of the current density that is normalized to total reactor volume, and this figure obtains by the external resistance (40 to 3000 Ω) that changes carbon paper anode MFC.According at two or more mean value of the output of the firm power in batch experiment period detecting independently, error range is ± S.D..Figure 20 B shows under each comfortable identical electric current of these carbon paper anodes MFC has similar anode potential.Not being both of these 4 MFC reactor generated outputs because the difference of cathode potential.The sleeve cathode electromotive force can improve as catalyst and/or increase cathodic surface area by adding CoTMPP.Have 13.5 or 27cm ²Sleeve cathode (C-T surface area, that apply CoTMPP ₁Co-I and C-T ₂Co-I) 0 to 60A/m ³Current density range in reached and carbon paper Pt negative electrode (C-CPt-I) electromotive force much at one.

The generating situation that contains the tubular reactor of brush shape anode

The tubular reactor that all that use in the present embodiment contain brush shape anode has formed repeatably power cycle (50mM PBS) after about 14 resting periods.Figure 21 A shows power density (open symbols) and the voltage (filled symbols) of conduct based on the function of the current density of reactor volume, and this figure obtains by the external resistances (40 to 3000 Ω) that change these brush shape anodes MFC.According at two or more mean value of the output of the firm power in batch experiment period detecting independently, error range is ± S.D..

After the concentration of buffer solution increased to 200mM, inside contained the reactor (B-T of two 3cm sleeve cathodes ₂Co-I, A _Cat=27cm ²) the maximum volume power density that produces is 17.7 ± 0.2W/m ³(R _Ext=250 Ω), shown in Figure 21 A.Contain the sleeve cathode reactor (C-T of the sleeve cathode reactor of brush shape anode than the same-type of carbon paper anode ₂Co-I, 8.8 ± 1.0W/m ³) flash-up that produces 200%, the rising appreciably of total slippage (from 89 to 66 Ω) of this and internal resistance and annode area is (from 7 to 2235cm ²) consistent.The power that reactor produced that inside contains brush shape anode and sleeve cathode is and the brush shape anode reactor maximum power 8.2 ± 0.2W/m that contains an independent 6cm cathode tube outside reactor equally ³(R _Ext=250 Ω) twice is shown in Figure 21 A.

Figure 21 B shows the electrode potential (negative electrode open symbols, anode filled symbols) of conduct based on the function of the current density of reactor volume, and it obtains by the external resistance (40-3000 Ω) that changes brush shape anode MFC.According at two or more mean value of the output of the firm power in batch experiment period detecting independently, error range is ± S.D..The increase of the power output of inside reactor cathode tube is by at 0-58A/m ³Current range in the electromotive force of brush shape anode the high cathode electromotive force causes when remaining unchanged, referring to Figure 21 B.The OCP of this negative electrode when negative electrode is positioned at reactor (250 ± 8mV, OCP (138 ± 16mV) the high 112mV when Ag/AgCl) being positioned at outside the reactor than it.Along with the increase of electric current, at 58A/m ³Following electrical potential difference further increases to 240mV, shown in Figure 21 B.

Coulombic efficiency when using sleeve cathode

The coulombic efficiency of all reactors is the function (table 1 of current density; Additional information in the support information).Using under the carbon paper anode situation, the coulombic efficiency of sleeve cathode with CoTMPP catalyst is up to 40%, and the coulombic efficiency with carbon paper negative electrode (C-CPt-I) of Pt is 7-19%.(C-T when not containing catalyst ₁C-I), the coulombic efficiency of sleeve cathode reactor is 18 to 22%.(B-T in the time of outside cathode tube is positioned at reactor ₂Co-O), also coulombic efficiency can be increased to 52-58% by using black lead brush shape anode and using 200mM PBS to increase solution ion strength, when cathode tube is positioned at reactor (B-T ₂Co-I) time, can increase to 70-74%.

What we thought that described sleeve cathode reactor obtains is to be lower than due to its diffusion rate of passing the carbon paper negative electrode by the diffusion rate that oxygen passes tubular milipore filter than high coulomb efficiency.For a clean pipe-shaped membrane, we measure its O ₂Mass tranfer coefficient is k=7.8 * 10 ^-5Cm/s, this can make nearly 0.03mgO ₂It is 13.5cm that the oxygen of/h is passed to the sleeve cathode surface area ²The MFC system in (C-T ₁Co-I and C-T ₁Or 0.06mgO C-I), ₂It is 27cm that the oxygen of/h is passed to the sleeve cathode surface area ²The MFC system in (C-T ₂Co-I, B-T ₂Co-I and B-T ₂Co-O).On the contrary, 7cm ²The oxygen transfer rate that the carbon paper negative electrode (C-CPt-I) of surface area produces is 0.187mg/h, referring to Liu, and H.et al., Environ.Sci.Technol.2004,38,4040-4046.Therefore, seem described sleeve cathode system support aerobic oxidation that substrate is reduced to cause owing to oxygen diffuses through negative electrode than high coulomb efficiency.

