CN108630950A - Monatomic air cathode, battery, electro-chemical systems and bioelectrochemical system - Google Patents
Monatomic air cathode, battery, electro-chemical systems and bioelectrochemical system Download PDFInfo
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Classifications
-
- 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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
-
- 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
- H01M4/9041—Metals or alloys
-
- 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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
Abstract
The invention discloses monatomic air cathode, battery, electro-chemical systems and bioelectrochemical systems.Specifically, the present invention relates to a kind of cathodes, including：Current collection layer；And catalyst layer, the catalyst layer are arranged on the current collection layer, the catalyst layer includes atom level dispersed metal catalyst.Thus, using the oxygen reduction reaction in the atom level dispersed metal catalyst cathode, not only have many advantages, such as that catalytic activity is good, rate of metal is high, of low cost, and when the cathode is used for electro-chemical systems, electronics utilization rate can be improved, and then improves the electricity generation performance of electro-chemical systems.
Description
Technical field
The present invention relates to environment, material, energy fields.In particular it relates to monatomic air cathode, battery, electrochemistry system
System and bioelectrochemical system, more particularly, to cathode, battery and electro-chemical systems.
Background technology
Environmental problem is that contemporary society develops two hang-ups faced with energy problem, and the energy is taken into account while purifying sewage
Recycling is the new challenge that sewage disposal technology faces.It is one by the bioelectrochemical system of Typical Representative of microbiological fuel cell
The emerging sewage disposal technology of kind, can convert the chemical energy in pollutant to electric energy, utilization is attached while treated sewage
The electricity-producing microorganism in anode by the oxidation operation in sewage, while cathode receives electronics and completes oxygen reduction reaction.
However, the performance of current cathode, battery, electro-chemical systems is still to be improved.
Invention content
The present invention be based on inventor couple on the fact that and problem discovery and understanding make：
Inventor has found that current electro-chemical systems generally existing electricity generation performance is poor and the higher problem of production cost.
Inventor had found by further investigation and many experiments, this be by electro-chemical systems, the catalyst efficiency of cathode compared with
Caused by poor and cost is higher.Especially in bioelectrochemical system, the oxygen reduction reaction of cathode is limitation bioelectrochemistry
One of key factor of electricity generation performance of system, what oxygen reduction reaction was mainly driven by cathod catalyst, and currently used for
The catalyst cost of cathode is higher and catalytic efficiency is poor, for example, traditional cathode uses platinum carbon as catalyst, platinum price is high
Expensive, scarcity of resources, and when longtime running cathode is contaminated, catalytic performance significant degradation.Therefore, if catalysis can be proposed
Efficient, stable in catalytic performance and low-cost cathod catalyst and cathode, and make it in electro-chemical systems and life
Preferable catalytic action is played in object electro-chemical systems, will largely be solved the above problems.
The present invention is directed to solve at least some of the technical problems in related technologies.
In the first aspect of the present invention, the present invention proposes a kind of cathode.According to an embodiment of the invention, the cathode packet
It includes：Current collection layer；And catalyst layer, the catalyst layer are arranged on the current collection layer, the catalyst layer includes atom level
Dispersed metal catalyst.The oxygen reduction reaction in the atom level dispersed metal catalyst cathode is used as a result, is not only had
The advantages that catalytic activity is good, rate of metal is high, of low cost, and when the cathode is used for electro-chemical systems, can improve
Electronics utilization rate, and then improve the electricity generation performance of electro-chemical systems.
According to an embodiment of the invention, the cathode further comprises：Diffusion layer, the diffusion layer are arranged in the current collection
Side of the layer far from the catalyst layer, or be arranged in side of the catalyst layer far from the current collection layer.As a result, when this
When cathode is air cathode, which can contact with air, be conducive to oxygen and diffuse in the air cathode, further carry
The high using effect of the cathode.
According to an embodiment of the invention, the atom level dispersed metal catalyst includes carrier and is supported on the carrier
On active metal, the active metal includes at least one of Fe, Co and Ni.The atom level dispersed metal catalyst as a result,
Type it is more, and the active metal is supported on carrier, the stability of catalyst layer can be improved, further increased
The performance of the cathode.
According to an embodiment of the invention, the atom level dispersed metal catalyst is prepared at low ambient temperatures.As a result,
Can the easily good atom level dispersed metal catalyst of processability, further increase the performance of the cathode.
In another aspect of this invention, the present invention proposes a kind of battery.According to an embodiment of the invention, the battery pack
It includes：Foregoing cathode；And anode, the anode are electrically connected with the cathode.The battery has foregoing as a result,
Whole features and advantage possessed by cathode, and the battery efficiency of fuel cell generation is high, and operation stability is preferable.
