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WO2019200895A1 - 单原子空气阴极、电池、电化学系统与生物电化学系统 - Google Patents

单原子空气阴极、电池、电化学系统与生物电化学系统 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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Prior art keywords
cathode
anode
present application
electrochemical system
catalyst
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Application number
PCT/CN2018/114155
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English (en)
French (fr)
Inventor
张潇源
徐婷
伍晖
黄凯
黄霞
Original Assignee
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/zh

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90Selection of catalytic material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/16Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel 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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Abstract

提出了单原子空气阴极、电池、电化学系统与生物电化学系统。该阴极包括:集电层;以及催化剂层,所述催化剂层设置在所述集电层上,所述催化剂层包括原子级分散金属催化剂。

Description

单原子空气阴极、电池、电化学系统与生物电化学系统
优先权信息
本申请请求2018年04月17日向中国国家知识产权局提交的、专利申请号为201810341661.9,以及2018年04月17日向中国国家知识产权局提交的、专利申请号为201820542336.4的专利申请的优先权和权益,并且通过参照将其全文并入此处。
技术领域
本申请涉及环境、材料、能源领域,具体地,涉及阴极、电池以及电化学系统。
背景技术
环境问题与能源问题是当代社会发展面临的两大难题,净化污水的同时兼顾能源回收是污水处理技术面对的新挑战。以微生物燃料电池为典型代表的生物电化学系统是一种新兴的污水处理技术,生物电化学系统能够在处理污水的同时将污染物中的化学能转化为电能。微生物燃料电池可以利用附着在阳极的产电微生物将污水中的有机物氧化,同时阴极接受电子完成氧还原反应。
然而,目前的阴极、电池、电化学系统的性能仍有待提高。
发明内容
本申请提出了一种阴极。该阴极包括:集电层;以及催化剂层,所述催化剂层设置在所述集电层上,所述催化剂层包括原子级分散金属催化剂。由此,采用原子级分散金属催化剂催化该阴极中的氧还原反应,不仅具有催化活性好、金属利用率高、成本低廉等优点,而且当该阴极用于电化学系统时,可以提高电子利用率,进而提升了电化学系统的产电性能。
根据本申请的实施例,所述阴极进一步包括:扩散层,所述扩散层设置在所述集电层远离所述催化剂层的一侧,或者设置在所述催化剂层远离所述集电层的一侧。由此,当该阴极为空气阴极时,该扩散层可以与空气接触,有利于氧气扩散至该空气阴极中,进一步提高了该阴极的使用效果。
根据本申请的实施例,所述原子级分散金属催化剂包括载体以及负载在所述载体上的活性金属,所述活性金属包括Fe、Co和Ni的至少之一。由此,该原子级分散金属催化剂的种类较多,并且将所述活性金属负载在载体上,可以提高催化剂层的稳定性,进一步提高该阴极的使用性能。
根据本申请的实施例,所述原子级分散金属催化剂是在低温环境下制备的。由此,可以简便地制备性能良好的原子级分散金属催化剂,进一步提高该阴极的使用性能。
在本申请的另一方面,本申请提出了一种电池。根据本申请的实施例,该电池包括:前面所述的阴极;以及阳极,所述阳极与所述阴极电连接。由此,该电池具有前面所述的阴极所具有的全部特征以及优点,并且该电池产电效率高,运行稳定性较好。
根据本申请的实施例,所述电池在外阻为50欧姆时,功率密度不小于2000mW/m 2。由此,该电池的产电效率较高,进一步提高了该电池的使用效果。
根据本申请的实施例,所述电池在运行500小时之后的电流密度衰减不超过5%。由此,该电池的运行稳定性较好,进一步提高了该电池的使用效果。
在本申请的又一方面,本申请提出了一种电化学系统。根据本申请的实施例,该电化学系统包括:壳体,所述壳体中限定出反应空间;以及模块化电极组件,所述模块化电极组件设置在所述反应空间中,所述模块化电极组件进一步包括:中空式阴极插槽,所述中空式阴极插槽包括:多个空气阴极,所述多个空气阴极设置在所述中空式阴极插槽的侧壁上,所述空气阴极包括前面所述的催化剂层;阳极,所述阳极与所述空气阴极电连接。由此,该电化学系统不仅具有前面所述的催化剂层所具有的全部特征以及优点,即该空气阴极的催化活性好、金属利用率高、成本低廉等,并且,该电化学系统还通过设置模块化电极组件,将多个空气阴极以及阳极整合在同一个反应空间中,进一步提高了该电化学系统的产电性能。
根据本申请的实施例,所述中空式阴极插槽包括多个所述侧壁以及底面,多个所述侧壁以及所述底面在所述中空式阴极插槽内部限定出中空空间,所述侧壁靠近所述中空空间的一侧与大气接触。由此,可以在将多个空气阴极整合在同一个中空空间的情况下,保证每个空气阴极与空气充分接触反应,进一步提高了电化学系统的产电性能。
根据本申请的实施例,所述阳极设置在所述中空式阴极插槽以及所述壳体之间。由此,进一步提高了电化学系统的使用效果。
