WO2019200895A1 - Cathode à air à atome unique, batterie, système électrochimique et système bioélectrochimique - Google Patents

Cathode à air à atome unique, batterie, système électrochimique et système bioélectrochimique Download PDF

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Publication number
WO2019200895A1
WO2019200895A1 PCT/CN2018/114155 CN2018114155W WO2019200895A1 WO 2019200895 A1 WO2019200895 A1 WO 2019200895A1 CN 2018114155 W CN2018114155 W CN 2018114155W WO 2019200895 A1 WO2019200895 A1 WO 2019200895A1
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cathode
anode
present application
electrochemical system
catalyst
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PCT/CN2018/114155
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English (en)
Chinese (zh)
Inventor
张潇源
徐婷
伍晖
黄凯
黄霞
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清华大学
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Priority claimed from CN201820542336.4U external-priority patent/CN208272026U/zh
Priority claimed from CN201810341661.9A external-priority patent/CN108630950B/zh
Application filed by 清华大学 filed Critical 清华大学
Publication of WO2019200895A1 publication Critical patent/WO2019200895A1/fr

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    • 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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • 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 application relates to the fields of environment, materials, and energy, and in particular, to cathodes, batteries, and electrochemical systems.
  • the bioelectrochemical system represented by a microbial fuel cell is an emerging sewage treatment technology that can convert the chemical energy in the pollutant into electric energy while treating the sewage.
  • the microbial fuel cell can oxidize the organic matter in the sewage by using the electric generating microorganism attached to the anode, and the cathode receives the electron to complete the oxygen reduction reaction.
  • the cathode includes: a collector layer; and a catalyst layer disposed on the collector layer, the catalyst layer including an atomic-level dispersed metal catalyst.
  • an atom-level dispersed metal catalyst to catalyze the oxygen reduction reaction in the cathode not only has the advantages of good catalytic activity, high metal utilization rate, low cost, etc., but also can improve the electron utilization rate when the cathode is used in an electrochemical system. , thereby improving the electrical performance of the electrochemical system.
  • the cathode further includes: a diffusion layer disposed on a side of the collector layer away from the catalyst layer, or disposed on the catalyst layer away from the collector layer One side.
  • the diffusion layer can be in contact with air, facilitating diffusion of oxygen into the air cathode, further improving the use effect of the cathode.
  • the atomic-level dispersed metal catalyst includes a support and an active metal supported on the support, the active metal including at least one of Fe, Co, and Ni.
  • the atomic-stage dispersed metal catalyst is various in type, and the active metal is supported on the carrier, whereby the stability of the catalyst layer can be improved, and the use performance of the cathode can be further improved.
  • the atomic-level dispersed metal catalyst is prepared under a low temperature environment. Thereby, an atom-level dispersed metal catalyst having good performance can be easily prepared, and the use performance of the cathode can be further improved.
  • the application proposes a battery.
  • the battery includes: a cathode as described above; and an anode electrically connected to the cathode.
  • the battery has all of the features and advantages of the cathode described above, and the battery has high power generation efficiency and good operational stability.
  • the battery has a power density of not less than 2000 mW/m 2 when the external resistance is 50 ohms. Thereby, the power generation efficiency of the battery is high, and the use effect of the battery is further improved.
  • the current density of the battery after 500 hours of operation is not more than 5%. Therefore, the battery has better running stability, and the use effect of the battery is further improved.
  • the present application proposes an electrochemical system.
  • the electrochemical system includes: a housing defining a reaction space therein; and a modular electrode assembly disposed in the reaction space, the modular The electrode assembly further includes: a hollow cathode socket including: a plurality of air cathodes disposed on sidewalls of the hollow cathode socket, the air cathode including The catalyst layer described above; an anode, the anode being electrically connected to the air cathode.
  • the electrochemical system not only has all the features and advantages of the catalyst layer described above, that is, the catalytic activity of the air cathode is good, the metal utilization rate is high, the cost is low, and the like, and the electrochemical system is also set.
  • the modular electrode assembly integrates multiple air cathodes and anodes in the same reaction space, further improving the electrical performance of the electrochemical system.
  • the hollow cathode slot includes a plurality of the sidewalls and a bottom surface, and the plurality of sidewalls and the bottom surface define a hollow space inside the hollow cathode slot, The side of the side wall adjacent to the hollow space is in contact with the atmosphere.
  • the anode is disposed between the hollow cathode socket and the housing. Therefore, the use effect of the electrochemical system is further improved.
  • the modular electrode assembly further includes an anode socket, and the anode is disposed on a sidewall of the anode socket.
  • the anode slot can be easily removed for easy replacement of the anode, and when a plurality of anodes are provided in the system, a plurality of anodes can be easily disposed in the same anode slot, further improving The use of electrochemical systems.
  • the air cathode includes a plurality of sub-cathodes.
  • a plurality of sub-cathodes an air cathode having a large area can be easily prepared, and the prepared air cathode has high surface flatness and good performance, and further improves the use effect of the electrochemical system.
  • a plurality of the sub-cathodes are connected in parallel or in series.
  • the plurality of sub-cathodes are connected in a plurality of ways, and can be combined as needed to form an air cathode, which further improves the use effect of the electrochemical system.
  • the air cathode further includes a conductive support frame, the plurality of sub-cathodes being directly disposed on the conductive support frame, the conductive support frame being electrically connected to the anode.
  • the air cathode further includes a plurality of wires, the plurality of wires being connected in one-to-one correspondence with the plurality of sub-cathodes, and the plurality of wires are electrically connected to the anode.
  • the anode is at least one of a carbon brush, carbon cloth, carbon paper, carbon felt, activated carbon, and graphite.
  • the electrochemical system is a bioelectrochemical system
  • the anode can increase the adhesion ability of the microorganism, and the cost of the electrochemical system can be further saved.