According to an embodiment of the invention, for the battery when extrernal resistance is 50 ohm, power density is not less than 2000mW/m2。
The efficiency of fuel cell generation of the battery is higher as a result, further improves the using effect of the battery.
According to an embodiment of the invention, current density decaying of the battery after running 500 hours is no more than 5%.
The operation stability of the battery is preferable as a result, further improves the using effect of the battery.
In still another aspect of the invention, the present invention proposes a kind of electro-chemical systems.According to an embodiment of the invention, the electricity
Chemical system includes：Shell limits reaction compartment in the shell；And modularization electrode assembly, the modularization electrode
Component is arranged in the reaction compartment, and the modularization electrode assembly further comprises：Hollow type cathode slot, it is described hollow
Formula cathode slot includes：Multiple air cathodes, the multiple air cathode are arranged on the side wall of the hollow type cathode slot,
The air cathode includes foregoing catalyst layer；Anode, the anode are electrically connected with the air cathode.As a result, should
Electro-chemical systems not only have the advantages that possessed by foregoing catalyst layer whole features and, i.e. the air cathode is urged
Change that activity is good, rate of metal is high, of low cost etc., also, the electro-chemical systems also pass through setup module polarizing electrode component, it will
Multiple air cathodes and anode organic combination further improve the electricity production of the electro-chemical systems in the same reaction compartment
Performance.
According to an embodiment of the invention, the hollow type cathode slot includes multiple side walls and bottom surface, Duo Gesuo
It states side wall and the bottom surface and limits hollow space inside the hollow type cathode slot, the side wall is close to described hollow
The side in space and atmosphere.Thus, it is possible in the case where multiple air cathodes are incorporated into the same hollow space, protect
It demonstrate,proves each air cathode and is come into full contact with air and reacted, further improve the electricity generation performance of electro-chemical systems.
According to an embodiment of the invention, the anode is arranged between the hollow type cathode slot and the shell.
The using effect of electro-chemical systems is further improved as a result,.
According to an embodiment of the invention, the modularization electrode assembly further comprises：Anode slot, the anode slot
Side wall on be provided with the anode.Anode slot can be dismantled easily as a result, convenient for being replaced to anode, and
And when being provided with multiple anodes in the system, easily multiple anodes can be arranged in the same anode slot, into one
Step improves the using effect of electro-chemical systems.
According to an embodiment of the invention, the air cathode includes multiple sub- cathodes.It is cloudy by the way that multiple sons are arranged as a result,
Pole can easily prepare the larger air cathode of area, and air cathode profile pattern obtained is high, functional,
Further improve the using effect of the electro-chemical systems.
According to an embodiment of the invention, multiple sub- cathodes are in parallel or series.The connection type of multiple sub- cathodes as a result,
It is various, it can be combined as needed, to form air cathode, further improve the using effect of electro-chemical systems.
According to an embodiment of the invention, the air cathode further comprises that conductive supporting frame, the multiple sub- cathode are straight
It connects and is arranged on the conductive supporting frame, the conductive supporting frame is electrically connected with the anode.Thus, it is possible to easily enable multiple
Sub- cathode is electrically connected with anode, further improves the using effect of electro-chemical systems.
According to an embodiment of the invention, the air cathode further comprises multiple conducting wires, the multiple conducting wire with it is described
Multiple sub- cathodes connect one to one, and the multiple conducting wire is electrically connected with the anode.Thus, it is possible to easily enable more
A sub- cathode is electrically connected with anode, further improves the using effect of electro-chemical systems.
According to an embodiment of the invention, the anode be carbon brush, carbon cloth, carbon paper, carbon felt, activated carbon, in graphite at least
One of.When the electro-chemical systems are bioelectrochemical system, the anode can improve the adhesive ability of microorganism, and can be into
One step saves the cost of the electro-chemical systems.
According to an embodiment of the invention, the anode is plane-shape electrode, and the electro-chemical systems further comprise：Diaphragm,
The diaphragm is arranged between the air cathode and the anode.The diaphragm can slow down the dirt of air cathode as a result,
Rate is contaminated, the electricity generation performance of electro-chemical systems is further improved.