The influence of sleeve cathode surface area

Use is placed on containing reactor brush shape the anode reactor interior or sleeve cathode that reactor is outer and has studied the influence that the sleeve cathode surface area brings.Figure 22 A and 22B show power (A) and volumetric power density (B), and they are the functions that contain the cathodic surface area of the sleeve cathode MFC that brushes the shape anode.According at two or more mean value of the output of the firm power in batch experiment period detecting independently, the error range among these figure is ± S.D..By in reactor, adding more 3cm cathode tube (B-T ₃Co-I and B-T ₄Co-I) or with the length of external cathode pipe increase to 12cm (B-T ₄Co-O) make the cathodic surface area of two kinds of configurations by 27cm ²(T ₂) increase to 40.5cm ²(T ₃) or 54cm ²(T ₄).For for the cathode tube in the reactor, peak power output increases with the increase of cathodic surface area, is respectively 0.51mW (B-T ₂Co-I), 0.66mW (B-T ₃Co-I) and 0.83mW (B-T ₄Co-I) (Figure 22 A).Because 3cm cathode tube of the every adding then volume of reactor also increases 8ml, but the different volumetric power density that reactor produced that these inside contain cathode tube when being normalized to volume is similar, and the maximum of Chan Shenging is about 18W/m in all cases ³(Figure 22 B).When cathode tube placed reactor outside, peak power output did not increase (Figure 22 A) with the increase of cathode tube length.Though two kinds of reactors all produce the power of about 0.3mW, the relatively shorter sleeve cathode volume of longer pipe shape negative electrode has increased 10ml, makes summation watt rating by 8.2W/m ³(B-T ₂Co-O) be reduced to 6.5W/m ³(B-T ₄Co-O) (Figure 22 B).

The Continuous Flow performance of sleeve cathode reactor

Move with continuous flow mode at inside reactor or outside two kinds of brush shape anode MFC that contain sleeve cathode.Figure 23 A and 23B show under 1000 fixing Ω resistance (except as otherwise noted) as the voltage (A) of the function of time and as the volumetric power density (B) of the function of the electric current that is normalized to volume, and they obtain by changing with external resistance (40-3000 Ω) continuous or the brush shape anode MFC that intermittent mode moves.Vertical line shows the time that external resistance changes in the polarization curve measurement.Arrow is represented the replacement of the sleeve cathode that reactor is outer.Contain (B-T under the situation of described cathode tube at this reactor ₂Co-I, A _Cat=27cm ²), output voltage can produce (520mV under 1000 Ω) immediately, and HRT is stable above 10 hours (Figure 23 A).Power density curve display performance is identical with the intermittent feeding test, produces about 18W/m ³Maximum power density (Figure 23 B).

Cathode tube also is similar (Figure 23 B) at the MFC of reactor outside measured power density curve with continuously with the intermittent feeding mode operation time.Yet, this reactor (B-T ₂Co-O, A _Cat=27cm ²) voltage that produced is unsettled in whole time span, it reduces to 380mV (1000 Ω) (Figure 23 A) from 500mV.

Use 1000 constant Ω external resistances to analyze the effluent of two kinds of reactors that move with continuous flow mode.MFC produces in reactor the time with cathode tube, and 37 ± 5% COD clearance is compared, and the reactor that has cathode tube outside MFC has produced 53 ± 5% COD clearance.

Internal resistance by the sleeve cathode contribution

Between two carbon electrodes of two chambers cube reactor, place a flat pipe-shaped membrane (7cm ²) time internal resistance measured be R _{Int, m+}=247 ± 6 Ω.When removing described film, internal resistance is R _{Int, m-}=84 ± 1 Ω.These resistances have shown that the proton conduction resistivity of described film is 1141 Ω cm ², so 13.5cm ²Or 27cm ²The internal resistance of pipe-shaped membrane negative electrode be respectively 84 Ω or 42 Ω.This shows that described film resistance is the highest and accounts for 64% of the total internal resistance of sleeve cathode reactor.

Any patent or publication mentioned in this specification are all included the application by reference in, and its degree of quoting is just included it in as mode by reference that each publication is illustrated particularly and seriatim.The mode that the U.S. Provisional Patent Application of submitting on May 2nd, 2,006 60/796,761 is quoted is in full included the application in.

Described composition of the application and method are represented preferred embodiment, are exemplary, rather than want to limit the scope of the invention.Those skilled in the art can change or otherwise use it.Can under the situation that does not depart from the described scope of the present invention of claims, carry out the use of this change and alternate manner.

Claims

1. microbiological fuel cell comprises:

A negative electrode, comprise a film, described film forms the cathode wall of sealing usually and defining an inner space, and described cathode wall has an inner surface and the opposed outer surface with described inner space adjacency, and described wall extends between first end and second end;

An anode, described anode is nontoxic substantially to close anode bacterium; And

A conduction connector connects described anode and described negative electrode.

2. the microbiological fuel cell of claim 1, wherein said film are selected from a NF membrane, milipore filter, and amberplex.

3. the microbiological fuel cell of claim 1 further comprises a kind of inner surface or the contacted electric conducting material of outer surface of and described film, and described electric conducting material is connected with described conduction connector conduction.