  • the anode is a planar electrode
  • the electrochemical system further includes a separator disposed between the air cathode and the anode.
  • the membrane can slow down the contamination rate of the air cathode, further improving the electrical production performance of the electrochemical system.
  • FIG. 1 shows a schematic structural view of a cathode according to an embodiment of the present application
  • FIG. 2 shows a flow chart of a method of preparing an atom-level dispersed metal catalyst according to an embodiment of the present application
  • FIG. 3 shows a schematic structural view of a cathode according to another embodiment of the present application.
  • FIG. 4 shows a schematic structural view of a cathode according to still another embodiment of the present application.
  • FIG. 5 is a schematic structural view of a cathode according to still another embodiment of the present application.
  • FIG. 6 is a schematic structural view of a battery according to an embodiment of the present application.
  • Figure 7 shows a schematic structural view of an electrochemical system according to an embodiment of the present application.
  • Figure 8 shows a schematic structural view of an electrochemical system according to another embodiment of the present application.
  • FIG. 9 shows a schematic structural view of an electrochemical system according to still another embodiment of the present application.
  • Figure 10 shows a schematic structural view of an electrochemical system according to still another embodiment of the present application.
  • Figure 11 shows a schematic structural view of an air cathode according to an embodiment of the present application.
  • FIG. 12 is a schematic structural view of an air cathode according to another embodiment of the present application.
  • Figure 13 is a graph showing the electrical performance test of an electrochemical system according to some embodiments and comparative examples of the present application.
  • Figure 14 is a graph showing the electrical performance test of a bioelectrochemical system according to further embodiments and comparative examples of the present application.
  • Figure 15 shows a graph of operational stability testing of an electrochemical system in accordance with some embodiments and comparative examples of the present application.
  • 10 catalyst layer; 20: collector layer; 30: diffusion layer; 40: support layer; 110: cathode; 100: shell; 200: reaction space; 300: modular electrode assembly; 310: hollow cathode slot; 311: sidewall; 320: air cathode; 321: sub-cathode; 322: conductive support; 323: wire; 330: anode; 350: external resistance; 360: anode socket; 1000: electrochemical system.
  • the conventional cathode uses platinum carbon as a catalyst, platinum is expensive, resources are scarce, and its catalytic performance is significantly degraded when the cathode is contaminated for a long period of time.
  • the application proposes a cathode.
  • the cathode 110 includes a catalyst layer 10 and a collector layer 20.
  • the catalyst layer 10 is disposed on the collector layer 20, and the catalyst layer 10 includes an atomic-level dispersed metal catalyst.
  • an atom-level dispersed metal catalyst for catalyzing the oxygen reduction reaction in the cathode 110 not only has the advantages of good catalytic activity, high metal utilization rate, but also can improve the electron utilization rate when the cathode 110 is used in an electrochemical system. Improve the electrical performance of the electrochemical system.
  • the atomic-level dispersed metal catalyst may include a support and an active metal supported on the support.
  • the specific type of the carrier is not particularly limited as long as the atom-level dispersed metal catalyst can be uniformly dispersed therein.
  • the carrier may be graphene, mesoporous carbon, carbon nanotube, Carbon black or activated carbon.
  • the specific kind of the active metal is not particularly limited as long as it can catalyze the oxygen reduction reaction, and specifically, the active metal may include at least one of Fe, Co, and Ni.
  • the active metal may be a unit metal, such as a single Co, a single Ni, a single Fe, or a binary metal, such as a Fe/Co binary metal, a Fe/Ni binary metal, a Co/Ni dual element.
  • the metal, the active metal may also be a ternary metal such as a Fe/Co/Ni ternary metal.
  • the preparation method of the atom-level dispersed metal catalyst is not particularly limited as long as the active metal can be dispersed as a metal mono atom.
  • the atom-level dispersed metal catalyst can be prepared by a dipping method, an etching method, a photo-assisted synthesis method, a metal organic framework-assisted synthesis method, or the like, whereby the atom-level dispersed metal catalyst in the catalyst layer 10 can have various preparation methods. Therefore, it is relatively easy to obtain, and it can be easily applied to the cathode to improve the efficiency of the cathode oxygen reduction reaction.
  • the atomic-level dispersed metal catalyst may be prepared under a low temperature environment. Thereby, an atom-level dispersed metal catalyst having good performance can be easily prepared, and the use performance of the cathode can be further improved.
  • the low-temperature solution synthesis method can be used to prepare a high-metal loading atomic-level dispersed metal catalyst on a large scale, which can improve the effective utilization ratio of the metal atom and reduce the application cost of the metal catalyst.
  • the nucleation can be suppressed by the ultra-low temperature liquid phase, so that the concentration of the metal atom in the solution is lower than the nucleation limit threshold of the metal monomer concentration, thereby obtaining a solution containing the atomic-level dispersed metal, and then obtaining the atomic level by further loading process. Disperse the metal catalyst.
  • the atom-scale dispersed metal catalyst can be synthesized on a large scale in an ultra-low temperature solution environment.
  • the method includes:
  • the metal compound in this step, is mixed with the first solvent to form a metal precursor solution.
  • the metal compound may be a soluble compound of at least one of Fe, Co, and Ni
  • the first solvent may include water, ethanol, ethylene glycol, acetone, chloroform, diethyl ether, tetrafluorohydrofuran, At least one of dimethylformamide and formaldehyde.
  • the concentration of the metal precursor solution may be 0.001-1.0 mol/L, and specifically, may be 0.005 mol/L, 0.008 mol/L, 0.01 mol/L, 0.02 mol/L, 0.05 mol/ L, 0.08 mol/L, 1.0 mol/L, and the like.
  • the atomic-level dispersed metal prepared by the method may include at least one of Fe, Co, and Ni.