根据本申请的实施例,所述模块化电极组件进一步包括:阳极插槽,所述阳极插槽的侧壁上设置有所述阳极。由此,阳极插槽可以简便地进行拆卸,便于对阳极进行更换,并且,当该系统中设置有多个阳极时,可以简便地将多个阳极设置在同一个阳极插槽中,进一步提高了电化学系统的使用效果。
根据本申请的实施例,所述空气阴极包括多个子阴极。由此,通过设置多个子阴极,可以简便地制备面积较大的空气阴极,并且制得的空气阴极表面平整性高,性能良好,进一步提高了该电化学系统的使用效果。
根据本申请的实施例,多个所述子阴极并联或串联。由此,多个子阴极的连接方式多 样,可以根据需要进行组合,以便形成空气阴极,进一步提高了电化学系统的使用效果。
根据本申请的实施例,所述空气阴极进一步包括导电支撑架,所述多个子阴极直接设置在所述导电支撑架上,所述导电支撑架与所述阳极电连接。由此,可以简便地令多个子阴极均与阳极电连接,进一步提高了电化学系统的使用效果。
根据本申请的实施例,所述空气阴极进一步包括多个导线,所述多个导线与所述多个子阴极一一对应连接,并且所述多个导线均与所述阳极电连接。由此,可以简便地令多个子阴极均与阳极电连接,进一步提高了电化学系统的使用效果。
根据本申请的实施例,所述阳极为碳刷、碳布、碳纸、碳毡、活性炭、石墨中的至少之一。当该电化学系统为生物电化学系统时,所述阳极可以提高微生物的附着能力,并可进一步节省该电化学系统的成本。
根据本申请的实施例,所述阳极为面状电极,所述电化学系统进一步包括:隔膜,所述隔膜设置在所述空气阴极以及所述阳极之间。由此,所述隔膜可以减缓空气阴极的污染速率,进一步提高了电化学系统的产电性能。
附图说明
图1显示了根据本申请一个实施例的阴极的结构示意图;
图2显示了根据本申请一个实施例的制备原子级分散金属催化剂的方法流程图;
图3显示了根据本申请另一个实施例的阴极的结构示意图;
图4显示了根据本申请又一个实施例的阴极的结构示意图;
图5显示了根据本申请又一个实施例的阴极的结构示意图;
图6显示了根据本申请一个实施例的电池的结构示意图;
图7显示了根据本申请一个实施例的电化学系统的结构示意图;
图8显示了根据本申请另一个实施例的电化学系统的结构示意图;
图9显示了根据本申请又一个实施例的电化学系统的结构示意图;
图10显示了根据本申请又一个实施例的电化学系统的结构示意图;
图11显示了根据本申请一个实施例的空气阴极的结构示意图;
图12显示了根据本申请另一个实施例的空气阴极的结构示意图;
图13显示了根据本申请一些具体实施例和对比例的电化学系统的产电性能测试图;
图14显示了根据本申请另一些具体实施例和对比例的生物电化学系统的产电性能测试图;以及
图15显示了根据本申请一些具体实施例和对比例的电化学系统的运行稳定性测试图。
附图标记:
10:催化剂层;20:集电层;30:扩散层;40:支撑层;110:阴极;100:壳体;200:反应空间;300:模块化电极组件;310:中空式阴极插槽;311:侧壁;320:空气阴极;321:子阴极;322:导电支撑架;323:导线;330:阳极;350:外阻;360:阳极插槽;1000:电化学系统。
具体实施方式
下面详细描述本申请的实施例,所述实施例的示例在附图中示出,其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的,仅用于解释本申请,而不能理解为对本申请的限制。
需要说明的是,在本申请的各个方面中所描述的特征和效果可以互相适用,在此不再赘述。
本申请是基于发明人对以下事实和问题的发现和认识作出的:
目前的电化学系统存在产电性能较差且生产成本较高的问题。发明人通过深入研究以及大量实验发现,这是由电化学系统中,阴极的催化剂催化效率较差且成本较高造成的。特别是在生物电化学系统中,阴极的氧还原反应是限制生物电化学系统的产电性能的关键因素之一,氧还原反应主要是由阴极催化剂来驱动的,而目前用于阴极的催化剂成本较高且催化效率较差,例如,传统的阴极采用铂碳作为催化剂,铂价格昂贵、资源稀缺,而且在长期运行阴极被污染时,其催化性能明显退化。在本申请的一个方面,本申请提出了一种阴极。根据本申请的实施例,参考图1,该阴极110包括:催化剂层10和集电层20。其中,催化剂层10设置在集电层20上,催化剂层10包括原子级分散金属催化剂。由此,采用原子级分散金属催化剂催化该阴极110中的氧还原反应,不仅具有催化活性好、金属利用率高等优点,而且当该阴极110用于电化学系统时,可以提高电子利用率,进而提升了电化学系统的产电性能。
根据本申请的实施例,原子级分散金属催化剂可以包括载体以及负载在载体上的活性金属。根据本申请的实施例,载体的具体类型不受特别限制,只要能使原子级分散金属催化剂较为均匀地分散在其中即可,具体的,载体可以为石墨烯、介孔碳、碳纳米管、炭黑或者活性炭等。根据本申请的实施例,活性金属的具体种类不受特别限制,只要能催化氧还原反应即可,具体的,活性金属可以包括Fe、Co和Ni的至少之一。具体的,活性金属可以为单元金属,例如单一的Co,单一的Ni,单一的Fe,也可以为双元金属,例如Fe/Co双元金属,Fe/Ni双元金属,Co/Ni双元金属,活性金属还可以为三元金属,例如Fe/Co/Ni三元金属。由此,该原子级分散金属催化剂的种类较多,来源广泛,并且提高了该阴极的 氧还原效率,降低了生产成本。
根据本申请的实施例,原子级分散金属催化剂的制备方法不受特别限制,只要能使活性金属以金属单原子的形式分散即可。例如,可以通过浸渍法、刻蚀法、光辅助合成法、金属有机框架辅助合成法等制备原子级分散金属催化剂,由此,催化剂层10中的原子级分散金属催化剂可以具有多种制备方法,因此其较容易获得,并且可以简便地将其应用于阴极中,提高阴极氧还原反应的效率。
根据本申请的具体实施例,原子级分散金属催化剂可以是在低温环境下制备的。由此,可以简便地制备性能良好的原子级分散金属催化剂,进一步提高该阴极的使用性能。根据本申请的实施例,采用低温溶液合成法可以大规模制备高金属负载量的原子级分散金属催化剂,可以提高金属原子的有效利用率,降低金属催化剂的应用成本。具体的,可以利用超低温液相抑制成核,使得溶液中金属原子的浓度低于金属单体浓度的成核极限阈值,从而得到含有原子级分散金属的溶液,然后通过进一步的负载过程得到原子级分散金属催化剂。由此,可以在超低温溶液环境中大规模合成原子级分散金属催化剂。