Description of the drawings
The above-mentioned and/or additional aspect and advantage of the present invention will become in the description from combination following accompanying drawings to embodiment
Obviously and it is readily appreciated that, wherein：
Fig. 1 shows the structural schematic diagram of cathode according to an embodiment of the invention；
Fig. 2 shows the method flow diagram according to an embodiment of the invention for preparing atom level dispersed metal catalyst；
Fig. 3 shows the structural schematic diagram of cathode in accordance with another embodiment of the present invention；
Fig. 4 shows the structural schematic diagram of the cathode according to another embodiment of the invention；
Fig. 5 shows the structural schematic diagram of the cathode according to another embodiment of the invention；
Fig. 6 shows the structural schematic diagram of battery according to an embodiment of the invention；
Fig. 7 shows the structural schematic diagram of electro-chemical systems according to an embodiment of the invention；
Fig. 8 shows the structural schematic diagram of electro-chemical systems in accordance with another embodiment of the present invention；
Fig. 9 shows the structural schematic diagram of the electro-chemical systems according to another embodiment of the invention；
Figure 10 shows the structural schematic diagram of the electro-chemical systems according to another embodiment of the invention；
Figure 11 shows the structural schematic diagram of air cathode according to an embodiment of the invention；
Figure 12 shows the structural schematic diagram of air cathode in accordance with another embodiment of the present invention；
Figure 13 is shown to be tested according to the electricity generation performance of the electro-chemical systems of particular embodiments of the invention and comparative example
Figure；
Figure 14 shows the electricity production of the bioelectrochemical system according to other specific embodiments of the invention and comparative example
It can test chart；And
Figure 15 is shown to be surveyed according to the operation stability of the electro-chemical systems of particular embodiments of the invention and comparative example
Attempt.
Reference numeral：
10：Catalyst layer；20：Current collection layer；30：Diffusion layer；40：Supporting layer；110：Cathode；100：Shell；200：Reaction
Space；300：Modularization electrode assembly；310：Hollow type cathode slot；311：Side wall；320：Air cathode；321：Sub- cathode；
322：Conductive supporting frame；323：Conducting wire；330：Anode；350：Extrernal resistance；360：Anode slot；1000：Electro-chemical systems.
Specific implementation mode
The embodiment of the present invention is described below in detail, examples of the embodiments are shown in the accompanying drawings, wherein from beginning to end
Same or similar label indicates same or similar element or element with the same or similar functions.Below with reference to attached
The embodiment of figure description is exemplary, and is only used for explaining the present invention, and is not considered as limiting the invention.
In one aspect of the invention, the present invention proposes a kind of cathode.It according to an embodiment of the invention, should with reference to figure 1
Cathode 110 may include：Catalyst layer 10 and current collection layer 20.Wherein, catalyst layer 10 is arranged on current collection layer 20, catalyst layer
10 include atom level dispersed metal catalyst.Oxygen in the atom level dispersed metal catalyst cathode 110 is used as a result, also
Original reaction, not only has many advantages, such as that catalytic activity is good, rate of metal is high, but also when the cathode 110 is used for electro-chemical systems,
Electronics utilization rate can be improved, and then improves the electricity generation performance of electro-chemical systems.
According to an embodiment of the invention, atom level dispersed metal catalyst may include carrier and be supported on carrier
Active metal.According to an embodiment of the invention, the concrete type of carrier is not particularly limited, as long as can make atom level dispersed metal
Catalyst is more uniformly dispersed therein, specifically, carrier can be graphene, mesoporous carbon, carbon nanotube, carbon black or
Person's activated carbon etc..According to an embodiment of the invention, the specific type of active metal is not particularly limited, as long as can catalytic oxidation-reduction
Reaction, specifically, active metal may include at least one of Fe, Co and Ni.Specifically, active metal can be unit
Metal, such as single Co, single Ni, single Fe, or double base metal, such as Fe/Co double base metals, Fe/Ni
Double base metal, Co/Ni double base metals, active metal can also be ternary metal, such as Fe/Co/Ni ternary metals.As a result, should
The type of atom level dispersed metal catalyst is more, derives from a wealth of sources, and improves the hydrogen reduction efficiency of the cathode, reduces life
Produce cost.
According to an embodiment of the invention, the preparation method of atom level dispersed metal catalyst is not particularly limited, as long as energy
Active metal is set to disperse in the form of metal is monoatomic.For example, can by infusion process, etching method, light assist synthetic method,
Metal organic frame assists synthetic method etc. to prepare atom level dispersed metal catalyst, as a result, the atom fraction in catalyst layer 10
Dispersed metallic catalyst can have a variety of preparation methods, therefore it is easier to obtain, and can easily be applied to the moon
In extremely, the efficiency of Cathodic oxygen reduction is improved.
According to a particular embodiment of the invention, atom level dispersed metal catalyst can be prepared at low ambient temperatures.
Thus, it is possible to which the easily good atom level dispersed metal catalyst of processability, further increases the performance of the cathode.