  • the atomic-level dispersed metal prepared by the method may be a unit metal catalyst, for example, an atom-level dispersed metal iron catalyst may be prepared by the method, or an atom-level dispersed metal cobalt catalyst may be prepared by the method, or may be utilized. This method produces an atomically dispersed metal nickel catalyst.
  • the atomic-level dispersed metal prepared by the method may also be a binary metal catalyst, for example, an atom-level dispersed iron/cobalt binary metal catalyst may be prepared by the method, or an atomic level may be prepared by the method.
  • a dispersed iron/nickel binary metal catalyst is used, or an atomically dispersed cobalt/nickel binary metal catalyst is prepared by this method.
  • the atomic-level dispersed metal prepared by the method may also be a ternary metal catalyst.
  • an atom-level dispersed iron/cobalt/nickel ternary metal catalyst can be prepared by this method.
  • the preparation of unit, binary and ternary metal catalysts can be achieved by this method.
  • the metal compound may be a soluble compound of Fe, or a soluble compound of Co, or a soluble compound of Ni, or a soluble compound of Fe, Co mixed, or A soluble compound in which Fe and Ni are mixed, or a soluble compound in which Co and Ni are mixed, or a soluble compound in which Fe, Co, and Ni are mixed.
  • unit, binary, and ternary metal catalysts can be prepared separately.
  • a reducing agent is mixed with a second solvent to form a reducing agent solution.
  • the reducing agent may include NaBH 4 , KBH 4 , N 2 H 4 , N 2 H 5 OH, formaldehyde, formic acid, ascorbic acid, Na 2 SO 3 , K 2 SO 3 , and H 2 C 2 O 4 .
  • At least one of the second solvent may include at least one of water, ethanol, ethylene glycol, acetone, chloroform, diethyl ether, tetrafluorohydrofuran, dimethylformamide, and formaldehyde.
  • the reducing agent solution formed by mixing the above solute and the solvent can be reacted with the metal precursor solution, and the reducing agent is reduced to obtain a solution containing the atomic-level dispersed metal.
  • the concentration of the reducing agent solution may be 0.001 to 10.0 mol/L, and specifically, may be 2 mol/L, 5 mol/L, 7 mol/L, and 8 mol/L.
  • the first solvent is water when it is not the same as the second solvent.
  • the carrier material is mixed with a third solvent to form a dispersion.
  • the carrier material may be a doped carbon nanomaterial.
  • the dopant atoms may form defects on the surface of the carbon nanomaterial, thereby increasing the adsorption of the carrier material on the metal atom, thereby increasing the carrier material to the metal atom.
  • the amount of load may include at least one of nitrogen-doped mesoporous carbon (CMK-3), nitrogen-doped graphene, and graphite phase carbonized nitrogen (gC 3 N 4 ).
  • CMK-3 nitrogen-doped mesoporous carbon
  • gC 3 N 4 graphite phase carbonized nitrogen
  • the third solvent may include at least one of water, ethanol, ethylene glycol, acetone, chloroform, diethyl ether, tetrafluorohydrofuran, dimethylformamide, and formaldehyde.
  • the concentration of the dispersion may be 0.1-10 g/L, and specifically, may be 2.5 g/L, 3.5 g/L, 4.5 g/L, 5.5 g/L, 6.5 g/L, 7.5. g/L, 8.5 g/L, 9.5 g/L.
  • the metal precursor solution is mixed with the reducing agent solution to obtain a solution containing an atomic-level dispersed metal.
  • the metal precursor solution may be mixed with the reducing agent solution at a low temperature environment of -100 to 0 °C.
  • the reactants are mixed at a low speed, thereby controlling the mass and heat transfer.
  • the preparation process of the above microfluidic method is too complicated, the yield is low, and the large-scale preparation of the atom-level dispersed metal catalyst is severely inhibited.
  • the nucleation barrier can be significantly increased by lowering the temperature, and nucleation is effectively suppressed, thereby increasing the concentration of dispersed metal atoms in the solution.
  • the dispersed metal atoms can be effectively adsorbed on different carrier surfaces, thereby facilitating the large-scale synthesis of atom-level dispersed metal catalysts in an ultra-low temperature solution environment.
  • the inventors have found that when the temperature is higher than the above temperature range, the concentration of metal atoms dispersed in the solution is low, and the effective utilization ratio of the metal atoms is low. When the temperature is lower than the above temperature range, the reaction kinetics and thermodynamics are too slow to efficiently prepare metal monoatoms.
  • the temperature can be set within the above temperature range, and the atomic-level dispersed metal catalyst can be synthesized on a large scale.
  • the metal precursor solution and the reducing agent may be first used before mixing the metal precursor solution and the reducing agent solution.
  • the solution is kept in a low temperature chamber for a certain period of time, for example, for 30 minutes. Thereby, the concentration of metal atoms in the solution can be further increased, and the utilization ratio of the metal atoms can be further improved.
  • the manner of mixing the metal precursor solution and the reducing agent solution is not particularly limited, and those skilled in the art can design according to specific conditions.
  • the injection pump can be used to control the drop rate, the metal precursor solution is added dropwise to the stirred reducing agent solution, or the reducing agent solution is added dropwise to the stirred metal precursor solution, thereby The metal precursor solution is sufficiently reacted with the reducing agent solution to obtain a solution containing an atomic-level dispersed metal.
  • the atomic-level dispersed metal may include at least one of Fe, Co, and Ni. Thereby, a plurality of atomic-scale dispersed metal catalysts containing the above metals can be prepared simply and efficiently.
  • the relative amounts of the metal precursor solution and the reducing agent solution can be determined by a chemical reaction equation, and the amount of the reducing agent solution can be made much larger than the metal in order to fully react the metal precursor solution with the reducing agent solution.
  • the amount of precursor solution is such that all metal atoms in the metal precursor solution are reduced.
