WO2019069851A1 - Ensemble électrode, et pile à combustible microbienne et dispositif de traitement de l'eau l'utilisant - Google Patents

Ensemble électrode, et pile à combustible microbienne et dispositif de traitement de l'eau l'utilisant Download PDF

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Publication number
WO2019069851A1
WO2019069851A1 PCT/JP2018/036686 JP2018036686W WO2019069851A1 WO 2019069851 A1 WO2019069851 A1 WO 2019069851A1 JP 2018036686 W JP2018036686 W JP 2018036686W WO 2019069851 A1 WO2019069851 A1 WO 2019069851A1
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WIPO (PCT)
Prior art keywords
oxygen
bag
electrode
spacer
oxygen supply
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PCT/JP2018/036686
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English (en)
Japanese (ja)
Inventor
道彦 谷
直毅 吉川
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パナソニックＩｐマネジメント株式会社
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Publication of WO2019069851A1 publication Critical patent/WO2019069851A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/08—Flat membrane modules
    • B01D63/089—Modules where the membrane is in the form of a bag, membrane cushion or pad
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/08—Flat membrane modules
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to an electrode assembly and a microbial fuel cell and a water treatment apparatus using the same.
  • the present invention relates to an electrode assembly capable of purifying wastewater and generating electrical energy, and a microbial fuel cell and a water treatment apparatus using the same.
  • a microbial fuel cell is an apparatus which oxidizes and decomposes the organic matter while converting the chemical energy of the organic matter contained in the wastewater into electric energy by the catalytic action (metabolic reaction, biochemical conversion) of the microorganism. That is, the microbial fuel cell produces electric energy directly from the organic matter by the action of the microorganism. Therefore, the microbial fuel cell can be expected to improve the energy recovery efficiency as compared with the conventional energy recovery system using the conversion step from organic matter to biogas. Moreover, the microbial fuel cell can be used not only for power generation but also as an incidental facility for waste water treatment, organic waste treatment, organic waste treatment, and the like.
  • a microbial fuel cell comprises an anode that holds microorganisms and a cathode that contacts an oxidizing substance.
  • An example of such a microbial fuel cell is an electrode assembly including a hollow member, a hollow member, an oxygen supply unit that supplies oxygen to the hollow member, and an oxygen-permeable unit that transmits oxygen supplied to the hollow unit.
  • Patent Document 1 discloses the disclosure.
  • the electrode complex is provided on the outside of the hollow member in the oxygen permeable part, and from the oxygen permeable part side, an electrode in which a water repellent layer having oxygen permeability and a conductive layer are laminated, and a hollow part And a shock-absorbing member provided with pressure resistance.
  • the said composite electrode body has air permeability from an oxygen supply part to an oxygen permeation part.
  • the electrode complex of Patent Document 1 includes the buffer member inside the hollow member as described above. Therefore, even under a high water pressure environment, a space for supplying oxygen sufficiently to the cathode is secured, so that it is possible to stably produce electrical energy while suppressing the deterioration of the battery characteristics.
  • an object of the present invention is to provide an electrode composite capable of sufficiently supplying oxygen to the electrode and suppressing the deterioration of the battery characteristics even in an environment such as the outdoors, a microbial fuel cell using the same, and It is in providing a water treatment device.
  • an electrode assembly comprises a hollow portion, an oxygen supply portion that supplies oxygen to the hollow portion, and oxygen permeation that transmits oxygen supplied to the hollow portion. And an air-permeable bag-like member extending from the oxygen supply portion to the oxygen-permeable portion. Furthermore, the electrode assembly includes a spacer provided in the hollow portion and accommodated in the bag-like member, and an electrode having a conductive layer provided outside the bag-like member in the oxygen permeable portion. And the bag-like member is sealed by the bag-like member or covered with a cover part so that the oxygen supply part side of the spacer is not exposed to the external space.
  • a microbial fuel cell includes an electrode complex and an anode supporting a microorganism, and the electrode in the electrode complex is a cathode.
  • a water treatment apparatus comprises an electrode complex and an anode carrying a microorganism that purifies a liquid to be treated, and the electrode in the electrode complex is a cathode.
  • FIG. 1 is a perspective view showing an example of an electrode complex according to an embodiment of the present invention in a disassembled state.
  • FIG. 2A is a perspective view showing an example of a bag-like member according to an embodiment of the present invention.
  • FIG. 2B is a perspective view showing a method of manufacturing the bag-like member of FIG. 2A.
  • FIG. 3A is a perspective view showing another example of the bag-like member according to the embodiment of the present invention.
  • FIG. 3B is a perspective view showing a method of manufacturing the bag-like member of FIG. 3A.
  • FIG. 4 is a perspective view showing an example of a spacer according to an embodiment of the present invention.
  • FIG. 5A is a plan view showing an example of a spacer according to an embodiment of the present invention.
  • FIG. 5A is a plan view showing an example of a spacer according to an embodiment of the present invention.
  • FIG. 5B is a plan view showing another example of the spacer according to the embodiment of the present invention.
  • FIG. 5C is a plan view showing another example of the spacer according to the embodiment of the present invention.
  • FIG. 6 is a perspective view showing another example of the electrode assembly according to the embodiment of the present invention in a disassembled state.
  • FIG. 7 is a perspective view showing an example of an electrode complex according to an embodiment of the present invention.
  • FIG. 8 is a cross-sectional view taken along the line AA in FIG.
  • FIG. 9 is a cross-sectional view showing another example of the electrode assembly according to the embodiment of the present invention.
  • FIG. 10 is a cross-sectional view showing another example of the electrode assembly according to the embodiment of the present invention.
  • FIG. 10 is a cross-sectional view showing another example of the electrode assembly according to the embodiment of the present invention.
  • FIG. 11 is a perspective view showing another example of the electrode assembly according to the embodiment of the present invention.
  • FIG. 12 is a cross-sectional view taken along the line BB in FIG.
  • FIG. 13 is a cross-sectional view showing an example of the microbial fuel cell according to the embodiment of the present invention.
  • FIG. 14 is a perspective view showing an example in which a through hole is formed in the bag-like member according to the embodiment of the present invention.
  • FIG. 15 is a front view showing an example of a fixing method by the bag-like member according to the embodiment of the present invention.
  • FIG. 16 is a side view showing an example of the fixing method using the bag-like member according to the embodiment of the present invention.
  • FIG. 17 is a side view showing another example of the bag-like fixing method according to the embodiment of the present invention.
  • FIG. 18 is a side view showing another example of the bag-like fixing method according to the embodiment of the present invention.
  • the electrode assembly 100 includes a bag-like member 10, a spacer 20, and an electrode 30.
  • the bag-like member 10 has a hollow portion 1, an oxygen supply portion 4 for supplying oxygen to the hollow portion 1, and an oxygen permeable portion 5 for transmitting the oxygen supplied to the hollow portion 1.
  • the bag-like member 10 has an oxygen permeable membrane formed into a bag shape, and has a hollow portion 1 inside.
  • the hollow portion 1 is a space formed inside the bag-like member 10. Specifically, the hollow portion 1 is a space surrounded by a sheet forming the bag-like member 10.
  • the oxygen supply unit 4 supplies oxygen to the hollow portion 1.
  • the oxygen supply unit 4 is an opening provided in the upper portion of the bag-like member 10, but is not limited to such an opening as long as oxygen can be supplied to the hollow portion 1.