Method according to an embodiment of the invention prepares atom level dispersed metal catalyst using cryogenic fluid synthetic method, may be implemented
On a large scale, the preparation of high metal load capacity reduces being applied to for metallic catalyst to improve the effective rate of utilization of metallic atom
This.Specifically, ultralow temperature liquid phase is utilized to inhibit nucleation so that the concentration of GOLD FROM PLATING SOLUTION category atom less than metallic monomer concentration at
Core limiting threshold value to obtain the solution containing atom level dispersed metal, and obtains atom level by further loading process
Dispersed metal catalyst.Thus, it is possible to synthesize atom level dispersed metal catalyst on a large scale in ultralow temperature solution environmental.
Below according to specific embodiments of the present invention, each step of this method is described in detail：
According to an embodiment of the invention, with reference to figure 2, this method includes：
S100：Metallic compound and the first solvent are mixed to form metal front liquid solution
According to an embodiment of the invention, in this step, metallic compound and the first solvent are mixed to form metal front
Liquid solution.According to an embodiment of the invention, metallic compound can be the soluble chemical combination of at least one of Fe, Co and Ni
Object, the first solvent may include water, ethyl alcohol, ethylene glycol, acetone, chloroform, ether, tetrafluoro hydrogen mutter, dimethylformamide and first
At least one of aldehyde.Thus, it is possible to above-mentioned solute and solvent are mixed to form metal front liquid solution, as in subsequent step
The source of atom level dispersed metal.According to an embodiment of the invention, the concentration of metal front liquid solution can be 0.001-
1.0mol/L, specifically can be 0.005mol/L, 0.008mol/L, 0.01mol/L, 0.02mol/L, 0.05mol/L,
0.08mol/L、1.0mol/L。
According to an embodiment of the invention, by this method prepare atom level dispersed metal may include Fe, Co and Ni extremely
It is one of few.It should be strongly noted that the atom level dispersed metal prepared by this method can be unit metal catalyst, example
Such as, according to a particular embodiment of the invention, this method can be utilized to prepare atom level dispersed metal iron catalyst, or utilizing should
Method prepares atom level dispersed metal Co catalysts, or prepares atom level dispersed metal Raney nickel using this method.According to
The embodiment of the present invention, the atom level dispersed metal prepared by this method can also be double base metallic catalyst, for example, according to this
The specific embodiment of invention can utilize this method to prepare iron/cobalt double base metallic catalyst of atom level dispersion, or utilizing should
Method prepares iron/nickel double base metallic catalyst of atom level dispersion, or double using cobalt/nickel of this method preparation atom level dispersion
First metallic catalyst.According to an embodiment of the invention, the atom level dispersed metal prepared by this method can also be ternary metal
Catalyst, for example, according to a particular embodiment of the invention, this method can be utilized to prepare iron/cobalt/nickel ternary of atom level dispersion
Metallic catalyst.Thus, it is possible to realize the preparation of unit, double base and ternary metallic catalyst using this method.
According to a particular embodiment of the invention, metallic compound can be the soluble compound of Fe, or be Co's
Soluble compound, either for the soluble compound of Ni either for Fe, Co mixing soluble compound or
For Fe, Ni mixing soluble compound, either for Co, Ni mixing soluble compound or be Fe, Co, Ni mix
The soluble compound closed.Thus, it is possible to difference preparation unit, double base and ternary metallic catalyst.
S200：Reducing agent and the second solvent are mixed to form reducing agent solution
According to an embodiment of the invention, in this step, reducing agent and the second solvent are mixed to form reducing agent solution.Root
According to the embodiment of the present invention, reducing agent may include NaBH4、KBH4、N2H4、N2H5OH, formaldehyde, formic acid, ascorbic acid, Na2SO3、
K2SO3And H2C2O4At least one of, the second solvent may include water, ethyl alcohol, ethylene glycol, acetone, chloroform, ether, tetrafluoro hydrogen
It mutters, at least one of dimethylformamide and formaldehyde.Thus, it is possible to which it is molten that above-mentioned solute and solvent are mixed to form reducing agent
Liquid, to make reducing agent solution react with metal front liquid solution in subsequent process, reduction obtains disperseing containing atom level
The solution of metal.According to an embodiment of the invention, the concentration of reducing agent solution can be 0.001-10.0mol/L, specifically may be used
Think 2mol/L, 5mol/L, 7mol/L, 8mol/L.It should be noted that being water when the first solvent and the second solvent difference.
S300：Carrier material and third solvent are mixed to form dispersion liquid
According to an embodiment of the invention, in this step, carrier material and third solvent are mixed to form dispersion liquid.According to
The embodiment of the present invention, carrier material can be the carbon nanomaterial of doping.According to an embodiment of the invention, due to foreign atom
Presence, can carbon nanomaterial surface formed defect, so as to increase suction-operated of the carrier material to metallic atom,
And then load capacity of the carrier material to metallic atom can be improved.According to a particular embodiment of the invention, carrier material can wrap
Include N doping mesoporous carbon (CMK-3), nitrogen-doped graphene and graphite-phase nitrogen carbide (g-C3N4At least one of).Thus, it is possible to
The atom level dispersed metal catalyst of high metal load capacity is obtained using above-mentioned material.