  • the metal precursor solution is added dropwise to the agitation reduction
  • the dropping rate may be 0.5-50 mL/h, and the stirring rate may be 0-3000 rpm. Thereby, the metal precursor solution and the reducing agent solution can be sufficiently reacted to obtain a solution containing an atomic-level dispersed metal. According to a specific embodiment of the present application, the dropping rate may be 2.5 mL/h, 7.5 mL/h, 15 mL/h, 30 mL/h, 45 mL/h.
  • the dispersion is added to a solution containing an atomic-level dispersed metal and stirred to obtain an atom-level dispersed metal catalyst.
  • an atom-level dispersed metal catalyst supported by a carbon nanomaterial is obtained by adsorbing a metal atom in an atom-level dispersed metal solution by using a solute in the dispersion.
  • the doped carbon nanomaterial has a strong adsorption effect on the metal atom, thereby increasing the loading of the carrier material on the metal atom and improving the effective utilization of the metal atom.
  • mixing the dispersion with a solution containing an atomic-level dispersed metal in a low-temperature environment of -100 to 0 ° C can ensure that the metal in the solution containing the atomic-level dispersed metal is adsorbed to the atom in the form of atoms.
  • an atomic-scale dispersed metal catalyst supported on the support material is obtained.
  • the mixed solution is stirred to promote adsorption of the carrier material to the atom-level dispersed metal, and then the solution is subjected to centrifugation or vacuum filtration treatment. And drying at room temperature in order to obtain a high metal loading atomically dispersed metal catalyst.
  • the stirring rate may be 0-3000 rpm, and the stirring time may be 0-300 min.
  • the method may further include: placing the atomic-level dispersed metal catalyst prepared through the above steps in a gas atmosphere for annealing treatment.
  • the gas atmosphere may be a high vacuum, nitrogen, argon or hydrogen argon mixture
  • the amount of gas may be 50-600 sccm
  • the annealing treatment temperature may be 200-1200 °C.
  • the atomic-scale metal catalyst prepared by the low-temperature solution method according to the embodiment of the present application has the advantages of large density, high yield, high efficiency, strong applicability, and can significantly reduce large-scale commercial application of atomic-scale metal catalysts.
  • the cost therefore, is applied to the cathode according to the embodiment of the present application, which has advantages such as good catalytic activity, high metal utilization rate, and the like, and can reduce the production cost.
  • the specific type of the cathode 110 is not particularly limited as long as the oxygen reduction reaction can be performed on the cathode.
  • the cathode 110 may be directly immersed in the electrolyte, and then by aeration, oxygen may reach the cathode, and oxygen may be on the cathode. An oxygen reduction reaction occurs.
  • the cathode 110 may also be an air cathode, and the cathode 110 may further include a diffusion layer 30, which may be in contact with air (not shown), so that The reduction reaction is carried out by using oxygen in the air to realize the function of using the cathode 110.
  • the diffusion layer 30 may be disposed on a side of the collector layer 20 away from the catalyst layer 10 and in contact with an electrolyte (not shown). Thereby, the diffusion layer 30 is in contact with the air so that oxygen can diffuse into the cathode 110, the collector layer 20 can enrich current, and improve the conductivity of the cathode 110, and the catalyst layer 10 can be utilized under the action of an atom-level dispersed metal catalyst. The electrons are reduced in reaction with oxygen, which in turn can improve the use effect of the cathode 110.
  • the cathode 110 may further have a structure in which the diffusion layer 30 is in contact with air (not shown), and the catalyst layer 10 is formed on the side of the diffusion layer 30 away from the air.
  • the collector layer 20 is formed on the side of the catalyst layer 10 away from the diffusion layer 30, and is in contact with the electrolyte (not shown). Further, the use effect of the cathode 110 can be improved.
  • the cathode 110 may further have a support layer 40, the support layer 40 may be formed between the catalyst layer 10 and the diffusion layer 30, and the support layer 40 It can be formed from a stainless steel mesh.
  • the cathode layer 110 can be provided with a better support structure through the support layer 40, and the support layer 40 and the collector layer 20 are respectively located on both sides of the catalyst layer 10, which can provide good protection for the catalyst layer 10 and prevent the actual use.
  • the loss of powdering of the catalyst layer 10 during the process adversely affects the use effect of the cathode 110.
  • the support layer 40 composed of a stainless steel mesh can further improve the conductivity of the cathode 110, thereby further improving the performance of the cathode 110.
  • the atom-level dispersed metal catalyst has a highly dispersed catalytic active site, and therefore, the atomic-level dispersed metal catalyst has good catalytic activity, high catalytic efficiency, high metal utilization rate, and low cost.
  • the inventors have found through extensive research and a large number of experiments that atomic-level dispersed metal catalysts can be applied to cathodes and applied to electrochemical systems as well as bioelectrochemical systems, thereby improving the efficiency of oxygen reduction of cathodes and improving electrochemical systems.
  • the electronic utilization rate which in turn increases the electrical performance of the electrochemical system.
  • the cathode structure according to the specific embodiment of the present application is particularly advantageous for the adhesion of the above-described atomic-level dispersed metal catalyst.
  • the atomic-level dispersed metal catalyst can be easily fixed in the catalyst layer, but also the fixed catalyst layer has good stability.
  • the atomic-level dispersed metal catalyst is used in the cathode, and the reduction reaction of the cathode by air also has a good catalytic effect.
  • the cathode 110 may be prepared by the following method:
  • the catalyst layer 10 is formed by mixing 60-300 mg atom-level dispersed metal catalyst with 24-350 ⁇ L of a polytetrafluoroethylene binder, and then uniformly coating the side of the stainless steel mesh of the diffusion layer 30 prepared in the step (1). ;
  • the collector layer 20 formed of the stainless steel mesh is pressed together with the structure prepared in the step (2) at 4.5-10 MPa, and heated at 60-100 ° C for 20-60 min to obtain an air cathode 320.