4. the microbiological fuel cell of claim 3, wherein said electric conducting material is a kind of carbon-based material.

5. the microbiological fuel cell of claim 3, wherein said electric conducting material is a graphite.

6. the microbiological fuel cell of claim 3, wherein said electric conducting material is a carbon-base coating, described carbon-base coating covers inner surface or the outer surface at least about 50% described film.

7. the microbiological fuel cell of claim 1 further comprises a kind of catalyst.

8. the microbiological fuel cell of claim 7, wherein said catalyst are selected from a kind of metallic catalyst, a kind of nonmetallic catalyst, and a kind of bond of above-mentioned substance of containing.

9. the microbiological fuel cell of claim 1, wherein said anode has greater than 100m ²/ m ³Specific area.

10. the microbiological fuel cell of claim 1, wherein said anode are a brush shape anode.

11. the microbiological fuel cell of claim 1 comprises two or more anodes.

12. the microbiological fuel cell of claim 1 comprises two or more negative electrodes.

13. the microbiological fuel cell of claim 1 further comprises a power supply, thereby produces hydrogen in order to the electromotive force that increases between described anode and described negative electrode in described microbiological fuel cell, described power supply is connected with described cathodic electricity with described anode.

14. the microbiological fuel cell of claim 13, wherein said power supply are a secondary microbiological fuel cell, described secondary microbiological fuel cell is designed in order to produce electric power.

15. a microbiological fuel cell comprises:

A specific area is greater than 100m ²/ m ³Anode, described anode is nontoxic substantially to close anode bacterium;

A negative electrode; And

A conduction connector that connects described anode and described negative electrode.

16. the microbiological fuel cell of claim 15, wherein said anode comprises one or more conductive fibers.

17. the microbiological fuel cell of claim 16, wherein said one or more conductive fibers are connected on the conductive cores supporter.

18. the microbiological fuel cell of claim 17, each single fiber of wherein said one or more conductive fibers all is connected on the described conductive cores supporter.

19. the microbiological fuel cell of claim 17, wherein described one or more fibers of at least a portion comprise one or more carbon fibers.

20. the microbiological fuel cell of claim 15 comprises two or more anodes.

21. the microbiological fuel cell of claim 15 comprises two or more negative electrodes.

22. the microbiological fuel cell of claim 15 further comprises a power supply, thereby makes hydrogen in order to the electromotive force that increases between described anode and described negative electrode in described microbiological fuel cell, described power supply is connected with described cathodic electricity with described anode.

23. the microbiological fuel cell of claim 23, wherein said power supply are a secondary microbiological fuel cell, described secondary microbiological fuel cell is designed in order to produce electric power.

24. a negative electrode that is used for microbiological fuel cell comprises:

A film, described film forms the cathode wall of sealing usually and defining an inner space, described cathode wall has an inner surface and the opposed outer surface with described inner space adjacency, described wall launches between first end and second end, and described wall has the shape of a routine.

25. the negative electrode that is used for microbiological fuel cell of claim 24, wherein said film are selected from a NF membrane, milipore filter, and amberplex.

26. the negative electrode that is used for microbiological fuel cell of claim 24 also comprises a kind of inner surface or the contacted electric conducting material of outer surface of and described film, described electric conducting material is connected with the conduction connector conduction.

27. the negative electrode that is used for microbiological fuel cell of claim 26, wherein said electric conducting material are a kind of carbon-based material.

28. the negative electrode that is used for microbiological fuel cell of claim 26, wherein said electric conducting material are graphite.

29. the negative electrode that is used for microbiological fuel cell of claim 26, wherein said electric conducting material are present on the inner surface or outer surface at least about 50% described film.

30. the negative electrode that is used for microbiological fuel cell of claim 24 further comprises a kind of catalyst that is selected from following material: a kind of catalyst and a kind of catalyst that promotes the proton reduction that promotes hydrogen reduction.

31. the negative electrode of claim 24, at least one in wherein said first end or second end is closed.

32. the negative electrode of claim 24, wherein said inner space are at least in part by a kind of liquid filling.

33. the negative electrode of claim 24, wherein said wall have a shape that is selected from common cylindrical shaped and conventional hollow sheeting shape.

34. a method that produces hydrogen comprises:

A microbiological fuel cell that contains a sleeve cathode and/or brush shape anode is provided; And apply an auxiliary voltage, increasing the electromotive force between described anode and described negative electrode, thereby produce hydrogen.

35. a method that produces electric power comprises:

A microbiological fuel cell that contains a sleeve cathode and/or brush shape anode is provided.

36. the generating and/or the method for hydrogen comprise:

The microbiological fuel cell of a claim 1 or 15 is provided; And

Provide waste water as the biodegradable substrate that is used for bacterial oxidation.

37. one kind in essence as the method for described generating of specification and/or hydrogen manufacturing.

38. one kind in essence as the described sleeve cathode of specification.

39. a specific area is greater than 100m ²/ m ³Anode, described anode is in essence as nontoxic to close anode bacterium substantially as described in the specification.

40. one kind in essence as the described fuel cell of specification.