下面根据本申请的具体实施例,对该方法的各个步骤进行详细说明:
根据本申请的实施例,参考图2,该方法包括:
S100:将金属化合物与第一溶剂混合,形成金属前驱体溶液
根据本申请的实施例,在该步骤中,将金属化合物与第一溶剂混合形成金属前驱体溶液。根据本申请的实施例,金属化合物可以为Fe、Co和Ni的至少之一的可溶解的化合物,第一溶剂可以包括水、乙醇、乙二醇、丙酮、氯仿、乙醚、四氟氢喃、二甲基甲酰胺以及甲醛的至少之一。由此,将上述溶质以及溶剂混合形成的金属前驱体溶液,可以作为后续步骤中原子级分散金属的来源。根据本申请的实施例,金属前驱体溶液的浓度可以为0.001-1.0mol/L,具体的,可以为0.005mol/L、0.008mol/L、0.01mol/L、0.02mol/L、0.05mol/L、0.08mol/L、1.0mol/L等。
根据本申请的实施例,由该方法制备的原子级分散金属可以包括Fe、Co和Ni的至少之一。根据本申请的实施例,由该方法制备的原子级分散金属可以为单元金属催化剂,例如,可以利用该方法制备原子级分散金属铁催化剂,或者利用该方法制备原子级分散金属钴催化剂,或者利用该方法制备原子级分散金属镍催化剂。根据本申请的实施例,由该方法制备的原子级分散金属还可以为双元金属催化剂,例如,可以利用该方法制备原子级分散的铁/钴双元金属催化剂,或者利用该方法制备原子级分散的铁/镍双元金属催化剂,或者利用该方法制备原子级分散的钴/镍双元金属催化剂。根据本申请的实施例,由该方法制备的原子级分散金属还可以为三元金属催化剂,例如,可以利用该方法制备原子级分散的铁/钴/镍三元金属催化剂。由此,可以利用该方法实现单元、双元以及三元金属催化剂的制备。
根据本申请的具体实施例,金属化合物可以为Fe的可溶解的化合物,或者为Co的可溶解的化合物,或者为Ni的可溶解的化合物,或者为Fe、Co混合的可溶解的化合物,或者为Fe、Ni混合的可溶解的化合物,或者为Co、Ni混合的可溶解的化合物,或者为Fe、Co、Ni混合的可溶解的化合物。由此,可以分别制备单元、双元以及三元金属催化剂。
S200:将还原剂与第二溶剂混合形成还原剂溶液
根据本申请的实施例,在该步骤中,将还原剂与第二溶剂混合形成还原剂溶液。根据本申请的实施例,还原剂可以包括NaBH 4、KBH 4、N 2H 4、N 2H 5OH、甲醛、甲酸、抗坏血酸、Na 2SO 3、K 2SO 3以及H 2C 2O 4的至少之一,第二溶剂可以包括水、乙醇、乙二醇、丙酮、氯仿、乙醚、四氟氢喃、二甲基甲酰胺以及甲醛的至少之一。由此,在后续过程中,将上述溶质以及溶剂混合形成的还原剂溶液可以与金属前驱体溶液发生反应,还原剂被还原,得到含有原子级分散金属的溶液。根据本申请的实施例,还原剂溶液的浓度可以为0.001-10.0mol/L,具体的,可以为2mol/L、5mol/L、7mol/L、8mol/L。需要说明的是,第一溶剂与第二溶剂不同时为水。
S300:将载体材料与第三溶剂混合形成分散液
根据本申请的实施例,在该步骤中,将载体材料与第三溶剂混合形成分散液。根据本申请的实施例,载体材料可以为掺杂的碳纳米材料。根据本申请的实施例,在掺杂的碳纳米材料中,掺杂原子会在碳纳米材料的表面形成缺陷,从而可以增加载体材料对金属原子的吸附作用,进而可以提高载体材料对金属原子的负载量。根据本申请的具体实施例,载体材料可以包括氮掺杂介孔碳(CMK-3)、氮掺杂石墨烯以及石墨相碳化氮(g-C 3N 4)的至少之一。由此,可以利用上述材料获得高金属负载量的原子级分散金属催化剂。
根据本申请的实施例,第三溶剂可以包括水、乙醇、乙二醇、丙酮、氯仿、乙醚、四氟氢喃、二甲基甲酰胺以及甲醛的至少之一。由此,可以将上述溶质以及溶剂混合形成分散液,在后续步骤中利用分散液中的溶质吸附金属原子,获得载体材料负载的原子级分散金属催化剂。根据本申请的实施例,分散液的浓度可以为0.1-10g/L,具体的,可以为2.5g/L、3.5g/L、4.5g/L、5.5g/L、6.5g/L、7.5g/L、8.5g/L、9.5g/L。
S400:将金属前驱体溶液与还原剂溶液混合,以便得到含有原子级分散金属的溶液
根据本申请的实施例,在该步骤中,将金属前驱体溶液与还原剂溶液混合,得到含有原子级分散金属的溶液。根据本申请的实施例,可以在-100~0℃的低温环境下,将金属前驱体溶液与还原剂溶液混合。本领域技术人员能够理解的是,溶液合成过程中存在着金属单体浓度的成核极限阈值,金属单体的浓度低于此阈值时,可以得到含有原子级分散金属的溶液。现有技术中常以微流控方法控制金属单体浓度,微流控方法通过创建局部低浓度,提高比表面积,减小扩散维度等,使得反应物低速混合,进而控制质量和热的传输。上述 微流控方法的制备流程过于复杂,产率较低,严重抑制原子级分散金属催化剂的大规模制备。
根据本申请的实施例,通过降低温度可以显著提升成核势垒,有效抑制成核,从而提高溶液中分散的金属原子的浓度。并且,降低温度后,分散的金属原子可以有效吸附在不同的载体表面,从而有利于在超低温溶液环境中,大规模合成原子级分散金属催化剂。发明人发现,在温度高于上述温度范围时,溶液中分散的金属原子的浓度较低,金属原子的有效利用率较低。而在温度低于上述温度范围时,会导致反应动力学和热力学过慢,无法有效制备金属单原子。由此,将温度设置在上述温度范围内,可以大规模合成原子级分散金属催化剂
根据本申请的实施例,为了使还原剂溶液与金属前驱体溶液的反应过程在上述温度范围内进行,在对金属前驱体溶液以及还原剂溶液混合之前,可以先将金属前驱体溶液以及还原剂溶液在低温箱中保温一定的时间,例如,保温30min。由此,可以进一步提高溶液中金属原子的浓度,进一步提高金属原子的利用率。
关于金属前驱体溶液与还原剂溶液的混合方式不受特别限制,本领域技术人员可以根据具体情况进行设计。例如,根据本申请的具体实施例,可以利用注射泵控制滴加速度,将金属前驱体溶液滴加到搅拌的还原剂溶液中,或者将还原剂溶液滴加到搅拌的金属前驱体溶液中,从而使金属前驱体溶液与还原剂溶液充分反应,得到含有原子级分散金属的溶液。根据本申请的实施例,原子级分散金属可以包括Fe、Co和Ni的至少之一。由此,可以简单、有效地制备含有上述金属的多种原子级分散金属催化剂。