  • the cathode not only has good catalytic activity, high metal utilization rate, low cost, and is simple and easy to prepare, and is suitable for large-area production.
  • the application proposes a battery.
  • the battery may include the cathode 110 and the anode 330 described above, and the anode 330 is electrically connected to the cathode 110.
  • the battery has all the features and advantages of the cathode described above. Since the catalyst in the cathode described above is an atomic-level dispersed metal catalyst, the catalytic activity is high and the stability is good, so the battery is produced. The efficiency is also high and the running stability is good.
  • the battery has a power density of 2000 mW/m 2 when the external resistance is 50 ohms.
  • the power generation efficiency of the battery is high, and the use effect of the battery is further improved.
  • the power density can reach 2540 mW/m 2 , which further improves the use effect of the battery.
  • the current density of the battery after 500 hours of operation is not more than 5%.
  • the battery has better running stability, and the use effect of the battery is further improved.
  • the current density attenuation may not exceed 5%, which further indicates that the battery has good running stability, and further improves the use effect of the battery.
  • the battery may be a fuel cell or a microbial fuel cell as long as an oxygen reduction reaction occurs at the cathode thereof.
  • the electrogenetic microorganism adheres to the surface of the anode, whereby the organic substance in the medium can be oxidatively decomposed by the electrogenic microorganism, and electrons and protons are generated, and electrons are received through the cathode, and the metal is dispersed through the atomic level.
  • the catalyst catalyzes the oxygen reduction reaction and produces water.
  • the anode may be formed of at least one of a carbon brush, a carbon cloth, a carbon fiber cloth, and granular activated carbon.
  • a carbon cloth or a carbon brush can be cut to an appropriate size and heat-treated at 450 ° C for 30 minutes in a muffle furnace to obtain an anode.
  • the anode can be easily obtained, thereby reducing the production cost of the microbial fuel cell.
  • the anode and the air cathode may be disposed perpendicular to each other; according to another embodiment of the present application, a separator may further be provided between the cathode and the anode. Therefore, those skilled in the art can make corresponding adjustments to the microbial fuel cell according to the embodiment of the present application according to actual conditions, and select a more suitable structure to constitute the microbial fuel cell, as long as the features according to the embodiments described above are satisfied. Just fine.
  • the present application proposes an electrochemical system.
  • the electrochemical system 1000 may include a housing 100 and a modular electrode assembly 300 defining a reaction space 200 in the housing 100, and the modular electrode assembly 300 is disposed in the reaction space 200.
  • the modular electrode assembly 300 may include a hollow cathode socket 310 and an anode 330.
  • the hollow cathode slot 310 may include a plurality of air cathodes 320 and a plurality of anodes 330 electrically connected to the air cathodes 320, and a plurality of air cathodes 320 may be disposed on the side walls 311 of the hollow cathode slots 310, and The plurality of air cathodes 320 may include the catalyst layer described above.
  • the electrochemical system 1000 not only has all the features and advantages of the catalyst layer described above, that is, the catalytic activity of the air cathode 320 is good, the metal utilization rate is high, the cost is low, and the like, and the electrochemical system 1000
  • the plurality of air cathodes 320 and the anodes 330 are also organically integrated in the same reaction space 200 by providing the modular electrode assembly 300, further improving the power generation performance of the electrochemical system 1000.
  • the hollow cathode slot 310 may include a plurality of sidewalls 311 and a bottom surface (not shown), and the plurality of sidewalls 311 and the bottom surface define a hollow space inside the hollow cathode slot 310.
  • the side of the side wall 311 near the hollow space is in contact with the atmosphere.
  • the air cathode is generally disposed on the top or side of the electrochemical system due to the need to contact the atmosphere.
  • the air cathode adopts an atomic-level dispersed metal catalyst to catalyze the oxygen reduction reaction, and the catalytic reaction efficiency is high, the stability is good, and the electron utilization rate and the production in the electrochemical system are improved.
  • a plurality of air cathodes can be disposed on the sidewall of the hollow cathode slot, that is, integrating multiple air cathodes in the same electrochemical system, saving not only Space, and can ensure that each air cathode can be in full contact with air, and the oxygen reduction reaction of each air cathode does not affect each other.
  • the electron utilization rate and the electricity generation performance in the electrochemical system are further improved.
  • the hollow cathode slot can be easily disassembled to facilitate the replacement of the electrodes, or the power of the entire system can be adjusted according to the actual treated water supply (can be achieved by increasing or decreasing the number of electrodes), thereby improving the electricity.
  • the flexibility and practicality of the chemical system can be easily disassembled to facilitate the replacement of the electrodes, or the power of the entire system can be adjusted according to the actual treated water supply (can be achieved by increasing or decreasing the number of electrodes), thereby improving the electricity.
  • the specific number of the plurality of air cathodes 320 is not particularly limited, and those skilled in the art can perform the setting according to actual needs.
  • 2-10 air cathodes 320 may be provided, and 2, 3 or 4 air cathodes 320 may be provided.
  • the specific number of the anodes 330 is also not particularly limited.
  • 1-10 anodes 330 may be provided, and one, two, three or four anodes 330 may be provided.
  • the manner in which the air cathode 320 is connected to the anode 330 is not particularly limited as long as each of the air cathodes 320 has an anode 330 connected thereto.
  • the air cathode 320 and the anode 330 may be connected in one-to-one correspondence, or the plurality of air cathodes 320 may be connected to one anode 330, or one air cathode 320 may be connected to the plurality of anodes 330.
  • the shape of the hollow cathode slot 310 is not particularly limited, and a person skilled in the art can make a reasonable design according to the number of air cathodes 320 to be provided.
  • the hollow cathode slot 310 may be a triangular prism type, a hexahedral type, or an octahedral type.
  • FIG. 1 For example, according to some embodiments of the present application, referring to FIG.