  • the bag-like member 10 itself can be used as the oxygen supply unit 4.
  • the oxygen permeable portion 5 permeates the oxygen supplied to the hollow portion 1.
  • the oxygen permeable portion 5 is a pore provided on the side surface 11 of the bag-like member 10. That is, the bag-like member 10 has oxygen permeability.
  • the side surface 11 of the bag-like member 10 preferably has pores in order to ensure oxygen permeability.
  • the bag-like member 10 is waterproof in order to prevent the electrolyte solution from flowing into the internal space of the bag-like member 10.
  • the material which comprises the bag-like member 10 is not specifically limited, For example, at least one chosen from the group which consists of resin, a metal, and a carbon material can be used.
  • the shape of the member constituting the bag-like member 10 is not particularly limited either, but may be made of, for example, a thin film having a plurality of pores, and is formed of a network structure having a plurality of pores. May be The size of the pore is not particularly limited as long as it has oxygen permeability and waterproofness, but preferably 0.01 ⁇ m to 10 ⁇ m. The pore size can be obtained by taking the average of the pore diameters measured by an electron microscope or the like.
  • Cellpore (trademark) by Sekisui Chemical Co., Ltd. can be used, for example.
  • the method for manufacturing the bag-like member 10 is not particularly limited. For example, after two sheets 10 a are stacked, the bag-like member 10 is heat-welded by heat welding each side (both sides and the base) of the sheet 10 a. It can be made. When two sheets 10a are stacked, as shown in FIGS. 2A and 2B, after one sheet 10a is folded in half and stacked, the inner surfaces of both sides of the sheet 10a are heat-welded. The seal portion 10b may be formed.
  • the bottom side of the bag-like member 10 is not a seal portion where two sheets of the sheet 10 a are laminated but a continuous sheet 10 a. Water resistance can be improved.
  • the both sides are folded so as to be the inside of the bag-like member 10, and the outer surfaces of both sides of the sheet 10a May be heat-welded to form the seal portion 10c.
  • the seal portion 10 c formed in this manner has a portion where four sheets 10 a are stacked.
  • the water resistance of the formed bag-like member 10 can be improved by about 50% as compared with the heat welding method of FIGS. 2A and 2B.
  • Such a seal portion 10c is formed by folding and overlapping the sheet 10a on the opposite side to FIGS. 2A and 2B and thermally welding both sides of the sheet 10a to form the seal portion 10c. It can also be formed by turning inside and outside.
  • the spacer 20 is provided in the hollow portion 1 and accommodated in the bag-like member 10. That is, the spacer 20 is disposed in the hollow portion 1 of the bag-like member 10.
  • the spacer 20 has a rectangular parallelepiped shape, and includes a right side wall 21a, a left side wall 21b, a front wall 21c, and a rear wall 21d, which form an internal space.
  • the upper surface of the spacer 20 is opened so that oxygen (air) can be ventilated.
  • the electrode assembly 100 includes an electrode 30 provided outside the bag-like member 10 in the oxygen permeable portion 5.
  • the electrode 30 is configured by laminating a water repellent layer 31 having oxygen permeability and a conductive layer 32 from the oxygen permeable portion 5 side.
  • oxygen air is supplied from the oxygen supply unit 4 of the bag-like member 10 to the internal space of the spacer 20.
  • at least the right side wall 21a and the left side wall 21b of the spacer 20 have oxygen permeability. Therefore, oxygen supplied from the oxygen supply unit 4 to the internal space of the spacer 20 is supplied to the water repellent layer 31 of the electrode 30 through the right side wall 21 a and the left side wall 21 b of the spacer 20 and the oxygen permeable portion 5 of the bag-like member 10. Be done. That is, in the present embodiment, the bag-like member 10 has air permeability from the oxygen supply unit 4 to the oxygen permeable unit 5.
  • the spacer 20 is disposed in the internal space of the bag-like member 10. Therefore, even if the electrode assembly 100 is immersed in the electrolytic solution and water pressure is applied to the electrode 30, the electrode 30 is held by the spacer 20. Therefore, the electrode 30 is prevented from being curved in the internal space of the bag-like member 10. Be done. As a result, the air permeability from the oxygen supply unit 4 of the bag-like member 10 to the oxygen permeation unit 5 is sufficiently secured, so that the oxygen supply performance to the water repellent layer 31 of the electrode 30 can be improved.
  • the ISO air permeability from the oxygen supply unit 4 to the oxygen permeable unit 5 is preferably 1 ⁇ 10 ⁇ 5 ⁇ m / Pa ⁇ s to 100 ⁇ m / Pa ⁇ s. That is, the ISO air permeability from the oxygen supply unit 4 to the spacer 20 and the oxygen permeable unit 5 to the surface of the water repellent layer 31 of the electrode 30 is preferably in the above range.
  • the air permeability is an average flow rate of air per unit area, unit pressure difference and unit time, and the higher the value, the easier the air will pass.
  • the oxygen permeability of the electrode complex 100 is improved by the ISO air permeability of the electrode complex 100 being 1 ⁇ 10 ⁇ 5 ⁇ m / Pa ⁇ s or more.
  • the contact rate can be increased.
  • the ISO air permeability from the oxygen supply unit 4 to the oxygen permeation unit 5 is preferably 2 ⁇ 10 ⁇ 5 ⁇ m / Pa ⁇ s or more, and 7.9 ⁇ 10 ⁇ 5 ⁇ m / Pa ⁇ s or more Is more preferable, and particularly preferably 2.9 ⁇ 10 ⁇ 4 ⁇ m / Pa ⁇ s or more.
  • the ISO air permeability of the electrode complex 100 can be measured in accordance with Japanese Industrial Standard JIS P8117: 2009 (Paper and board-air permeability and air resistance test method (intermediate range)-Gurley method). it can.
  • compressive strength of the surface electrodes 30 is preferably 0.01kgf / cm 2 ⁇ 10kgf / cm 2.
  • compressive strength of the electrode assembly 100 is in this range, the electrode 30 is maintained in a flat state by suppressing the curvature of the electrode 30, even when the electrode assembly 100 is enlarged and a large water pressure is applied to the electrode 30. It is possible to maintain high oxygen permeability.
  • compressive strength is the value which remove
  • the compressive strength in this specification shows the compressive stress reached when relative deformation is within 10% according to ISO844: 2004 (hard foam plastic-measurement of compressive properties) specified by the International Organization for Standardization. . Therefore, the compressive strength of the surface on which the electrode 30 is provided in the electrode assembly 100 can be measured in accordance with ISO 844: 2004.
  • the spacer 20 has a rectangular parallelepiped shape, and the upper surface is opened to secure oxygen permeability, and an inner space is formed by the right side wall 21a, the left side wall 21b, the front wall 21c, and the rear wall 21d. There is. Then, in order to further improve the compressive strength of the spacer 20, the support member 22 may be provided in the internal space of the spacer 20. By providing the supporting member 22, since the space between the right side wall 21 a and the left side wall 21 b of the spacer 20 facing the electrode 30 is supported and reinforced, the above-described compressive strength is enhanced and deformation of the electrode 30 is further suppressed. It becomes possible.
  • the shape of the support member 22 is not particularly limited as long as the compressive strength of the spacer 20 can be increased.