根据本申请的实施例,金属前驱体溶液以及还原剂溶液相对的量,可以通过化学反应方程式确定,为了使金属前驱体溶液与还原剂溶液充分反应,可以使还原剂溶液的量远远大于金属前驱体溶液的量,以保证金属前驱体溶液中的金属原子全部被还原。
根据本申请的实施例,将金属前驱体溶液滴加到搅拌的还原
剂溶液中,或者将还原剂溶液滴加到搅拌的金属前驱体溶液中时,滴加速率可以为0.5-50mL/h,搅拌速率可以为0-3000rpm。由此,可以促进金属前驱体溶液与还原剂溶液充分反应,获得含有原子级分散金属的溶液。根据本申请具体的实施例,滴加速率可以为2.5mL/h、7.5mL/h、15mL/h、30mL/h、45mL/h。
S500:将分散液加入到含有原子级分散金属的溶液中并搅拌,以便获得原子级分散金属催化剂
根据本申请的实施例,在该步骤中,将分散液加入到含有原子级分散金属的溶液中并搅拌,获得原子级分散金属催化剂。根据本申请的实施例,利用分散液中的溶质吸附含有原子级分散金属溶液中的金属原子,获得掺杂碳纳米材料负载的原子级分散金属催化剂。 根据本申请的实施例,掺杂的碳纳米材料对金属原子具有很强的吸附作用,从而可以提高载体材料对金属原子的负载量,提高金属原子的有效利用率。
根据本申请的实施例,在-100~0℃的低温环境下,将分散液与含有原子级分散金属的溶液混合,可以保证含有原子级分散金属的溶液中的金属以原子的形式被吸附到载体材料上,进而获得载体材料负载的原子级分散金属催化剂。
根据本申请的实施例,将分散液与含有原子级分散金属的溶液混合后,对上述混合溶液进行搅拌,促进载体材料对原子级分散金属的吸附,随后对上述溶液进行离心或者真空抽滤处理,并在室温下进行干燥,以便获得高金属负载量的原子级分散金属催化剂。根据本申请的实施例,搅拌的速率可以为0-3000rpm,搅拌的时间可以为0-300min。
根据本申请的实施例,为了增加原子级分散金属催化剂的热稳定性,该方法还可以包括:将经过上述步骤制备好的原子级分散金属催化剂放置在气体环境中进行退火处理。根据本申请的实施例,气体环境可以为高真空、氮气、氩气或氢氩混合气,气体的量可以为50-600sccm,退火处理的温度可以为200-1200℃。由此,可以获得热稳定的原子级分散金属催化剂。关于退火处理的具体步骤不受特别限制,本领域技术人员可以根据具体情况进行设计。
综上可知,根据本申请实施例的利用低温溶液法制备的原子级金属催化剂,具有大密度、高产量、高效率、适用性强等优点,且可显著降低原子级金属催化剂大规模商业化应用的成本,因此,将其应用到根据本申请实施例的阴极中,不仅具有催化活性好、金属利用率高等优点,并且可以降低生产成本。
根据本申请的实施例,阴极110的具体类型不受特别限制,只要能在阴极上发生氧还原反应即可。根据本申请的一些实施例,将催化剂层10设置在集电层20上形成阴极110后,阴极110可以直接浸没在电解液中,然后通过曝气,氧气可到达阴极,并且,氧气在阴极上发生氧还原反应。根据本申请的另一些实施例,参考图3以及图4,阴极110也可以为空气阴极,阴极110可以进一步包括扩散层30,扩散层30可以与空气相接触(图中未示出),以便利用空气中的氧气发生还原反应,进而实现该阴极110的使用功能。
根据本申请的一些实施例,参考图3,扩散层30可以设置在集电层20远离催化剂层10的一侧,并与电解液接触(图中未示出)。由此,扩散层30与空气接触,以便氧气可以扩散至该阴极110中,集电层20可以富集电流,并提高阴极110的导电性,催化剂层10在原子级分散金属催化剂作用下,利用电子与氧气发生还原反应,进而可以提高该阴极110的使用效果。
根据本申请的另一些实施例,参考图4,该阴极110还可以具有以下结构:扩散层30与空气相接触(图中未示出),催化剂层10形成在扩散层30远离空气的一侧,集电层20 形成在催化剂层10远离扩散层30的一侧,并与电解液接触(图中未示出)。进而可以提高阴极110的使用效果。
为了进一步提高阴极110的使用效果,根据本申请的实施例,参考图5,阴极110还可以进一步具有支撑层40,支撑层40可以形成在催化剂层10与扩散层30之间,并且支撑层40可以由不锈钢网形成。由此,可以通过支撑层40为阴极110提供更加良好的支撑结构,并且支撑层40与集电层20分别位于催化剂层10的两侧,可以为催化剂层10提供良好的保护,防止在实际使用过程中催化剂层10粉化损失,对该阴极110的使用效果造成不利影响。此外,由不锈钢网构成的支撑层40还可以进一步提高该阴极110的导电性,进而可以进一步提高该阴极110的性能。
发明人发现,原子级分散金属催化剂具有高度分散的催化活性位点,因此,原子级分散金属催化剂的催化活性好,催化效率高,并且金属利用率高,成本较低。发明人通过深入研究以及大量实验发现,可以将原子级分散金属催化剂应用到阴极中,并且应用到电化学系统以及生物电化学系统中,从而可以提高阴极的氧还原反应效率,提高电化学系统中的电子利用率,进而提升电化学系统的产电性能。并且,发明人发现,根据本申请具体实施例的阴极结构,特别有利于上述原子级分散金属催化剂的附着。在上述电极结构下,不仅可以简便的将原子级分散金属催化剂固定在催化剂层中,且固定后的催化剂层也具有较好的稳定性。并且,原子级分散金属催化剂用于阴极中,对于阴极利用空气进行的还原反应也具有较好的催化作用。
根据本申请的实施例,阴极110可以是通过下述方法制备的:
(1)将150-300mg碳黑粉末和650-750mg聚四氟乙烯粘结剂混合,多次滚压后,与支撑材料(不锈钢网)在4.5-10MPa下压制成片,再在340℃下高温稳定10-40min,即可得到扩散层30;
(2)将60-300mg原子级分散金属催化剂与24-350μL聚四氟乙烯粘结剂混合,然后均匀涂抹在步骤(1)制备的扩散层30的不锈钢网一侧,即可形成催化剂层10;
(3)将不锈钢网形成的集电层20和步骤(2)中制备的结构一起在4.5-10MPa下压制,并在60-100℃加热20-60min成型,即可得空气阴极320。
综上可知,该阴极不仅催化活性好、金属利用率高、成本低廉,并且制备工艺简便易行,适合大面积生产。