According to an embodiment of the invention, third solvent may include water, ethyl alcohol, ethylene glycol, acetone, chloroform, ether, tetrafluoro
Hydrogen mutters, at least one of dimethylformamide and formaldehyde.Thus, it is possible to which above-mentioned solute and solvent are mixed to form dispersion
Liquid obtains the atom level dispersion gold of carrier material load using the Adsorption of solute metallic atom in dispersion liquid in subsequent step
Metal catalyst.According to an embodiment of the invention, the concentration of dispersion liquid can be 0.1-10g/L, specifically can be 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：Metal front liquid solution is mixed with reducing agent solution, to obtain containing the molten of atom level dispersed metal
Liquid
According to an embodiment of the invention, in this step, metal front liquid solution is mixed with reducing agent solution, so as to
To the solution containing atom level dispersed metal.According to an embodiment of the invention, under -100~0 DEG C of low temperature environment, by metal
Precursor solution is mixed with reducing agent solution.It will be appreciated to those of skill in the art that existing in solution building-up process
The nucleation limiting threshold value of metallic monomer concentration, when being less than this threshold value, the solution containing atom level dispersed metal can be obtained.And
Metallic monomer concentration often is controlled with microfluidic methods in the prior art, is embodied in the mixed on low speed process of reactant：Pass through
Local low concentration is created, increasing specific surface area reduces the transmission of the control quality and heat such as diffusion dimension.However the system of the above method
Standby flow is excessively complicated, and yield is relatively low, the serious extensive preparation for inhibiting atom level dispersed metal catalyst.
According to an embodiment of the invention, it can be obviously improved nucleating potential barrier by reducing temperature, effectively inhibits nucleation, to
The concentration of the metallic atom disperseed in solution is improved, and is effectively adsorbed on different carrier surfaces, realizes ultralow temperature solution environmental
The extensive synthesis of middle atom fraction dispersed metallic catalyst.Inventor has found, when temperature is higher than above-mentioned temperature range, in solution
The concentration of the metallic atom of dispersion is relatively low, and the effective rate of utilization of metallic atom is relatively low.And when temperature is less than above-mentioned temperature range,
Kinetics and thermodynamics can be caused excessively slow, can not effectively be prepared.As a result, within the said temperature range by temperature setting, may be used
To realize the extensive synthesis of atom level dispersed metal catalyst.
According to an embodiment of the invention, in order to make the reaction process of reducing agent solution and metal front liquid solution in above-mentioned temperature
It spends in range and carries out, it, can be first by metal front liquid solution before to metal front liquid solution and reducing agent solution mixing
And reducing agent solution keeps the temperature the regular hour in cryogenic box, for example, heat preservation 30min.Thus, it is possible to further increase solution
The concentration of middle metallic atom further increases the utilization rate of metallic atom.
Hybrid mode about metal front liquid solution and reducing agent solution is not particularly limited, and those skilled in the art can
To be designed as the case may be.For example, according to a particular embodiment of the invention, syringe pump can be utilized to control, by metal
Precursor solution is added drop-wise in the reducing agent solution of stirring, or reducing agent solution is added drop-wise to the metal front liquid solution of stirring
In, to make metal front liquid solution fully be reacted with reducing agent solution, obtain the solution containing atom level dispersed metal.According to
The embodiment of the present invention, atom level dispersed metal may include at least one of Fe, Co and Ni.Thus, it is possible to simply and effectively
Prepare a variety of atom level dispersed metal catalyst containing above-mentioned metal.
According to an embodiment of the invention, metal front liquid solution and the opposite amount of reducing agent solution, can pass through chemistry
Reaction equation determines, in order to make metal front liquid solution fully be reacted with reducing agent solution, can make the amount of reducing agent solution
It is far longer than the amount of metal front liquid solution, to ensure that the metallic atom in metal precursor solution is completely reduced.