  • the spacer 20 is internally provided with the plate member 22a, and the shape of the cross section along the stacking direction X of the bag-like member 10 and the electrode 30 in the spacer 20 is a truss shape Is preferred. That is, it is preferable that the support member 22 is formed of a plate member 22a, and a truss structure is formed by the plate member 22a and the right side wall 21a, the left side wall 21b, the front wall 21c and the rear wall 21d of the spacer 20.
  • the spacer 20 includes a plate member 22b inside, and the shape of the cross section in the stacking direction X of the bag-like member 10 and the electrode 30 in the spacer 20 is preferably a wave shape. That is, the support member 22 is formed of a corrugated plate member 22b, and the apex 22c of the plate member 22b is in contact with the right side wall 21a and the left side wall 21b of the spacer 20. Also by providing such a corrugated support member 22, the stability of the spacer 20 is improved, and the compressive strength can be further improved.
  • the spacer 20 preferably comprises one or more cylindrical members. That is, the support member 22 is formed of a cylindrical member 22d having a cylindrical shape, and a plurality of cylindrical members 22d are disposed so as to contact the right side wall 21a, the left side wall 21b, the front wall 21c and the rear wall 21d of the spacer 20 There is.
  • the stability of the spacer 20 can be improved, and the compressive strength can be further improved.
  • the support member 22 may be provided on the entire inside of the spacer 20 from the top surface to the bottom surface of the spacer 20 along the vertical direction Y perpendicular to the stacking direction X of the bag-like member 10 and the electrode 30. Further, the support member 22 may be provided only at the central portion of the top and bottom surfaces of the spacer 20 in the vertical direction Y. Furthermore, the support member 22 may be provided on the entire inside of the spacer 20 from the front wall 21 c to the rear wall 21 d of the spacer 20 along the depth direction Z perpendicular to the stacking direction X and the vertical direction Y. Further, the support member 22 may be provided only at the central portion of the front wall 21 c and the rear wall 21 d of the spacer 20 in the depth direction Z.
  • the plate members constituting the support member 22 are disposed along the vertical direction Y. That is, the plate members are arranged such that the cross section along the XZ plane is in a truss shape, a wave shape, or a circular shape.
  • the plate members constituting the support member 22 may be disposed along the depth direction Z. That is, the plate members may be arranged such that the cross section along the XY plane is truss-shaped, wave-shaped, or circular.
  • the material of the member which comprises the spacer 20 is not specifically limited, For example, at least one chosen from the group which consists of resin, a metal, glass, and a carbon material can be used. Further, as the resin, at least one selected from the group consisting of polystyrene, polyethylene, polypropylene, polyvinyl chloride and polycarbonate can be used. Further, as the metal, at least one of stainless steel and aluminum can be used.
  • the shape of the members constituting the spacer 20 is also not particularly limited.
  • the electrode assembly 100 according to this embodiment needs to have air permeability from the oxygen supply unit 4 to the oxygen permeable unit 5 in a state where the spacer 20 is inserted in the hollow portion 1 of the bag-like member 10 There is. Therefore, since the spacer 20 itself needs to have high air permeability, it is preferable that the spacer 20 be formed of a flat plate having a plurality of pores. Moreover, it is also preferable that the spacer 20 is comprised from the network-like structure which has a several pore. Furthermore, the spacers 20 preferably have a plurality of pores formed at a constant pitch.
  • the present invention is not limited to these configurations. For example, it may be a structure in which a part of a flat plate penetrates largely.
  • the electrode assembly 100 needs to have air permeability from the oxygen supply unit 4 to the oxygen permeable unit 5. Therefore, in the spacer 20, preferably, pores are formed in at least the right side wall 21a and the left side wall 21b facing the electrode 30. And the pore may not be formed in the front wall 21c and the rear wall 21d which do not face the electrode 30.
  • the material and shape of the support member 22 are not particularly limited either, but may be the same as the spacer 20.
  • the electrode 30 is made of a gas diffusion electrode including a water repellent layer 31 having oxygen permeability and a conductive layer 32 stacked on the water repellent layer 31.
  • a gas diffusion electrode By using such a gas diffusion electrode, oxygen in the gas phase can be easily supplied. Furthermore, there are the following advantages as compared to the case of supplying the electrode 30 with dissolved oxygen dissolved in water, for example. In the case where the dissolved oxygen is supplied to the electrode 30, there is a problem that the oxidation and power generation of the organic substance contained in the liquid to be treated (the electrolytic solution) such as wastewater is limited by the diffusion rate of the dissolved oxygen.
  • the diffusion rate of oxygen in the gas phase is extremely larger than the diffusion rate of dissolved oxygen, oxidation and power generation of organic substances can be efficiently performed. Therefore, it is possible to improve the output of the fuel cell.
  • the conductive layer 32 has water repellency, oxygen in the gas phase can be easily supplied, so that the electrode 30 is necessarily provided with the water-repellent layer 31 as a layer different from the conductive layer 32. It does not have to be That is, the electrode 30 may have the conductive layer 32 provided outside the bag-like member 10 in the oxygen permeable portion 5.
  • the electrodes 30 are provided on both the right side surface and the left side surface of the bag-like member 10.
  • the present embodiment is not limited to this configuration, and the electrode 30 may be provided on only one side surface of the bag-like member 10.
  • the water repellent layer 31 is a layer having both water repellency and gas permeability.
  • the water repellent layer 31 is configured to allow the movement of the gas from the gas phase to the liquid phase while well separating the gas phase and the liquid phase in the electrochemical system in the microbial fuel cell. That is, the water repellent layer 31 is configured to transmit oxygen in the gas phase and move it to the conductive layer 32. It is preferable that such a water repellent layer 31 be porous. In this case, the water repellent layer 31 can have high gas permeability.
  • the conductive layer 32 preferably includes, for example, a porous conductive material and a catalyst supported on the conductive material.
  • the conductive layer 32 may be made of a porous and conductive catalyst.
  • the electrode 30 preferably further includes an oxygen permeable layer 33 disposed between the water repellent layer 31 and the conductive layer 32 and having oxygen permeability. Since the oxygen permeable layer 33 has oxygen permeability, it has a function of supplying oxygen to the conductive layer 32.
  • the water repellent layer 31, the conductive layer 32, and the oxygen permeable layer 33 of the electrode 30 in the present embodiment will be described in more detail.
  • the water repellent layer 31 diffuses oxygen and supplies oxygen to the conductive layer 32 substantially uniformly. Therefore, the water repellent layer 31 is preferably a porous body so as to diffuse the oxygen.
  • the water repellent layer 31 preferably has water repellency. When the water repellent layer 31 has water repellency, the pores of the porous body are blocked by condensation or the like, and the decrease in the oxygen diffusivity can be suppressed.
  • the electrode assembly 100 is used in a microbial fuel cell or a water treatment apparatus, the liquid phase hardly penetrates into the water repellent layer 31, and the water repellent layer 31 easily contacts with oxygen.
  • the material constituting the water repellent layer 31 is not particularly limited as long as oxygen can be diffused.
  • a material which comprises the water repellent layer 31 for example, at least one selected from the group consisting of polyethylene, polypropylene, nylon, and polytetrafluoroethylene can be used. These materials tend to form a porous body and also have high water repellency, so that clogging of pores can be suppressed to improve gas diffusion.
  • the water repellent layer 31 is preferably a non-woven fabric or a film made of the above material. When the water repellent layer 31 is formed of a film of the above material, it is preferable to have a plurality of through holes in the laminating direction X of the water repellent layer 31 and the conductive layer 32.