在本申请的另一方面,本申请提出了一种电池。根据本申请的实施例,参考图6,该电池可以包括:前面所述的阴极110以及阳极330,阳极330与阴极110电连接。由此,该电池具有前面所述的阴极所具有的全部特征以及优点,由于前面所述的阴极中的催化剂为原 子级分散金属催化剂,其催化活性高并且稳定性好,因此该电池的产电效率也较高,并且运行稳定性较好。
根据本申请的实施例,该电池在外阻为50欧姆时,功率密度可达到2000mW/m 2。由此,该电池的产电效率较高,进一步提高了该电池的使用效果。具体的,该电池的外阻为50欧姆时,功率密度可达到2540mW/m 2,进一步提高了该电池的使用效果。
根据本申请的实施例,该电池在运行500小时之后的电流密度衰减不超过5%。由此,该电池的运行稳定性较好,进一步提高了该电池的使用效果。具体的,该电池在运行700小时后,其电流密度的衰减也可以不超过5%,进一步说明该电池的运行稳定性较好,进一步提高了该电池的使用效果。
根据本申请的实施例,该电池可以为燃料电池,也可以为微生物燃料电池,只要其阴极发生氧还原反应即可。当该电池为微生物燃料电池时,产电微生物附着在阳极表面,由此,可以通过产电微生物将介质中的有机物氧化分解,并产生电子以及质子,并通过阴极接受电子,通过原子级分散金属催化剂催化氧还原反应并生成水。根据本申请的实施例,阳极可以为碳刷、碳布、碳纤维布以及颗粒活性炭的至少之一形成的。具体地,可以将碳布或者碳刷剪裁成适当大小,并在马弗炉中450摄氏度下热处理30分钟,获得阳极。由此,可以简便地获得阳极,进而降低该微生物燃料电池的生产成本。
此外,本领域技术人员能够理解,在不付出创造性劳动的前提下,对根据本申请实施例的微生物燃料电池进行的改进也属于本申请的保护范围。例如,根据本申请的一个实施例,在微生物燃料电池中,阳极以及空气阴极可以互相垂直设置;根据本申请的另一个实施例,在阴极以及阳极之间,还可以进一步具有隔膜。由此,本领域技术人员可以根据实际情况,对根据本申请实施例的微生物燃料电池做出相应调整,选择更加合适的结构来组成微生物燃料电池,只要满足前面描述的根据本申请实施例的特征即可。
在本申请的又一方面,本申请提出了一种电化学系统。根据本申请的实施例,参考图7,该电化学系统1000可以包括:壳体100以及模块化电极组件300,壳体100中限定出反应空间200,模块化电极组件300设置在反应空间200中。根据本申请的实施例,模块化电极组件300可以包括:中空式阴极插槽310以及阳极330。中空式阴极插槽310可以包括:多个空气阴极320以及多个阳极330,阳极330与空气阴极320电连接,多个空气阴极320可以设置在中空式阴极插槽310的侧壁311上,并且多个空气阴极320可以包括前面所述的催化剂层。由此,该电化学系统1000不仅具有前面所述的催化剂层所具有的全部特征以及优点,即该空气阴极320的催化活性好、金属利用率高、成本低廉等,并且,该电化学系统1000还通过设置模块化电极组件300,将多个空气阴极320以及阳极330有机整合在同 一个反应空间200中,进一步提高了该电化学系统1000的产电性能。
根据本申请的实施例,中空式阴极插槽310可以包括多个侧壁311以及底面(图中未示出),多个侧壁311以及底面在中空式阴极插槽310内部限定出中空空间,侧壁311靠近中空空间的一侧与大气接触。由此,不仅可以将多个空气阴极320整合在同一个中空空间中,而且可以保证每个空气阴极320与空气充分接触反应,进一步提高了电化学系统1000的产电性能。
发明人发现,目前的电化学系统,普遍只含有一个空气阴极以及一个阳极,其在运行过程中,整体的产电效率有限。并且,空气阴极由于需要接触大气,一般设置在电化学系统的顶面或是侧面上。而根据本申请实施例的电化学系统,一方面,空气阴极采用原子级分散金属催化剂来催化氧还原反应,其催化反应效率高,稳定性好,提高了电化学系统中的电子利用率以及产电性能;另一方面,通过设置中空式阴极插槽,可以将多个空气阴极设置在该中空式阴极插槽的侧壁上,即将多个空气阴极整合在同一个电化学系统中,不仅节省了空间,而且可以保证各个空气阴极可以和空气充分接触,并且各个空气阴极的氧还原反应互不影响。由此,进一步提高了电化学系统中的电子利用率以及产电性能。并且,中空式阴极插槽可以简便地进行拆卸,便于对电极进行更换,或是根据实际处理的来水情况,调整整个系统的功率(可通过增减电极数量实现),由此提高了该电化学系统的灵活性和实用性。
根据本申请的实施例,多个空气阴极320的具体数目不受特别限制,本领域技术人员可以根据实际需要进行设置。例如,可以设置2-10个空气阴极320,可以设置2个、3个或者4个空气阴极320。根据本申请的实施例,阳极330的具体数目也不受特别限制,例如,可以设置1-10个阳极330,可以设置1个、2个、3个或者4个阳极330。根据本申请的实施例,空气阴极320与阳极330的连接方式不受特别限制,只要每个空气阴极320都有与其连接的阳极330即可。具体的,空气阴极320与阳极330可以为一一对应连接,也可以多个空气阴极320与1个阳极330连接,也可以1个空气阴极320与多个阳极330连接。
根据本申请的实施例,中空式阴极插槽310的形状不受特别限制,本领域技术人员可以根据想要设置的空气阴极320的数目来进行合理的设计。具体的,中空式阴极插槽310可以为三棱柱型、六面体型或八面体型。例如,根据本申请的一些实施例,参考图7,中空式阴极插槽310可以为六面体型,在中空式阴极插槽的侧壁311上可以设置2个空气阴极320,2个空气阴极320可以相对设置,也可以相邻设置。根据本申请的另一些实施例,参考图8,也可以在该六面体中空式阴极插槽310的4个侧壁311上设置4个空气阴极320。根据本申请的又一些实施例,参考图9,中空式阴极插槽310可以为三棱柱型,3个空气阴极320可以设置在该三棱柱中空式阴极插槽310的3个侧壁上。
根据本申请的实施例,阳极330的材料不受特别限制,当该电化学系统为生物电化学系统时,阳极330只要有利于微生物附着即可。具体的,阳极330可以为碳刷、碳布、碳纸、碳毡、活性炭以及石墨中的至少之一。具体的,阳极330中可以包括一个碳刷,也可以设置多组碳刷。类似地,当阳极为碳布时,可以为单层碳布,也可以为用隔膜间隔开的、具有多层碳布的组合。由此,可以进一步提高微生物在阳极的附着能力,并且可以节省该电化学系统的成本。