  • the hollow cathode slot 310 may be a hexahedral type, and two air cathodes 320 may be disposed on the sidewall 311 of the hollow cathode slot, and the two air cathodes 320 may be Relative settings can also be set adjacently.
  • four air cathodes 320 may be disposed on the four side walls 311 of the hexahedral hollow cathode slot 310.
  • the hollow cathode slot 310 may be of a triangular prism type, and three air cathodes 320 may be disposed on three side walls of the triangular prism hollow cathode slot 310.
  • the material of the anode 330 is not particularly limited, and when the electrochemical system is a bioelectrochemical system, the anode 330 is only required to facilitate microbial attachment.
  • the anode 330 may be at least one of a carbon brush, carbon cloth, carbon paper, carbon felt, activated carbon, and graphite.
  • the anode 330 may include a carbon brush or a plurality of carbon brushes.
  • the anode when the anode is a carbon cloth, it may be a single layer of carbon cloth or a combination of multiple layers of carbon cloth separated by a separator. Thereby, the adhesion ability of the microorganism at the anode can be further improved, and the cost of the electrochemical system can be saved.
  • the specific shape of the anode 330 is not particularly limited, and when the anode 330 is a planar electrode, such as carbon paper or carbon cloth, the electrochemical system 1000 may further include an air cathode 320 and an anode 330. Inter-membrane (not shown).
  • the specific material of the separator is not particularly limited, and may be, for example, glass fiber, plastic mesh, nylon cloth, or the like.
  • the separator can prevent short-circuiting between the air cathode and the anode, further shorten the vertical distance between the cathode and the anode, improve the electrode reaction efficiency, enhance ion diffusion between the electrodes, and slow down the cathode contamination rate.
  • the arrangement and position of the anode 330 are not particularly limited.
  • the anode 330 may be disposed between the hollow cathode slot 310 and the housing 100.
  • the modular electrode assembly 300 may further include an anode socket 360, and the anode 330 may also be disposed on a sidewall of the anode socket 360.
  • the anode socket 360 can be disposed around the hollow cathode slot 310, whereby the anode socket 360 can be easily removed for easy replacement of the electrodes.
  • the anodes 360 can be used to easily integrate the plurality of anodes 330 into the same electrochemical system, which not only saves space, but also does not affect each anode, and can also be processed according to actual conditions.
  • adjust the power of the entire system can be achieved by increasing or decreasing the number of electrodes). Thereby, the use effect of the electrochemical system 1000 is further improved.
  • the electrochemical system 1000 may further include a plurality of external resistors 350 disposed between the air cathode 320 and the anode 330 and electrically connected to the air cathode 320 and the anode 330.
  • the total resistance of the plurality of external resistors 350 during operation of the electrochemical system 1000 is not particularly limited. For example, it may be 0 ohms, that is, short-circuit operation, or may be infinite, that is, open circuit operation, or It is 2-1000 ohms. Thereby, the use effect of the electrochemical system is further improved.
  • the air cathode 320 may include a plurality of sub-cathodes 321 .
  • the air cathode 320 having a large area can be easily prepared by using the plurality of sub-cathodes 321, and the air cathode 320 obtained has high surface flatness and good performance, and further improves the use effect of the electrochemical system.
  • the connection manner of the plurality of sub-cathodes 321 is not particularly limited, and the plurality of sub-cathodes 321 may be connected in series or in parallel. Thereby, the plurality of sub-cathodes are connected in various ways, and can be combined as needed to form the air cathode 320, thereby further improving the use effect of the electrochemical system.
  • each air cathode may comprise a plurality of equally sized sub-cathodes arranged in an array.
  • each sub-cathode is relatively moderate, and the sub-cathode can be prepared simply and quickly, and the quality of the catalyst layer can be ensured.
  • the plurality of sub-cathodes are connected by a simple series or parallel connection to constitute a monolithic air cathode, and each of the sub-cathodes may have a structure of a cathode including a diffusion layer as described above. The specific structure of the cathode has been described in detail above and will not be described herein.
  • the plurality of sub-cathodes 321 may be directly disposed on the sidewall of the hollow cathode slot 310; according to an embodiment of the present application, when hollow When the cathode slot 310 is formed of a non-conductive material, such as formed of plastic, according to an embodiment of the present application, referring to FIG. 11, the air cathode 320 may further include a conductive support frame 322, and the plurality of sub-cathodes 321 may be disposed on the conductive support frame. At 322, the conductive support frame 322 is electrically coupled to the anode 330.
  • the material of the conductive support frame 322 is not particularly limited as long as the sub-cathode 321 can be fixed to the surface thereof and can be made conductive.
  • the conductive support frame 322 can be a stainless steel mesh.
  • the conductive support frame may be formed without using a conductive material, but by means of providing a wire, A series or parallel connection of the plurality of sub-cathodes 321 is achieved.
  • the air cathode 320 may further include a plurality of wires 323 that are in one-to-one correspondence with the plurality of sub-cathodes 321 and are electrically connected to the anodes 330.
  • each sub-cathode 321 can be directly disposed on the side wall 311 of the hollow cathode socket, and then each sub-cathode is electrically connected to the anode 330 through a plurality of wires, which simplifies the preparation process and further improves the electrochemistry.
  • the effect of the system 1000 is not limited to:
  • the specific type of the electrochemical system according to the embodiment of the present application is not particularly limited as long as the cathode thereof undergoes an oxygen reduction reaction.
  • it may be a fuel cell, a microbial fuel cell, a microbial electrolysis cell or a microbial desalination battery, etc.
  • the electrochemical system according to the embodiment of the present application has a wide application scenario, for example, it can be used for treating domestic sewage, industrial sewage, etc., and The organic matter in the sewage is converted into electric energy by microorganisms, and at the same time as the pollution is eliminated, the available energy is generated, and the energy consumption is low and the efficiency is high.