  • the water repellent layer 31 may be subjected to a water repellent treatment using a water repellent agent as needed in order to enhance the water repellency.
  • a water repellent such as polytetrafluoroethylene (PTFE) may be attached to the porous body constituting the water repellent layer 31 to improve the water repellency.
  • PTFE polytetrafluoroethylene
  • the conductive layer 32 can be configured to include a porous conductive material and a catalyst supported by the conductive material.
  • the conductive material in the conductive layer 32 can be, for example, at least one material selected from the group consisting of carbon-based materials, conductive polymers, semiconductors, and metals.
  • the carbon-based material at least one selected from the group consisting of carbon paper, carbon cloth and graphite sheet can be used.
  • the conductive layer 32 may be made of one selected from the group consisting of carbon paper, carbon cloth, and a graphite sheet, or may be a laminate obtained by laminating a plurality of these.
  • Carbon paper which is a non-woven fabric of carbon fibers, carbon cloth which is a woven fabric of carbon fibers, and a graphite sheet made of graphite have high corrosion resistance and have an electrical resistivity equal to that of a metal material. It is possible to achieve both durability and conductivity.
  • the conductive polymer is a generic term for polymer compounds having conductivity.
  • the conductive polymer for example, polymers of single monomers having aniline, aminophenol, diaminophenol, pyrrole, thiophene, paraphenylene, fluorene, furan, acetylene or derivatives thereof as a constitutional unit, and two or more kinds of monomers And copolymers thereof.
  • examples of the conductive polymer include polyaniline, polyaminophenol, polydiaminophenol, polypyrrole, polythiophene, polyparaphenylene, polyfluorene, polyfuran, polyacetylene and the like.
  • the conductive material made of metal include conductive metals such as aluminum, copper, stainless steel, nickel and titanium. In consideration of availability, cost, corrosion resistance, durability and the like, the conductive material is preferably a carbon-based material.
  • the shape of the conductive material is preferably powdery or fibrous.
  • the conductive material may be supported by a support.
  • the support refers to a member which itself is rigid and can give the gas diffusion electrode a certain shape.
  • the support may be an insulator or a conductor.
  • examples of the support include glass, plastic, synthetic rubber, ceramics, paper treated with water or water repellent, plant pieces such as wood pieces, and animal pieces such as bone pieces and shells. .
  • Examples of supports having a porous structure include porous ceramics, porous plastics, sponges and the like.
  • examples of the support include carbon paper, carbon fibers, carbon-based materials such as carbon rods, metals, conductive polymers, and the like.
  • the conductive material supporting a carbon-based material is disposed on the surface of the support, and the support can also function as a current collector.
  • the catalyst in the conductive layer 32 is preferably a carbon-based material doped with metal atoms.
  • the metal atom is not particularly limited, but titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium It is preferable that it is at least one selected from the group consisting of platinum, and gold.
  • the carbon-based material exhibits excellent performance as a catalyst for particularly promoting the oxygen reduction reaction and the oxygen generation reaction.
  • the amount of metal atoms contained in the carbon-based material may be appropriately set so that the carbon-based material has excellent catalytic performance.
  • the carbon-based material is preferably further doped with one or more nonmetallic atoms selected from nitrogen, boron, sulfur and phosphorus.
  • the amount of nonmetal atoms doped in the carbon-based material may also be appropriately set so that the carbon-based material has excellent catalytic performance.
  • the carbon-based material is based on a carbon source material such as graphite and amorphous carbon, and the carbon source material is doped with metal atoms and one or more nonmetal atoms selected from nitrogen, boron, sulfur and phosphorus It is obtained by
  • the combination of metal atoms and nonmetal atoms doped in the carbon-based material is appropriately selected.
  • the nonmetal atom contains nitrogen and the metal atom contains iron.
  • the carbon-based material can have particularly excellent catalytic activity.
  • the nonmetal atom may be only nitrogen.
  • the metal atom may be only iron.
  • the nonmetal atom may contain nitrogen, and the metal atom may contain at least one of cobalt and manganese. Also in this case, the carbon-based material can have particularly excellent catalytic activity.
  • the nonmetal atom may be only nitrogen.
  • the metal atom may be only cobalt, only manganese, or only cobalt and manganese.
  • the shape of the carbon-based material is not particularly limited.
  • the carbon-based material may have a particulate shape or may have a sheet-like shape.
  • the dimensions of the carbon-based material having a sheet-like shape are not particularly limited, and, for example, the carbon-based material may have minute dimensions.
  • the carbonaceous material having a sheet-like shape may be porous. It is preferable that the porous carbon-based material having a sheet-like shape has, for example, a woven-like shape, a non-woven-like shape or the like.
  • Such a carbon-based material can constitute the conductive layer 32 without the conductive material.
  • the carbon-based material configured as a catalyst in the conductive layer 32 can be adjusted as follows. First, a mixture containing, for example, a nonmetal compound containing at least one nonmetal selected from the group consisting of nitrogen, boron, sulfur, and phosphorus, a metal compound, and a carbon source material is prepared. Then, the mixture is heated at a temperature of 800 ° C. or more and 1000 ° C. or less for 45 seconds or more and less than 600 seconds. Thereby, a carbon-based material configured as a catalyst can be obtained.
  • a nonmetal compound containing at least one nonmetal selected from the group consisting of nitrogen, boron, sulfur, and phosphorus, a metal compound, and a carbon source material is prepared. Then, the mixture is heated at a temperature of 800 ° C. or more and 1000 ° C. or less for 45 seconds or more and less than 600 seconds. Thereby, a carbon-based material configured as a catalyst can be obtained.
  • the carbon source material for example, graphite or amorphous carbon can be used.
  • the metal compound is not particularly limited as long as it is a compound containing a metal atom which can coordinately bond with a nonmetal atom doped in the carbon source material.
  • metal compounds include inorganic metal salts such as metal chlorides, nitrates, sulfates, bromides, iodides and fluorides, organic metal salts such as acetates, hydrates of inorganic metal salts, and organic metal salts It is possible to use at least one selected from the group consisting of hydrates of For example, when graphite is doped with iron, the metal compound preferably contains iron (III) chloride.
  • the metal compound when graphite is doped with cobalt, the metal compound preferably contains cobalt chloride.
  • the metal compound when manganese is doped to the carbon source material, the metal compound preferably contains manganese acetate.
  • the amount of the metal compound used is preferably determined so that, for example, the ratio of metal atoms in the metal compound to the carbon source material is in the range of 5 to 30% by mass, and this ratio is further preferably 5 to 20% by mass More preferably, it is determined to be within the range.
  • the nonmetallic compound is preferably at least one nonmetallic compound selected from the group consisting of nitrogen, boron, sulfur and phosphorus as described above.
  • nonmetal compounds include pentaethylenehexamine, ethylenediamine, tetraethylenepentamine, triethylenetetramine, octylboronic acid, 1,2-bis (diethylphosphinoethane), triphenyl phosphite, and benzyl disulfide.
  • At least one compound selected from the group consisting of The amount of the nonmetallic compound used is appropriately set according to the doping amount of the nonmetallic atom to the carbon source material.
  • the amount of the nonmetallic compound used is preferably determined such that the molar ratio of the metal atom in the metallic compound to the nonmetallic atom in the nonmetallic compound is in the range of 1: 1 to 1: 2. More preferably, it is determined to be in the range of 1: 1.5 to 1: 1.8.