根据本申请的实施例,阳极330的具体形状不受特别限制,并且当阳极330为面状电极时,例如碳纸或碳布,电化学系统1000可以进一步包括设置在空气阴极320以及阳极330之间的隔膜(图中未示出)。根据本申请的实施例,隔膜的具体材料不受特别限制,例如可以为玻璃纤维、塑料网、尼龙布等。由此,该隔膜可以防止空气阴极以及阳极之间接触发生短路,进一步缩短阴极以及阳极之间的垂直距离,提高电极反应效率,加强电极之间的离子扩散,同时减缓阴极污染速率。根据本申请的实施例,本领域技术人员可以根据实际情况,对根据本申请实施例的电化学系统做出相应调整,选择更加合适的结构来组成电化学系统,只要满足前面描述的根据本申请实施例的特征即可。
根据本申请的实施例,阳极330的设置方式和位置不受特别限制,例如,参考图7,阳极330可以设置在中空式阴极插槽310以及壳体100之间。由此,进一步提高了电化学系统的使用效果。根据本申请的实施例,参考图10,模块化电极组件300可以进一步包括阳极插槽360,阳极330也可以设置在阳极插槽360的侧壁上。根据本申请的实施例,阳极插槽360可以环绕中空式阴极插槽310设置,由此,阳极插槽360可以简便地进行拆卸,便于对电极进行更换。当系统中包括多个阳极330时,利用阳极插槽360,可以简便地将多个阳极330整合在同一个电化学系统中,不仅节省空间,各个阳极之间互不影响,还可以根据实际处理的来水情况,调整整个系统的功率(可通过增减电极数量实现)。由此,进一步提高了电化学系统1000的使用效果。
根据本申请的实施例,电化学系统1000可以进一步包括多个外阻350,外阻350设置在空气阴极320以及阳极330之间,并且与空气阴极320以及阳极330电连接。根据本申请的实施例,电化学系统1000运行时的多个外阻350的总阻值不受特别限制,例如,可以为0欧姆,即短路运行,也可以为无穷大,即开路运行,也可以为2-1000欧姆。由此,进一步提高了电化学系统的使用效果。
根据本申请的实施例,参考图11以及图12,空气阴极320可以包括多个子阴极321。由此,利用多个子阴极321,可以简便地制备面积较大的空气阴极320,并且制得的空气阴极320表面平整性高,性能良好,进一步提高了该电化学系统的使用效果。根据本申请的实施例,多个子阴极321的连接方式不受特别限制,多个子阴极321可以串联也可以并联。 由此,多个子阴极的连接方式多样,可以根据需要进行组合,以便形成空气阴极320,进一步提高了电化学系统的使用效果。
需要说明的是,在实际工业应用中,制作一整块面积较大的空气阴极时,目前的制作方法较难保证其表面的平整性以及使用性能,因此,根据本申请实施例的空气阴极320,通过设置多个面积较小的的子阴极321,并将其串联或并联,可以简便地制备大面积并且性能良好的空气阴极320,更加有利于该电化学系统1000的工业化应用。根据本申请的具体实施例,每个空气阴极,可以包括阵列排布的多个面积相等的子阴极。由此,每个子阴极的面积都较为适中,可以简便、快捷的制备子阴极,并保证催化剂层的质量。多个子阴极通过简单的串联或并联连接,构成整块的空气阴极,并且每个子阴极均可以具有如前面描述的包括扩散层的阴极的结构。阴极的具体结构前面已经进行了详细的描述,在此不再赘述。
根据本申请的实施例,当中空式阴极插槽310是由导电材料形成时,多个子阴极321可以直接设置在中空式阴极插槽310的侧壁上;根据本申请的实施例,当中空式阴极插槽310是由不导电材料形成时,例如由塑料形成时,根据本申请的实施例,参考图11,空气阴极320可以进一步包括导电支撑架322,多个子阴极321可以设置在导电支撑架322上,导电支撑架322与阳极330电连接。根据本申请的实施例,导电支撑架322的材料不受特别限制,只要能将子阴极321固定在其表面,并且可以导电即可。例如,导电支撑架322可以为不锈钢网。由此,可以简便地令多个子阴极321均与阳极330电连接,进一步提高了电化学系统1000的使用效果。
根据本申请的实施例,当中空式阴极插槽310是由不导电材料形成时,例如由塑料形成时,参考图12,也可不采用导电材料形成导电支撑架,而是通过设置导线的方式,实现多个子阴极321的串联或者并联。具体的,空气阴极320可以进一步包括多个导线323,多个导线323与多个子阴极321一一对应,并且与阳极330电连接。由此,可以将多个子阴极321直接设置在中空式阴极插槽的侧壁311上,然后通过多个导线使各个子阴极均与阳极330电连接,简化了制备工艺,并且进一步提高了电化学系统1000的使用效果。
需要说明的是,根据本申请实施例的电化学系统,其具体类型不受特别限制,只要其阴极发生氧还原反应即可。例如可以为燃料电池、微生物燃料电池、微生物电解池或者微生物脱盐电池等,并且根据本申请实施例的电化学系统,其应用场景非常广泛,例如可以用于处理生活污水、工业污水等,并且其将污水中的有机物通过微生物转化为电能,在消除污染的同时,产生可利用的能量,能耗低且效率高。
下面将结合实施例对本申请的方案进行解释。本领域技术人员将会理解,下面的实施例仅用于说明本申请,而不应视为限定本申请的范围。实施例中未注明具体技术或条件的,按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注 明生产厂商者,均为可以通过市面购获得的常规产品。
实施例1:制备原子级分散Co催化剂
(1)配置反应溶液A:0.01M CoCl 2溶液,溶剂为体积比为1:9的水/乙醇混和溶剂;配制还原剂溶液B:含0.05M KOH的5.0M N 2H 5OH水合肼溶液;配制载体分散液C:2.5mg mL -1的氮掺杂介孔碳分散液。
(2)将上述反应溶液A和载体分散液C置于低温箱中,降温至零下60℃并保温30分钟;用注射泵控制滴加速度,将5mL上述CoCl 2反应溶液A以0.125mL min -1的速率滴加至20mL的还原性溶液B中;上述混和液体在零下60℃条件下继续反应2h,之后混入20mL上述载体分散液C,继续搅拌3-5小时。
(3)利用低温真空抽滤将步骤(2)中制得的介孔碳负载的钴单原子样品进行回收并清洗,之后在室温自然干燥。