  • Example 1 Preparation of atomic-scale dispersed Co catalyst
  • reaction solution A 0.01 M CoCl 2 solution, the solvent is a water/ethanol mixed solvent having a volume ratio of 1:9; preparing a reducing agent solution B: 5.0 M N 2 H 5 OH hydrazine hydrate solution containing 0.05 M KOH; A carrier dispersion C: 2.5 mg mL -1 of a nitrogen-doped mesoporous carbon dispersion was prepared.
  • the sample prepared in the step (3) is thermally activated under the following conditions: the temperature is raised to 900 ° C in 90 minutes, the temperature is kept for 60 minutes, the temperature is naturally cooled to room temperature, and the gas condition is 500 sccm high purity argon gas, thereby obtaining a thermally stable atomic level. Disperse the Co catalyst.
  • Example 2 Preparation of a cathode containing an atomic-stage dispersed Co catalyst
  • Example 3 Fabrication of an electrochemical system containing atomically dispersed Co catalyst
  • the reactor adopts a double chamber configuration with an anode chamber length of 4 cm.
  • the upper middle portion has a hole with a diameter of 1 cm for placing a platinum electrode as an anode; the cathode chamber is 2 cm long with a hole having a diameter of 1 cm for placement.
  • the two chambers are separated by a cation exchange membrane.
  • the titanium piece and the cathode containing the atomic-stage dispersed Co catalyst prepared in Example 2 were attached, and then fixed by a cathode baffle, and then fixed by screws and screws at the four corners of the reactor, and the reactor (ie, electrochemical system) was assembled. .
  • the electrolyte was 50 mM phosphate buffer.
  • Example 3 For other production methods, reference is made to Example 3, except that in the cathode of the comparative example, the catalyst is Co nanoparticle.
  • Example 3 For other production methods, reference is made to Example 3, except that in the cathode of the comparative example, the catalyst is a platinum carbon catalyst.
  • Example 3 For other production methods, reference is made to Example 3, except that in the cathode of the comparative example, the catalyst is an activated carbon catalyst.
  • the cathode reduction current of the electrochemical system produced in Example 3 and Comparative Examples 1-3 was measured by chronoamperometry. After the electrochemical system was opened for 3 hours, the measurement was started from a starting potential of 0.2 V (the reference electrode was Ag/AgCl), and one set was measured every 0.1 V, and the end potential was -0.4 V (the reference electrode was Ag/AgCl).
  • the reduction current of the cathode containing the atomic-dispersed Co catalyst is higher than that of the cathode containing Co nanoparticles, platinum carbon, and activated carbon.
  • the air cathode containing the atomic-dispersed Co catalyst obtained the highest current density of 26 A/m 2 , while the platinum carbon air cathode had a current density of only 16 A/m 2 , obviously, according to the embodiment of the present application.
  • the cathode containing the atomic-dispersed Co catalyst has superior electrical properties than the conventional electrode widely used at present.
  • Example 4 Preparation of a microbial fuel cell containing an atomic-grade dispersed Co catalyst
  • the carbon brush was used as the anode, and the anaerobic electrogenic bacteria were attached.
  • the anode material was calcined at 450 ° C for 30 min in a muffle furnace for pretreatment.
  • the reactor adopts a single-chamber configuration with a thickness of 4 cm.
  • the pole plates are sealed and fixed by O-rings and gaskets, and the titanium plate and the air cathode containing the atomic-level dispersed Co catalyst prepared in Example 2 are attached, and then fixed by the cathode baffle, and the screw is used at the four corners of the reactor. After the screw is fixed, the reactor (ie microbial fuel cell) is assembled.
  • the inoculation source was effluent from a microbial fuel cell anode that had been operated normally.
  • the substrate was 50 mM phosphate buffer to prepare a concentration of 1 g/L sodium acetate, and 12.5 mL/L mineral and 5 mL/L vitamin were added.
  • the manner of preparation was as described in Example 4, except that in the air cathode in the comparative example, the catalyst was Co nanoparticles.
  • Comparative Example 5 Preparation of a microbial fuel cell containing a platinum carbon catalyst
  • Example 5 The manner of preparation was as described in Example 5, except that in the air cathode of the comparative example, the catalyst was a platinum carbon catalyst.
  • the manner of preparation was as described in Example 6, except that in the air cathode of the comparative example, the catalyst was an activated carbon catalyst.
  • the polarization curves of the microbial fuel cells produced in Example 4 and Comparative Examples 4-6 were measured using a rapid change external resistance method.
  • the rapid change of the external resistance method means that the external resistance is replaced and the microbial fuel cell is stabilized in a short period of time in the operation cycle of the microbial fuel cell, and the reactor is stabilized under the external resistance of 5000 ⁇ after replacing the 1 g/L sodium acetate substrate. Hour, record the output voltage and anode potential, and then reduce the external resistance every 20min, so that the external resistance is 1000 ⁇ , 500 ⁇ , 300 ⁇ , 200 ⁇ , 100 ⁇ , 50 ⁇ , 30 ⁇ , 20 ⁇ , 10 ⁇ , 5 ⁇ , 2 ⁇ , and record the resistance in real time.
  • the area power density curve is plotted, as shown in FIG. It can be seen from the figure that the maximum power density of the cathode of the microbial fuel cell containing the atomic-grade dispersed Co catalyst is about 2500 mW/m 2 , the maximum power density of the Co nanoparticle air cathode is about 2100 mW/m 2 , and the maximum of the activated carbon air cathode.
  • an air cathode is a carbon platinum maximum power density of 1500mW / m 2 or so, apparently atomically dispersed Co ,, containing catalyst microbial fuel cell is higher than a Co-containing nanoparticles, platinum Microbial fuel cells with carbon and activated carbon.