  • the mixture containing the nonmetal compound, the metal compound, and the carbon source material when preparing the carbon-based material configured as a catalyst is obtained, for example, as follows. First, the carbon source material, the metal compound and the nonmetal compound are mixed, and if necessary, a solvent such as ethanol is added to adjust the total amount. These are further dispersed by ultrasonic dispersion. Subsequently, after heating them to a suitable temperature (for example 60 ° C.), the mixture is dried to remove the solvent. Thereby, a mixture containing the nonmetal compound, the metal compound and the carbon source material is obtained.
  • a suitable temperature for example 60 ° C.
  • the resulting mixture is then heated, for example under a reducing atmosphere or under an inert gas atmosphere.
  • the carbon source material is doped with the nonmetal atom, and the metal atom is also doped by the coordination bond between the nonmetal atom and the metal atom.
  • the heating temperature is preferably in the range of 800 ° C. to 1000 ° C., and the heating time is preferably in the range of 45 seconds to less than 600 seconds. Since the heating time is short, the carbon-based material is efficiently produced, and the catalytic activity of the carbon-based material is further enhanced.
  • the temperature increase rate of the mixture at the time of a heating start in heat processing is 50 degrees C / s or more. Such rapid heating can further improve the catalytic activity of the carbon-based material.
  • the carbon-based material may be further acid-washed.
  • the carbon-based material may be dispersed in pure water for 30 minutes with a homogenizer, and then the carbon-based material may be placed in 2 M sulfuric acid and stirred at 80 ° C. for 3 hours. In this case, the elution of the metal component from the carbon-based material can be suppressed.
  • the material of the oxygen permeable layer 33 is not particularly limited as long as it is a material having oxygen permeability, more preferably water repellency.
  • a material of the oxygen permeable layer 33 for example, at least one of silicone rubber and polydimethylsiloxane can be used. These materials have excellent oxygen permeability because they have high oxygen solubility and oxygen diffusibility derived from the molecular structure of silicone. Furthermore, these materials are excellent in water repellency because they have low surface free energy. Therefore, the oxygen permeable layer 33 particularly preferably contains silicone.
  • the oxygen permeable layer 33 As a material of the oxygen permeable layer 33, at least one selected from the group consisting of ethyl cellulose, poly-4-methylpentene-1, polybutadiene, polytetrafluoroethylene and butyl rubber can be used. These materials are also preferable because they have high oxygen permeability and water repellency.
  • nonwoven fabrics such as a waterproof permeable film, and nonwoven fabrics of polyethylene and a polypropylene can also be used.
  • Gore-Tex registered trademark formed by combining a film obtained by drawing and processing polytetrafluoroethylene with a polyurethane polymer can be used.
  • the oxygen permeable layer 33 be in contact with the water repellent layer 31 and the conductive layer 32, as shown in FIG. As a result, oxygen is directly supplied to the conductive layer 32, and further, oxygen reaches the catalyst through the inside of the conductive layer 32, so that a local cell reaction described later is likely to proceed.
  • gaps may exist between the water repellent layer 31 and the oxygen permeable layer 33 or between the conductive layer 32 and the oxygen permeable layer 33.
  • the oxygen permeable layer 33 has water repellency. That is, the oxygen permeable layer 33 is more preferably a sheet having water repellant performance. As will be described later, the oxygen permeable layer 33 is arranged to separate an oxygen-containing gas phase from an electrolyte as a liquid phase held inside the waste water tank.
  • the term "separation" as used herein means to physically shut off. Thereby, it can suppress that the organic substance and nitrogen-containing compound in electrolyte solution move to the gaseous phase side.
  • the oxygen permeable layer 33 can adjust the oxygen permeation amount according to the material to be used, and can suppress excessive permeation of oxygen molecules on the gas phase side into the electrolytic solution. Therefore, as described later, the inside of the wastewater tank can be reliably maintained under anaerobic conditions in which no oxygen is present. As a result, since the growth of aerobic microorganisms can be suppressed in the wastewater tank, liquid treatment can be performed under anaerobic conditions.
  • the bag-like member 10 is sealed by the bag-like member 10 or covered with the cover portion 15 so that the oxygen supply portion 4 side of the spacer 20 is not exposed to the external space S. ing.
  • foreign matter such as rain and dew and dust can be prevented from entering the hollow portion 1 from the external space S.
  • the spacer 20 is accommodated in the bag-like member 10. And the spacer 20 is included in the bag-like member 10 so that the oxygen supply part 4 side of the spacer 20 is not exposed to the external space S of the bag-like member 10.
  • the bag-like member 10 has oxygen permeability, and a part of the bag-like member 10 constitutes the oxygen supply unit 4.
  • the oxygen supply unit 4 is a pore formed in the bag-like member 10 and is formed between the external space S and the hollow portion 1. Then, oxygen is supplied from the external space S to the hollow portion 1 through the pores forming the oxygen supply unit 4. Therefore, for example, when immersing the electrode assembly 100 in the electrolytic solution, the oxygen supply unit 4 is disposed in a state of being exposed to the external space S (outside air).
  • the oxygen permeable portion 5 is a pore provided on the side surface 11 of the bag-like member 10. Then, the oxygen supplied from the oxygen supplier 4 to the hollow part 1 is supplied to the water repellent layer 31 of the electrode 30 through the oxygen permeable part 5 of the bag-like member 10.
  • the pore diameter of the oxygen supplying portion 4 and the oxygen transmitting portion 5 is not particularly limited as long as it has oxygen permeability and waterproofness, but preferably 0.01 ⁇ m to 10 ⁇ m, respectively.
  • the pore diameter can be obtained by taking the average of the diameters of the pores measured by an electron microscope or the like.
  • the bag-like member 10 is sealed by the bag-like member 10 so that the oxygen supply portion 4 side of the spacer 20 is not exposed to the external space S.
  • the sealing here means that the external space S and the hollow portion 1 are formed by the bag-like member 10 It means being physically isolated.
  • foreign matter such as rain and dew and dust can be prevented from entering the hollow portion 1 from the external space S.
  • the method of sealing the bag-like member 10 is not particularly limited, for example, as shown in FIG. 8 to FIG. 10, the bag-like member 10 is thermally welded by opening the opening of the bag-like member 10 containing the spacer 20. It can be sealed. A seal portion 12 is formed on the thermally welded bag-like member 10, and the external space S and the hollow portion 1 of the bag-like member 10 are separated by the bag-like member 10.
  • the method to heat-weld the bag-like member 10 is not specifically limited, either.
  • the bag-like member 10 can be sealed by superposing and heat-welding the inner surfaces of the bag-like member 10 to form the seal portion 12a.
  • the seal portion 12a is disposed between the spacer 20 and the external space S in FIG. 8, the position of the seal portion 12a is particularly limited as long as oxygen supply to the electrode 30 is not impeded. I will not.
  • the outer surface of one end of the opening of the bag-like member 10 and the inner surface of the other end are superposed and heat-welded to form a seal portion 12b to form a bag-like member 10 can be sealed.
  • the seal portion 12 b is disposed between the spacer 20 and the electrode 30 in FIG. 9, the seal portion 12 b may be disposed between the spacer 20 and the external space S.
  • the outer surface of one end of the opening of the bag-like member 10 and the outer surface of the other end are superposed and heat-welded to form a seal portion 12c.
  • the member 10 can also be sealed. Specifically, the inner surfaces of one end of the opening of the bag-like member 10 are adhered to each other. Similarly, the other end of the opening of the bag-like member 10 is also bonded to the inner surface.