(4)将步骤(3)中制备的样品进行热活化,条件为:90min升温至900℃,保温60min,自然冷却至室温,气体条件为500sccm高纯氩气,即可获得热稳定的原子级分散Co催化剂。
实施例2:制备含原子级分散Co催化剂的阴极
(1)制备扩散层:将212mg的碳黑粉末与705.5mg聚四氟乙烯粘结剂(质量分数为60%)混合,加入1.4mL无水乙醇,水浴超声20秒,均匀搅拌至具有粘性的泥状物。将泥状物放置在塑料平板上用滚轮反复滚压2次,使得扩散层料混合更均匀,然后将其滚压至支撑材料不锈钢网上,用粉末压片机在4.5MPa下压制10min,然后放入340℃马弗炉里烧制20min,取出后冷却至室温。
(2)制备催化剂层以及阴极:称量60mg实施例1中制备的原子级分散Co催化剂,加入70μL聚四氟乙烯粘结剂(质量分数为60%)、388μL去离子水,在超声下搅拌混合20s,然后均匀涂抹在扩散层的不锈钢网上,在其上侧覆盖一片不锈钢网(即集电层),一起在10MPa下压制10min,然后放入80℃烘箱里干燥30min,取出后冷却至室温,剪成直径为3cm的圆形,即制得了含原子级分散Co催化剂的阴极。
实施例3:制作含原子级分散Co催化剂的电化学系统
反应器采用双室型构型,阳极室长4cm,上方中间部位有一个直径为1cm的孔,用于放置铂电极作为阳极;阴极室长2cm,中间有一个直径为1cm的孔,用于放置参比电极,两个腔室采用阳离子交换膜分隔。装上钛片及实施例2中制备的含原子级分散Co催化剂的阴极,然后用阴极挡板固定后,在反应器四角用螺杆和螺丝拧紧固定,则反应器(即电化学系统)组装完成。电解液采用50mM磷酸盐缓冲液。
对比例1:制作含Co纳米颗粒催化剂的电化学系统
其他制作方式参考实施例3,不同之处在于该对比例中的阴极中,催化剂为Co纳米颗 粒。
对比例2:制作含铂碳催化剂的电化学系统
其他制作方式参考实施例3,不同之处在于该对比例中的阴极中,催化剂为铂碳催化剂。
对比例3:制作含活性炭催化剂的电化学系统
其他制作方式参考实施例3,不同之处在于该对比例中的阴极中,催化剂为活性炭催化剂。
产电性能测试
采用计时电流伏安法对空气阴极性能进行评价
采用计时电流伏安法测定实施例3以及对比例1-3中制作的电化学系统的阴极还原电流。电化学系统开路3小时后,从起始电势0.2V(参比电极为Ag/AgCl)开始测量,每隔0.1V测定一组,终点电势为–0.4V(参比电极为Ag/AgCl),取每一组电势下稳定的电流值,以有效阴极面积7cm 2折算为电流密度(电流密度i=U/(RA),U为输出电压,R为外阻值,A为阴极面积)。参考图13,在0.2V到–0.4V电势下,含原子级分散Co催化剂的阴极的还原电流高于含Co纳米颗粒、铂碳以及活性炭的阴极。以–0.4V为例,含原子级分散Co催化剂的空气阴极获得了最高的电流密度26A/m 2,而铂碳空气阴极的电流密度仅为16A/m 2,明显地,根据本申请实施例的含原子级分散Co催化剂的阴极具有比目前广泛应用的传统电极更加优越的电学性能。
实施例4:制作含原子级分散Co催化剂的微生物燃料电池
采用碳刷作为阳极,附着厌氧产电菌,阳极材料在马弗炉中450℃煅烧30min进行预处理。反应器采用单室型构型,厚度为4cm,反应室上方中间部位有两个并排的直径为6mm的孔,一个用于放置阳极碳刷,另一个用于放置参比电极;腔体与阴阳极挡板之间用O形环和垫片密封固定,装上钛片及实施例2中制备的含原子级分散Co催化剂的空气阴极,然后用阴极挡板固定后,在反应器四角用螺杆和螺丝拧紧固定,则反应器(即微生物燃料电池)组装完成。接种源采用已经正常运行的微生物燃料电池阳极出水,基质为50mM磷酸盐缓冲液配制浓度为1g/L乙酸钠,加入12.5mL/L矿物质和5mL/L维他命。
对比例4:制作含Co纳米颗粒催化剂的微生物燃料电池
其制作方式参考实施例4,不同之处在于该对比例中的空气阴极中,催化剂为Co纳米颗粒。
对比例5:制作含铂碳催化剂的微生物燃料电池
其制作方式参考实施例5,不同之处在于该对比例中的空气阴极中,催化剂为铂碳催化剂。
对比例6:制作含活性炭催化剂的微生物燃料电池
其制作方式参考实施例6,不同之处在于该对比例中的空气阴极中,催化剂为活性炭催化剂。
产电性能测试
采用快速外阻改变法测定极化曲线
采用快速改变外阻法来测定实施例4以及对比例4-6中制作的微生物燃料电池的极化曲线。快速改变外阻法是指在微生物燃料电池的一个运行周期中,在短时间内更换外电阻并使微生物燃料电池达到稳定,反应器更换1g/L乙酸钠基质后,在5000Ω外阻下稳定一小时,记录输出电压和阳极电势,然后每隔20min降低外电阻,使外电阻依次为1000Ω、500Ω、300Ω、200Ω、100Ω、50Ω、30Ω、20Ω、10Ω、5Ω、2Ω,并且实时记录该电阻下稳定的输出电压和阳极电势,根据数据可以计算出每个外电阻下的功率密度P=Ui,其中,电流密度i=U/(RA),U为输出电压,R为外阻值,A为阴极面积。以电流密度i为横坐标,面积功率密度P为纵坐标,绘制出面积功率密度曲线,如图14所示出。从图中可以看出,含原子级分散Co催化剂的微生物燃料电池的阴极最大功率密度为2500mW/m 2左右,Co纳米颗粒空气阴极的最大功率密度为2100mW/m 2左右,活性炭空气阴极的最大功率密度为1600mW/m 2左右,铂碳空气阴极的最大功率密度为1500mW/m 2左右,很显然,,含原子级分散Co催化剂的微生物燃料电池的最大功率密度高于含Co纳米颗粒、铂碳以及活性炭的微生物燃料电池。
综上可知,原子级分散Co催化剂的催化性能良好,催化效率较高,采用原子级分散Co催化剂的电化学系统以及微生物燃料电池均具有较佳的产电性能。
运行稳定性测试