According to an embodiment of the invention, metal front liquid solution is added drop-wise in the reducing agent solution of stirring, or will be also
Former agent solution is added drop-wise in the metal front liquid solution of stirring, and wherein drop rate can be 0.5-50mL/h, and stir speed (S.S.) can
Think 0-3000rpm.Thus, it is possible to promote metal front liquid solution fully to be reacted with reducing agent solution, to obtain containing original
The solution of sub- grade dispersed metal.According to specific embodiment of the present invention, drop rate can be 2.5mL/h, 7.5mL/h, 15mL/
h、30mL/h、45mL/h。
S500：Dispersion liquid is added in the solution containing atom level dispersed metal and is stirred, to obtain atom fraction
Dispersed metallic catalyst
According to an embodiment of the invention, in this step, dispersion liquid is added to the solution containing atom level dispersed metal
In and stir, to obtain atom level dispersed metal catalyst.According to an embodiment of the invention, it is inhaled using the solute in dispersion liquid
Metallic atom in the attached dispersed metal solution containing atom level obtains the nanometer carbon material supported atom level dispersed metal of doping and urges
Agent.According to an embodiment of the invention, the carbon nanomaterial of doping has very strong suction-operated to metallic atom, so as to
Carrier material is improved to the load capacity of metallic atom, improves the effective rate of utilization of metallic atom.
According to an embodiment of the invention, dispersion liquid is mixed with the solution containing atom level dispersed metal, be -
It is carried out under 100~0 DEG C of low temperature environment, to ensure the metal in the solution containing atom level dispersed metal with the shape of atom
Formula is adsorbed on carrier material, and then obtains the atom level dispersed metal catalyst of carrier material load.
According to an embodiment of the invention, after dispersion liquid being mixed with the solution containing atom level dispersed metal, to above-mentioned mixed
Close solution to be stirred, promote absorption of the carrier material to atom level dispersed metal, then to above-mentioned solution carry out centrifugation or
Vacuum filtration processing, and be dried at room temperature, to obtain the atom level dispersed metal catalyst of high metal load capacity.Root
According to the embodiment of the present invention, the rate of stirring can be 0-3000rpm, and the time of stirring can be 0-300min.
According to an embodiment of the invention, in order to increase the thermal stability of atom level dispersed metal catalyst, this method may be used also
To include：The atom level dispersed metal catalyst prepared by above-mentioned steps is placed in gaseous environment and is carried out at annealing
Reason.According to an embodiment of the invention, gaseous environment can be high vacuum, nitrogen, argon gas or hydrogen-argon-mixed, and the amount of gas can be with
Temperature for 50-600sccm, annealing can be 200-1200 DEG C.Thus, it is possible to obtain heat-staple atom level dispersion gold
Metal catalyst.Specific steps about annealing are not particularly limited, those skilled in the art can as the case may be into
Row design.
In summary, the atom level metallic catalyst according to the ... of the embodiment of the present invention prepared using low temperature solution polycondensation, is had
The advantages that big density, high yield, high efficiency, strong applicability, and atom level metallic catalyst large-scale commercial can be significantly reduced
Therefore the cost of application applies it in cathode according to the ... of the embodiment of the present invention, not only have that catalytic activity is good, metal is sharp
The advantages that high with rate, and production cost can be reduced.
According to an embodiment of the invention, the concrete type of cathode 110 is not particularly limited, as long as oxygen can occur on cathode
Reduction reaction.According to some embodiments of the present invention, catalyst layer 10 is arranged on current collection layer 20 and forms cathode 110
Afterwards, cathode 110 can be directly immersed in electrolyte, and by aeration, oxygen can be made to reach cathode, and occur on cathode
Oxygen reduction reaction.Other embodiments according to the present invention, with reference to figure 3 and Fig. 4, cathode 110 or air cathode are cloudy
Pole 110 may further include diffusion layer 30, and diffusion layer 30 can be in contact (not shown) with air, to utilize air
In oxygen reduction reaction occurs, and then realize the use function of the cathode 110.According to some embodiments of the present invention, it refers to
Fig. 3, diffusion layer 30 can be arranged in side of the current collection layer 20 far from catalyst layer 10, and (not show in figure with electrolyte contacts
Go out).Diffusion layer 30 is contacted with air as a result, so that oxygen can diffuse in the cathode 110, while current collection layer 20 is for richness
Colleeting comb, and the electric conductivity of cathode 110 is improved, catalyst layer 10 utilizes electronics under atom level dispersed metal catalyst action
Reduction reaction occurs with oxygen, and then the using effect of the cathode 110 can be improved.
Other embodiments according to the present invention, with reference to figure 4, which can also have following structure：Diffusion layer 30
Be in contact (not shown) with air, and catalyst layer 10 is formed in side of the diffusion layer 30 far from air, the formation of current collection layer 20
In side of the catalyst layer 10 far from diffusion layer 30, and with electrolyte contacts (not shown).And then cathode 110 can be improved
Using effect.
In order to further increase the using effect of cathode 110, according to an embodiment of the invention, with reference to figure 5, cathode 110 is also
Can further have supporting layer 40, supporting layer 40 can be formed between catalyst layer 10 and diffusion layer 30, and supporting layer
40 can be formed by stainless (steel) wire.Thus, it is possible to more good support construction is provided for cathode 110 by supporting layer 40, and
And supporting layer 40 is located at the both sides of catalyst layer 10 with current collection layer 20, and then can be that catalyst layer 10 provides good guarantor
Shield prevents 10 dusting of catalyst layer in actual use from losing and being adversely affected to the using effect of the cathode 110.