  • sticker part 12c is formed so that the sheet
  • the seal portion 12c is disposed between the spacer 20 and the external space S in FIG. 10, the position of the seal portion 12a is particularly limited as long as oxygen supply to the electrode 30 is not impeded. I will not.
  • the spacer 20 is accommodated in the bag-like member 10.
  • the oxygen supply unit 4 is an opening that is open at one end of the bag-like member 10.
  • the spacer 20 has a protrusion 20 a, and the protrusion 20 a is disposed so as to protrude from the oxygen supply unit 4.
  • the bag-like member 10 is covered by the cover portion 15 so that the oxygen supply portion 4 side of the spacer 20 is not exposed to the external space S.
  • the protrusion 20 a of the spacer 20 and the oxygen supply unit 4 are covered by the cover 15 so that the protrusion 20 a of the spacer 20 is not exposed to the external space S.
  • the end of the spacer 20 on the oxygen supply unit 4 side is in contact with the inside of the top surface of the cover unit 15, whereby the cover unit 15 is supported by the spacer 20.
  • the cover portion 15 is formed in a substantially L shape in a cross sectional view.
  • the cover portion 15 has an oxygen inlet 16 which is an opening formed by a plate-like member, and an attachment opening 17 which is an opening formed by a plate-like member.
  • the attachment port 17 is connected to the oxygen supply unit 4 of the bag-like member 10, and an opening forming the oxygen supply unit 4 is accommodated in the cover unit 15.
  • the cover portion 15 is formed of a plate-like member so as to be hollow inside, and is formed such that the oxygen suction port 16 and the attachment port 17 communicate with each other. Then, oxygen supplied from the external space S of the electrode assembly 100 via the oxygen inlet 16 is supplied to the oxygen supply unit 4 through the inside of the cover unit 15. That is, the cover portion 15 has the oxygen suction port 16 formed such that the external space S and the oxygen supply portion 4 communicate with each other.
  • the oxygen permeable portion 5 is a pore provided on the side surface 11 of the bag-like member 10. Therefore, as described above, the oxygen supplied from the oxygen supplying unit 4 to the hollow portion 1 is supplied to the water repellent layer 31 of the electrode 30 through the oxygen permeable unit 5 of the bag-like member 10.
  • the oxygen inlet 16 is between the thickness direction X of the conductive layer 32 and the direction perpendicular to the thickness direction X of the conductive layer 32 and opposite to the oxygen supply portion 4 side of the bag-like member 10. It opens in either direction.
  • the oxygen suction port 16 is a direction Y perpendicular to the thickness direction X of the conductive layer 32 and is a bag It is preferable to form so that it may face the opposite direction to the oxygen supply part 4 side in the rod-shaped member 10.
  • the cover portion 15 is formed in a substantially L shape in a cross sectional view.
  • the oxygen suction port 16 is formed in a plate-like member forming a substantially L-shaped right angle in the cover portion 15. Further, in the cover portion 15, the opening that forms the oxygen suction port 16 faces in substantially the same direction as the opening that forms the oxygen supply unit 4. Further, when the electrode assembly 100 is immersed in the electrolyte, the oxygen inlet 16 is attached in the vertical direction Y perpendicular to the thickness direction X of the conductive layer 32 so as not to contact the electrolyte.
  • the bag-like member 10 is disposed closer to the oxygen supply unit 4 than the space 17.
  • the electrode assembly 100 includes the hollow portion 1, the oxygen supply portion 4 for supplying oxygen to the hollow portion 1, and the oxygen permeable portion 5 for transmitting the oxygen supplied to the hollow portion 1.
  • the bag-like member 10 having air permeability from the oxygen supply unit 4 to the oxygen permeable unit 5.
  • the electrode complex 100 is provided in the hollow portion 1 and the spacer 20 housed in the bag-like member 10, and the electrode 30 having the conductive layer 32 provided outside the bag-like member 10 in the oxygen permeable portion 5 And. Then, the bag-like member 10 is sealed by the bag-like member 10 or covered with the cover portion 15 so that the oxygen supply unit 4 side of the spacer 20 is not exposed to the external space S.
  • the electrode assembly 100 is immersed in the electrolytic solution, and oxygen is sufficiently supplied to the electrode 30 even in a high water pressure environment. Space is secured.
  • the bag-like member 10 is sealed by the bag-like member 10 or covered with the cover portion 15 so that the oxygen supply portion 4 side of the spacer 20 is not exposed to the external space S. Therefore, even in an environment such as the outdoors, foreign matter such as rain dew and dust can be prevented from entering the hollow portion 1, and accumulation of the foreign matter inside the bag-like member 10 can be suppressed. it can. Therefore, a space for supplying oxygen sufficiently to the electrode 30 can be secured, and it becomes possible to suppress the deterioration of the battery characteristics and stably produce electric energy.
  • the bag-like member 10 is preferably sealed by the bag-like member 10 so that the oxygen supply portion 4 side of the spacer 20 is not exposed to the external space S.
  • the bag-like member 10 having the oxygen supply unit 4 for supplying oxygen to the hollow portion 1 and the oxygen permeable portion 5 for transmitting the oxygen supplied to the hollow portion 1 is provided. Therefore, although oxygen can be taken into the hollow portion 1 from the external space S through the oxygen supplying portion 4, the spacer 20 provided in the hollow portion 1 is a bag-like member so that the oxygen supplying portion 4 side is not exposed to the external space S 10 is sealed.
  • the electrode complex 100 according to the present embodiment foreign matter such as rain and dew and dust can be prevented from entering the hollow portion 1. Therefore, according to the present embodiment, even in an environment such as the outdoors, oxygen can be sufficiently supplied to the electrode 30, and a decrease in battery characteristics can be suppressed.
  • the bag-like member 10 is preferably covered by the cover portion 15 so that the oxygen supply portion 4 side of the spacer 20 is not exposed to the external space S.
  • the cover portion 15 has an oxygen suction port 16 formed such that the external space S and the oxygen supply portion 4 communicate with each other.
  • the oxygen suction port 16 has a thickness direction X of the conductive layer 32 and a direction perpendicular to the thickness direction X of the conductive layer 32 and opposite to the oxygen supply portion 4 side of the bag-like member 10. Opening in either direction between.
  • the microbial fuel cell 110 according to the present embodiment is separated from the anode 40 supporting a microorganism, an ion transfer layer 50 transmitting hydrogen ions, and the ion transfer layer 50 as shown in FIG. And a cathode 60 comprising the electrode 30 described above.
  • the anode 40 has a structure in which microorganisms are supported on a conductive sheet having conductivity.
  • a conductive sheet at least one selected from the group consisting of a porous conductive sheet, a woven conductive sheet and a non-woven conductive sheet can be used.
  • the conductor sheet may be a laminate in which a plurality of sheets are laminated.
  • the conductor sheet of the anode 40 has a space (void) continuous in the stacking direction X of the electrode 30, the anode 40, and the ion transfer layer 50, that is, the thickness direction. Is preferred.
  • the conductor sheet may be a metal plate having a plurality of through holes in the thickness direction. Therefore, as a material constituting the conductive sheet of the anode 40, for example, at least one selected from the group consisting of conductive metals such as aluminum, copper, stainless steel, nickel and titanium, carbon paper and carbon felt Can.
  • conductive metals such as aluminum, copper, stainless steel, nickel and titanium, carbon paper and carbon felt Can.