对实施例4以及对比例5制作的微生物燃料电池进行运行稳定性测试。运行稳定性测试即在一定的外电阻条件下,测试电池在运行不同时间时的输出电压U,并根据数据计算出电池运行不同时间时的电流密度值i(i=U/(RA),U为输出电压,R为外阻值,A为阴极面积),例如分别测试电池50Ω的外电阻条件下,在运行50h、100h、150h、200h、250h、300h、350h、400h、450h、500h、550h、600h、650h以及700h时的输出电压。为了进一步证明含原子级分散Co催化剂的微生物燃料电池产电性能的稳定性,含铂碳催化剂的微生物燃料电池在运行200h后,将空气阴极表面的生物膜刮除,之后继续测试其在不同时间时的输出电压,并计算其电流密度值,测试结果如图15所示出。从图中可以看出,含有原子级分散Co催化剂的微生物燃料电池,其产电性能非常稳定,几乎不随电池运行时间的变化而变化,在运行700h后,其电流密度值仍然较为稳定,和起始时相比,几乎没有下降。而含有铂碳催化剂的微生物燃料电池,随电池运行时间的增加,其产电性能降低比较明显,在运行700h后,其产电性能仅为起始时的65%。刮除阴极的生物膜后,含铂碳催化剂的微 生物燃料电池的产电性能有所提高,说明含铂碳催化剂的空气阴极易被污染,阻碍了其与空气接触,阻碍了阴极的氧还原反应,并且降低了阳极对有机物的分解能力,进而造成电池产电性能的降低。而含原子级分散Co催化剂的空气阴极上,微生物不易聚集,抗污染能力强,其产电性能较为稳定,循环性能好。对比可知,原子级分散Co催化剂的催化性能良好,并且稳定性很高,含有原子级分散Co催化剂的微生物燃料电池的产电稳定性较佳。
实施例5:制作含有2个空气阴极的电化学系统
其他制作方法同实施例3,不同之处是该电化学系统的电极采用模块化电极组件,参考图7,中空式阴极插槽310为六面体型,2个空气阴极320放置在中空式阴极插槽310的两个侧壁上,其中,空气阴极320中含有按实施例2的方法制备的含原子级分散Co催化剂的催化剂层,中空式阴极插槽310中间充满空气,然后插入充满基质的反应空间200中;再将每个空气阴极320与附着厌氧产电菌的碳刷阳极330用导线连接,并接上外阻350,即可制得含有2个空气阴极的电化学系统。
实施例6:制作含有3个空气阴极的电化学系统
其他制作方法同实施例5,参考图9,不同之处在于所用中空式阴极插槽310为三棱柱型,3个空气阴极320放置在中空式阴极插槽310的三个侧壁上,其中,空气阴极320中含有按实施例2的方法制备的含原子级分散Co催化剂的催化剂层。
实施例7:制作含有4个空气阴极的电化学系统
其他制作方法同实施例4,参考图8,不同之处在于4个空气阴极320放置在中空式阴极插槽310的四个侧壁上,其中,空气阴极320中含有按实施例2的方法制备的含原子级分散Co催化剂的催化剂层。
以上详细描述了本申请的实施方式,但是,本申请并不限于上述实施方式中的具体细节,在本申请的技术构思范围内,可以对本申请的技术方案进行多种简单变型,这些简单变型均属于本申请的保护范围。
另外需要说明的是,在上述具体实施方式中所描述的各个具体技术特征,在不矛盾的情况下,可以通过任何合适的方式进行组合。
此外,本申请的各种不同的实施方式之间也可以进行任意组合,只要其不违背本申请的思想,其同样应当视为本申请所公开的内容。
在本申请的描述中,需要理解的是,术语“上”、“下”等指示的方位或位置关系为基于附图所示的方位或位置关系,仅是为了便于描述本申请和简化描述,而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作,因此不能理解为对本申请的限制。

Claims (17)

  1. 一种阴极,包括:
    集电层;以及
    催化剂层,所述催化剂层设置在所述集电层上,所述催化剂层包括原子级分散金属催化剂。
  2. 根据权利要求1所述的阴极,进一步包括:
    扩散层,所述扩散层设置在所述集电层远离所述催化剂层的一侧,或者设置在所述催化剂层远离所述集电层的一侧。
  3. 根据权利要求1所述的阴极,所述原子级分散金属催化剂包括载体以及负载在所述载体上的活性金属,所述活性金属包括Fe、Co和Ni的至少之一。
  4. 根据权利要求1所述的阴极,所述原子级分散金属催化剂是在低温环境下制备的。
  5. 一种电池,包括:
    权利要求1-4任一项所述的阴极;以及
    阳极,所述阳极与所述阴极电连接。
  6. 根据权利要求5所述的电池,所述电池在外阻为50欧姆时,功率密度不小于2000mW/m 2
  7. 根据权利要求5所述的电池,所述电池在运行500小时之后的电流密度衰减不超过5%。
  8. 一种电化学系统,包括:
    壳体,所述壳体中限定出反应空间;以及
    模块化电极组件,所述模块化电极组件设置在所述反应空间中,所述模块化电极组件进一步包括:
    中空式阴极插槽,所述中空式阴极插槽包括:多个空气阴极,所述多个空气阴极设置在所述中空式阴极插槽的侧壁上,所述空气阴极包括权利要求1-4任一项所述的催化剂层;以及
    阳极,所述阳极与所述空气阴极电连接。
  9. 根据权利要求8所述的电化学系统,所述中空式阴极插槽包括多个所述侧壁以及底面,多个所述侧壁以及所述底面在所述中空式阴极插槽内部限定出中空空间,所述侧壁靠近所述中空空间的一侧与大气接触。
  10. 根据权利要求8所述的电化学系统,所述阳极设置在所述中空式阴极插槽以及所 述壳体之间。
  11. 根据权利要求8所述的电化学系统,所述模块化电极组件进一步包括:
    阳极插槽,所述阳极设置在所述阳极插槽的侧壁上。
  12. 根据权利要求8所述的电化学系统,所述空气阴极包括多个子阴极。
  13. 根据权利要求12所述的电化学系统,多个所述子阴极并联或串联。
  14. 根据权利要求12所述的电化学系统,所述空气阴极进一步包括导电支撑架,所述多个子阴极直接设置在所述导电支撑架上,所述导电支撑架与所述阳极电连接。
  15. 根据权利要求12所述的电化学系统,所述空气阴极进一步包括多个导线,所述多个导线与所述多个子阴极一一对应连接,并且所述多个导线均与所述阳极电连接。
  16. 根据权利要求8所述的电化学系统,所述阳极为碳刷、碳布、碳纸、碳毡、活性炭、石墨中的至少之一。
  17. 根据权利要求8所述的电化学系统,所述阳极为面状电极,所述电化学系统进一步包括:隔膜,所述隔膜设置在所述空气阴极以及所述阳极之间。
PCT/CN2018/114155 2018-04-17 2018-11-06 单原子空气阴极、电池、电化学系统与生物电化学系统 WO2019200895A1 (zh)

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