In addition, the supporting layer 40 being made of stainless (steel) wire can also further increase the electric conductivity of the cathode 110, and then can be further
Improve the performance of the cathode 110.
Inventor has found that atom level dispersed metal catalyst has the active site of high degree of dispersion, therefore it is catalyzed
Active good, high catalytic efficiency, and rate of metal is high, and cost is relatively low.Inventor is sent out by further investigation and many experiments
It is existing, atom level dispersed metal catalyst can be applied in cathode, and be applied to electro-chemical systems and bioelectrochemistry
In system, so as to improve the oxygen reduction reaction efficiency of cathode, the electronics utilization rate in electro-chemical systems is improved, and then promoted
The electricity generation performance of electro-chemical systems.Also, inventor has found, particularly advantageous according to the cathode construction of the specific embodiment of the invention
In the attachment of above-mentioned atom level dispersed metal catalyst.Under above-mentioned electrode structure, easy atom level can not only be disperseed
Metallic catalyst is fixed in catalyst layer, and the catalyst layer after fixing also has preferable stability.Also, atom fraction
Dispersed metallic catalyst is used in cathode, also has preferable catalytic action using the reduction reaction that air carries out for cathode.
According to an embodiment of the invention, cathode 110 can be prepared by following methods：
(1) 150-300mg carbon black powders are mixed into 650-750mg polytetrafluoroethylene (PTFE) binders, by repeatedly rolling, with branch
Timbering material stainless (steel) wire is tabletted at 4.5-10MPa, using 340 DEG C of high-temperature stable 10-40min, you can spread
Layer 30；
(2) 60-300mg atom level dispersed metal catalyst is mixed with 24-350 μ L polytetrafluoroethylene (PTFE) binders, then
Uniformly it is applied to the stainless (steel) wire side of the diffusion layer 30 of step (1) preparation, you can form catalyst layer 10；
(3) structure prepared in the current collection layer 20 and step (2) that form stainless (steel) wire is pushed in 4.5-10MPa together
System, and 20-60min moldings are heated at 60-100 DEG C, you can obtain air cathode 320.
In summary, not only catalytic activity is good, rate of metal is high, of low cost for the cathode, and preparation process is easy
It is easy, it is suitble to large area production.
In another aspect of this invention, the present invention proposes a kind of battery.It according to an embodiment of the invention, should with reference to figure 6
Battery may include：Foregoing cathode 110 and anode 330, anode 330 are electrically connected with cathode 110.The battery as a result,
Have the advantages that possessed by foregoing cathode whole features and, since the catalyst in foregoing cathode is atom
Grade dispersed metal catalyst, catalytic activity is high and stability is good, therefore the efficiency of fuel cell generation of the battery is also higher, and runs
Stability is preferable.
According to an embodiment of the invention, for the battery when extrernal resistance is 50 ohm, power density can reach 2000mW/m2.By
This, the efficiency of fuel cell generation of the battery is higher, further improves the using effect of the battery.Specifically, the extrernal resistance of the battery is 50
When ohm, power density can reach 2540mW/m2, further improve the using effect of the battery.
According to an embodiment of the invention, current density decaying of the battery after running 500 hours is no more than 5%.By
This, the operation stability of the battery is preferable, further improves the using effect of the battery.Specifically, the battery is in operation 700
After hour, the decaying of current density can not also be more than 5%, further illustrate that the operation stability of the battery is preferable, into one
Step improves the using effect of the battery.
According to an embodiment of the invention, which can be fuel cell, or microbiological fuel cell, as long as its
Oxygen reduction reaction occurs for cathode.When the battery is microbiological fuel cell, electricity-producing microorganism is attached to anode surface, by
This, can be decomposed the oxidation operation in medium by electricity-producing microorganism, and generate electronics and proton, and connect by cathode
By electronics, by atom level dispersed metal catalyst oxygen reduction reaction and water is generated.According to an embodiment of the invention, anode
Can be what at least one of carbon brush, carbon cloth, carbon cloth and granular activated carbon were formed.Specifically, anode can be by carbon
Cloth or carbon brush are cut into appropriately sized, and are heat-treated under 450 degrees Celsius 30 minutes and obtain in Muffle furnace.Thus, it is possible to simple
Just anode is obtained, and then reduces the production cost of the microbiological fuel cell.