  • the atomic-grade dispersed Co catalyst has good catalytic performance and high catalytic efficiency. Both the electrochemical system using atomic-scale dispersed Co catalyst and the microbial fuel cell have better electrical performance.
  • the operational stability tests were carried out on the microbial fuel cells produced in Example 4 and Comparative Example 5.
  • R is the external resistance value
  • A is the cathode area
  • the microbial fuel cell containing platinum carbon catalyst scraped the biofilm on the air cathode surface after running for 200 h, and then continued to test it at different times.
  • the output voltage of the time, and calculate its current density value the test results are shown in Figure 15. It can be seen from the figure that the microbial fuel cell containing atomically dispersed Co catalyst has very stable electricity production performance and hardly changes with the running time of the battery. After 700 hours of operation, the current density value is still relatively stable. Compared to the beginning, there is almost no decline.
  • the microbial fuel cell containing platinum carbon catalyst has a significant decrease in power generation performance with the increase of battery running time.
  • the electricity production performance of the microbial fuel cell containing platinum carbon catalyst is improved, indicating that the air cathode containing the platinum carbon catalyst is easily contaminated, hindering its contact with air, and hindering the oxygen reduction reaction of the cathode. And reduce the decomposition ability of the anode to the organic matter, thereby causing a decrease in the power generation performance of the battery.
  • the air cathode containing the atomic-grade dispersed Co catalyst the microorganisms are not easy to aggregate, and the anti-pollution ability is strong, and the electricity generation performance is relatively stable, and the cycle performance is good.
  • the atomic-stage dispersed Co catalyst has good catalytic performance and high stability, and the microbial fuel cell containing the atom-level dispersed Co catalyst has better power generation stability.
  • Example 5 Fabrication of an electrochemical system containing two air cathodes
  • the other manufacturing method is the same as that in Embodiment 3, except that the electrode of the electrochemical system adopts a modular electrode assembly.
  • the hollow cathode slot 310 is a hexahedron type, and two air cathodes 320 are placed in a hollow cathode slot.
  • the air cathode 320 contains the catalyst layer containing the atomic-level dispersed Co catalyst prepared by the method of Embodiment 2, and the hollow cathode slot 310 is filled with air and then inserted into the reaction space filled with the matrix.
  • each of the air cathodes 320 is connected to the carbon brush anode 330 to which the anaerobic electrogenic bacteria are attached, and the external resistance 350 is connected to obtain an electrochemical system containing two air cathodes.
  • Example 6 Fabrication of an electrochemical system containing three air cathodes
  • the other manufacturing method is the same as that of Embodiment 5, with reference to FIG. 9 , except that the hollow cathode slot 310 used is a triangular prism type, and three air cathodes 320 are placed on three sidewalls of the hollow cathode slot 310, wherein The air cathode 320 contains the catalyst layer containing the atomic-stage dispersed Co catalyst prepared by the method of Example 2.
  • Example 7 Fabrication of an electrochemical system containing four air cathodes
  • the other manufacturing method is the same as that of Embodiment 4, with reference to FIG. 8, except that four air cathodes 320 are placed on the four sidewalls of the hollow cathode slot 310, wherein the air cathode 320 is prepared according to the method of Embodiment 2.
  • a catalyst layer containing an atomic-stage dispersed Co catalyst is prepared according to the method of Embodiment 2.

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  • Inert Electrodes (AREA)

Abstract

L'invention concerne une cathode à air à atome unique, une batterie, un système électrochimique et un système bioélectrochimique. La cathode comprend : une couche de collecteur de courant, et une couche de catalyseur, la couche de catalyseur étant disposée sur la couche de collecteur de courant, et la couche de catalyseur comprenant un catalyseur métallique dispersé au niveau atomique.
PCT/CN2018/114155 2018-04-17 2018-11-06 Cathode à air à atome unique, batterie, système électrochimique et système bioélectrochimique WO2019200895A1 (fr)

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CN201820542336.4U CN208272026U (zh) 2018-04-17 2018-04-17 电化学系统、阴极、电池
CN201810341661.9A CN108630950B (zh) 2018-04-17 2018-04-17 单原子空气阴极、电池、电化学系统与生物电化学系统
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Citations (5)

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Publication number Priority date Publication date Assignee Title
CN1617373A (zh) * 2003-11-14 2005-05-18 鸿富锦精密工业（深圳）有限公司 一种燃料电池用催化剂及其燃料电池
CN101380594A (zh) * 2008-09-05 2009-03-11 南京师范大学 质子交换膜燃料电池催化剂的氮化钛载体或氮化钛和炭载体混合载体
CN101607781A (zh) * 2009-07-17 2009-12-23 广东省生态环境与土壤研究所 一种微生物电池装置及城市污泥的处置方法
CN102334221A (zh) * 2008-12-30 2012-01-25 宾夕法尼亚州研究基金会 用于微生物电解电池和微生物燃料电池的阴极
CN108630950A (zh) * 2018-04-17 2018-10-09 清华大学 单原子空气阴极、电池、电化学系统与生物电化学系统

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1617373A (zh) * 2003-11-14 2005-05-18 鸿富锦精密工业（深圳）有限公司 一种燃料电池用催化剂及其燃料电池
CN101380594A (zh) * 2008-09-05 2009-03-11 南京师范大学 质子交换膜燃料电池催化剂的氮化钛载体或氮化钛和炭载体混合载体
CN102334221A (zh) * 2008-12-30 2012-01-25 宾夕法尼亚州研究基金会 用于微生物电解电池和微生物燃料电池的阴极
CN101607781A (zh) * 2009-07-17 2009-12-23 广东省生态环境与土壤研究所 一种微生物电池装置及城市污泥的处置方法
CN108630950A (zh) * 2018-04-17 2018-10-09 清华大学 单原子空气阴极、电池、电化学系统与生物电化学系统

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