  • the microorganism carried on the anode 40 is not particularly limited as long as it is a microorganism that decomposes an organic substance in the liquid to be treated (electrolytic solution) or a compound containing nitrogen (nitrogen-containing compound). It is preferred to use anaerobic microorganisms that do not Anaerobic microbes do not require air for oxidatively decomposing organic matter in the liquid to be treated. Therefore, the power required to feed the air can be significantly reduced. In addition, since the free energy obtained by microorganisms is small, it is possible to reduce the amount of sludge generated.
  • the anaerobic microbes be retained by superimposing and fixing a biofilm containing an anaerobic microbe on the anode 40.
  • Biofilm generally refers to a three-dimensional structure including a microbial population and an extracellular polymeric substance (EPS) produced by the microbial population.
  • EPS extracellular polymeric substance
  • the anaerobic microorganism may be held on the anode 40 without using the biofilm.
  • the anaerobic microorganism retained on the anode 40 is preferably, for example, an electroproducing bacterium having an extracellular electron transfer mechanism.
  • anaerobic microorganisms include, for example, bacteria belonging to the genus Geobacter, bacteria belonging to the genus Shewanella, bacteria belonging to the genus Aeromonas, bacteria belonging to the genus Geothrix, and bacteria belonging to the genus Saccharomyces.
  • the microbial fuel cell 110 of the present embodiment is provided with an ion transfer layer 50 which transmits hydrogen ions.
  • the ion transfer layer 50 has a function of transmitting hydrogen ions generated at the anode 40 and moving it to the cathode 60 side.
  • an ion exchange membrane using an ion exchange resin can be used as the ion transfer layer 50.
  • the ion exchange resin for example, NAFION (registered trademark) manufactured by DuPont Co., Ltd., and Flemion (registered trademark) and Seremion (registered trademark) manufactured by Asahi Glass Co., Ltd. can be used.
  • the ion transfer layer 50 a porous membrane having pores through which hydrogen ions can permeate may be used. That is, the ion transfer layer 50 may be a sheet having a space (air gap) for hydrogen ions to move between the anode 40 and the cathode 60. Therefore, it is preferable that the ion transfer layer 50 includes at least one selected from the group consisting of a porous sheet, a woven sheet, and a non-woven sheet.
  • the ion transfer layer 50 may be at least one selected from the group consisting of a glass fiber membrane, a synthetic fiber membrane, and a plastic non-woven fabric, and may be a laminate formed by laminating a plurality of these.
  • Such a porous sheet has a large number of pores inside, so that hydrogen ions can be easily moved.
  • the pore diameter of the ion transfer layer 50 is not particularly limited as long as hydrogen ions can move from the anode 40 to the cathode 60.
  • the ion transfer layer 50 has a function of transmitting hydrogen ions generated at the anode 40 and moving them to the cathode 60 side.
  • hydrogen ions can move from the anode 40 to the cathode 60 without providing the ion transfer layer 50 if the anode 40 and the cathode 60 are not in contact with each other and in proximity. Therefore, in the microbial fuel cell 110 of the present embodiment, the ion transfer layer 50 is not an essential component.
  • hydrogen ions can be efficiently transferred from the anode 40 to the cathode 60. Therefore, it is preferable to provide the ion transfer layer 50 from the viewpoint of output improvement.
  • the microbial fuel cell 110 of the present embodiment includes the above-described electrode assembly 100, and the electrode 30 further includes a water repellent layer 31 and a conductive layer 32. Further, the ion transfer layer 50 is disposed outside the conductive layer 32. The conductive layer 32 and the anode 40 of the cathode 60 are electrically connected to an external circuit (not shown).
  • the wastewater tank 80 has the electrode assembly 100, the anode 40 and the ion transfer layer 50 installed therein.
  • the electrode assembly 100 is exposed so that the oxygen supply unit 4 is exposed to the outside air. It is preferable to be immersed in the electrolytic solution 81.
  • the electrode complex 100 may be immersed in the electrolyte 81 so that the oxygen inlet 16 is exposed to the outside air. preferable. With such a configuration, air permeability to the inside of the bag-like member 10 can be secured.
  • the wastewater tank 80 holds the electrolytic solution 81 inside, the electrolytic solution 81 may flow.
  • the waste water tank 80 is provided with a liquid supply port 82 for supplying the electrolytic solution 81 to the waste water tank 80, and a liquid discharge for discharging the treated electrolytic solution 81 from the waste water tank 80.
  • An outlet 83 may be provided.
  • the inside of the waste water tank 80 is maintained under anaerobic conditions in which, for example, molecular oxygen is not present or molecular oxygen is present, the concentration thereof is extremely small.
  • the electrolyte 81 can be held in the waste water tank 80 so as to be hardly in contact with oxygen.
  • the operation of the microbial fuel cell 110 of the present embodiment will be described.
  • the anode 40 is supplied with an electrolyte 81 containing at least one of an organic substance and a nitrogen-containing compound, and the cathode 60 is supplied with air (or oxygen).
  • air is continuously supplied through the oxygen supply unit 4 provided on the top of the electrode assembly 100.
  • the electrolytic solution 81 is also preferably supplied continuously through the liquid supply port 82 and the liquid discharge port 83.
  • the generated electrons move to the external circuit through the conductive sheet of the anode 40, and further move to the conductive layer 32 of the cathode 60 from the external circuit. Then, the hydrogen ions and electrons transferred to the conductive layer 32 combine with oxygen by the action of the catalyst to be consumed as water. At this time, the external circuit recovers the electrical energy flowing to the closed circuit.
  • an electron transfer mediator molecule may be modified in the anode 40 according to the present embodiment.
  • the electrolyte 81 in the wastewater tank 80 may contain an electron transfer mediator molecule. Thereby, electron transfer from the anaerobic microorganism to the anode 40 can be promoted, and more efficient liquid processing can be realized.
  • an electron transfer mediator molecule is not particularly limited, but for example, at least one selected from the group consisting of neutral red, anthraquinone-2,6-disulfonic acid (AQDS), thionine, potassium ferricyanide, and methyl viologen Can.
  • a through hole 91 be provided at the edge of the bag-like member 10 opposite to the oxygen supply unit 4.
  • the through hole 91 is provided with a reinforcing portion 92 formed by bonding the inner surface of the edge portion of the bag-like member 10 so that oxygen supplied from the oxygen supply portion 4 does not permeate. Is formed.
  • the size of the through hole 91 is not particularly limited, but can be, for example, 1 mm to 100 mm.
  • a reinforcing member 94 such as a grommet at the edge of the through hole 91.
  • the grommet can be formed of, for example, metal, rubber, and plastic.
  • the bag-like member 10 is fixed to at least one of the side wall 80 a and the bottom 80 b of the wastewater tank 80 by the fixing member 93. Therefore, it can suppress that the bag-like member 10 deform
  • the method of fixing the bag-like member 10 by the fixing member 93 is not particularly limited.
  • string-like fixing members 93 can be passed through the respective through holes 91 in the electrode assembly 100 to connect the respective electrode assemblies 100 and fix them in the waste water tank 80.
  • the bag-like member 10 can be fixed to the wastewater tank 80 using a rod-like fixing member 93 instead of the string-like fixing member 93.
  • each electrode complex 100 and the bottom 80 b of the waste water tank 80 can be fixed using a string-like fixing member 93.
  • the microbial fuel cell 110 includes the electrode assembly 100 and the anode 40 that carries the microorganism.
  • the electrode 30 in the electrode assembly 100 is a cathode 60.
  • the cathode 60 exhibits high pressure resistance. As a result, a space for supplying oxygen to the cathode 60 is secured even when the microbial fuel cell 110 is enlarged or when the water depth of the microbial fuel cell 110 is deep, so that sufficient space for the cathode 60 can be obtained. Can be supplied with oxygen.
  • the electrode assembly 100 can suppress foreign matter such as rain and dew and dust from entering the hollow portion 1 even in an environment such as the outdoors, and the inside of the bag-like member 10 Deposit of foreign matter on the Therefore, it is possible to stably produce electrical energy by suppressing the decrease in the power generation performance of the microbial fuel cell 110.
  • the microbial fuel cell 110 is preferably provided between the electrode 30 and the anode 40 in the electrode assembly 100 and further includes an ion transfer layer 50 having proton permeability.
  • an ion transfer layer 50 having proton permeability.
  • the bag-like member 10 is sealed by the bag-like member 10 so that the oxygen supply portion 4 side of the spacer 20 is not exposed to the external space S.
  • the electrode assembly 100 in order to ensure air permeability to the inside of the bag-like member 10, it is preferable that the electrode assembly 100 be immersed in the electrolytic solution 81 so that the oxygen supply unit 4 is exposed to the outside air. As a result, it is possible to ensure high air permeability from the oxygen supply unit 4 to the oxygen permeable unit 5 of the bag-like member 10.
  • the bag-like member 10 is covered by the cover portion 15 so that the oxygen supply portion 4 side of the spacer 20 is not exposed to the external space S. Further, the cover portion 15 has an oxygen suction port 16 formed such that the external space S and the oxygen supply portion 4 communicate with each other. Furthermore, the oxygen suction port 16 is between the thickness direction X of the conductive layer 32 and the direction perpendicular to the thickness direction of the conductive layer 32 and opposite to the oxygen supply portion 4 side of the bag-like member 10 It is open in either direction. In this case, in order to ensure air permeability to the inside of the bag-like member 10, the electrode assembly 100 is preferably immersed in the electrolyte 81 so that the oxygen inlet 16 is exposed to the outside air. As a result, it is possible to ensure high air permeability from the oxygen supply unit 4 to the oxygen permeable unit 5 of the bag-like member 10.
  • the water treatment apparatus of the present embodiment includes an electrode complex 100 and an anode 40 carrying a microorganism that purifies the liquid to be treated.
  • the electrode 30 in the electrode assembly 100 is a cathode 60.
  • the microbial fuel cell 110 of the present embodiment supplies, to the anode 40, the electrolytic solution 81 (liquid to be treated) containing at least one of the organic substance and the nitrogen-containing compound. Then, carbon dioxide or nitrogen is generated from the organic substance and / or the nitrogen-containing compound in the electrolytic solution 81 together with hydrogen ions and electrons by the metabolism of the microorganism supported on the anode 40.
  • anode 40 C 6 H 12 O 6 + 6 H 2 O ⁇ 6 CO 2 + 24 H + + 24 e ⁇
  • the cathode 60 6O 2 + 24H + + 24e - ⁇ 12H 2 O
  • Anode 40 4 NH 3 ⁇ 2 N 2 + 12 H + + 12 e ⁇
  • the cathode 60 3O 2 + 12H + + 12e - ⁇ 6H 2 O
  • the wastewater tank 80 is provided with a liquid supply port 82 for supplying the electrolytic solution 81 to the wastewater tank 80, and a liquid outlet 83 for discharging the treated electrolytic solution 81 from the wastewater tank 80.
  • the electrolyte 81 can be continuously supplied. Therefore, it becomes possible to make the electrolytic solution 81 contact the anode 40 continuously and to process the electrolytic solution 81 efficiently.
  • the water treatment apparatus of the present embodiment preferably further includes an ion transfer layer 50 provided between the electrode 30 and the anode 40 in the electrode assembly 100 and having proton permeability.
  • an ion transfer layer 50 provided between the electrode 30 and the anode 40 in the electrode assembly 100 and having proton permeability.
  • the support member constitutes a part of the spacer. Therefore, the spacer may be configured of only the support member as long as a space for sufficiently supplying oxygen to the cathode is secured.
  • an electrode complex capable of sufficiently supplying oxygen to the electrode and suppressing the deterioration of the battery characteristics even in an environment such as the outdoors, a microbial fuel cell using the same, and a water treatment
  • An apparatus can be provided.

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  • Inert Electrodes (AREA)

Abstract

L'invention concerne un ensemble électrode (100) qui comprend un élément en forme de sac (10) comportant une section creuse (1), une section d'alimentation en oxygène (4) qui fournit de l'oxygène à la section creuse (1), et une section perméable à l'oxygène (5) à travers laquelle passe l'oxygène fourni à la section creuse (1), ledit élément en forme de sac (10) permettant le passage d'air de la section d'alimentation en oxygène (4) à la section perméable à l'oxygène (5). L'ensemble électrode (100) comprend en outre : un élément d'espacement (20) qui est disposé dans la section creuse (1) et est logé dans l'élément en forme de sac (10) ; et, au niveau de la section perméable à l'oxygène (5), une électrode (30) qui comporte une couche conductrice (32) disposée du côté extérieur de l'élément en forme de sac (10). La section de l'élément en forme de sac (10) côté section d'alimentation en oxygène (4) de l'élément d'espacement (20) est soit hermétiquement fermée par l'élément en forme de sac (10) soit recouverte par une partie de recouvrement (15) de manière que ledit côté section d'alimentation en oxygène (4) ne soit pas exposé à l'espace externe (S).
PCT/JP2018/036686 2017-10-03 2018-10-01 Ensemble électrode, et pile à combustible microbienne et dispositif de traitement de l'eau l'utilisant WO2019069851A1 (fr)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN111420547A (zh) * 2020-02-28 2020-07-17 天津大学 光催化微生物燃料电池高效去除挥发性有机污染物的装置

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JP2013016413A (ja) * 2011-07-06 2013-01-24 Sony Corp バイオ燃料電池
JP2016115413A (ja) * 2014-12-11 2016-06-23 日新電機株式会社 微生物燃料電池用の電極部、電極部集合体、及び微生物燃料電池
WO2016194374A1 (fr) * 2015-06-05 2016-12-08 パナソニック株式会社 Complexe à électrode, et pile à combustible microbienne et dispositif de traitement des eaux l'utilisant

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
JP2009093861A (ja) * 2007-10-05 2009-04-30 Kajima Corp 微生物燃料電池及び微生物燃料電池用の隔膜カセット
JP2013016413A (ja) * 2011-07-06 2013-01-24 Sony Corp バイオ燃料電池
JP2016115413A (ja) * 2014-12-11 2016-06-23 日新電機株式会社 微生物燃料電池用の電極部、電極部集合体、及び微生物燃料電池
WO2016194374A1 (fr) * 2015-06-05 2016-12-08 パナソニック株式会社 Complexe à électrode, et pile à combustible microbienne et dispositif de traitement des eaux l'utilisant

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111420547A (zh) * 2020-02-28 2020-07-17 天津大学 光催化微生物燃料电池高效去除挥发性有机污染物的装置
CN111420547B (zh) * 2020-02-28 2022-04-08 天津大学 光催化微生物燃料电池高效去除挥发性有机污染物的装置

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