In addition, it will be appreciated by those skilled in the art that without creative efforts, to according to of the invention real
The improvement for applying the microbiological fuel cell progress of example also belongs to protection scope of the present invention.For example, a reality according to the present invention
Example is applied, in microbiological fuel cell, anode and air cathode orthogonal can be arranged；Another reality according to the present invention
Example is applied, between cathode and anode, can also further have diaphragm.Those skilled in the art can be according to reality as a result,
Situation makes corresponding adjustment to microbiological fuel cell according to the ... of the embodiment of the present invention, more suitable structure is selected to form
Microbiological fuel cell, as long as meeting previously described feature according to the ... of the embodiment of the present invention.
In still another aspect of the invention, the present invention proposes a kind of electro-chemical systems.According to an embodiment of the invention, it refers to
Fig. 7, the electro-chemical systems 1000 may include：Shell 100 and modularization electrode assembly 300 limit reaction in shell 100
Space 200, modularization electrode assembly 300 are arranged in reaction compartment 200.According to an embodiment of the invention, modularization electrode group
Part 300 may include：Hollow type cathode slot 310 and anode 330.Wherein, hollow type cathode slot 310 may include：It is more
A air cathode 320, multiple air cathodes 320 can be arranged on the side wall 311 of hollow type cathode slot 310, and multiple
Air cathode 320 may include foregoing catalyst layer；Anode 330 is electrically connected with air cathode 320.The electrification as a result,
System 1000 not only have the advantages that possessed by foregoing catalyst layer whole features and, i.e. the air cathode 320
Catalytic activity it is good, rate of metal is high, of low cost etc., also, the electro-chemical systems 1000 also pass through setup moduleization electricity
Pole component 300 is further carried by multiple air cathodes 320 and 330 organic combination of anode in the same reaction compartment 200
The high electricity generation performance of the electro-chemical systems 1000.
According to an embodiment of the invention, hollow type cathode slot 310 may include multiple side walls 311 and bottom surface (in figure
It is not shown), multiple side walls 311 and bottom surface limit hollow space inside hollow type cathode slot 310, and side wall 311 is close
The side of hollow space and atmosphere.Thus, it is possible in the feelings that multiple air cathodes 320 are incorporated into the same hollow space
Under condition, ensures that each air cathode 320 comes into full contact with air and react, further improve the electricity production of electro-chemical systems 1000
Energy.
Inventor has found that current electro-chemical systems are being transported generally containing only there are one air cathode and an anode
During row, whole efficiency of fuel cell generation is limited.Also, air cathode contacts air due to needing, and is generally located on electrochemistry system
On the top surface or side of system.And electro-chemical systems according to the ... of the embodiment of the present invention, on the one hand, air cathode uses atom fraction
Dispersed metallic catalyst carrys out catalytic oxidation-reduction reaction, and catalysis reaction efficiency is high, and stability is good, improves the electricity in electro-chemical systems
Sub- utilization rate and electricity generation performance；On the other hand, by the way that hollow type cathode slot is arranged, multiple air cathodes can be arranged
On the side wall of the hollow type cathode slot, i.e., multiple air cathodes is incorporated into the same electro-chemical systems, is not only saved
Space, and can ensure that each air cathode can come into full contact with air, and the oxygen reduction reaction of each air cathode
It is independent of each other.Electronics utilization rate and the electricity generation performance in electro-chemical systems are further improved as a result,.Also, hollow type is cloudy
Pole slot can be dismantled easily, and convenient for being replaced to electrode, or according to the water situation of actual treatment, adjustment is whole
The power (can be realized by increasing and decreasing number of electrodes) of a system, which thereby enhances flexibility and the practicability of the electro-chemical systems.
According to an embodiment of the invention, the specific number of multiple air cathodes 320 is not particularly limited, people in the art
Member can be configured according to actual needs.For example, 2-10 air cathode 320 can be arranged, can be arranged 2,3 or
4 air cathodes 320.According to an embodiment of the invention, the specific number of anode 330 is also not particularly limited, for example, can set
1-10 anode 330 is set, 1,2,3 or 4 anode 330 can be set.According to an embodiment of the invention, air cathode
320 are not particularly limited with the connection type of anode 330, as long as each air cathode 320 has anode 330 connected to it i.e.
It can.Specifically, air cathode 320 can be to connect one to one with anode 330, it can also multiple air cathodes 320 and 1 sun
Pole 330 connect, can also 1 air cathode 320 connect with multiple anodes 330.According to an embodiment of the invention, hollow type cathode
The shape of slot 310 is not particularly limited, those skilled in the art can according to the number of the air cathode 320 wanted to set up come
Reasonably designed.Specifically, hollow type cathode slot 310 can be triangular prism-shaped, hexahedron type or octahedral build.Example
Such as, according to some embodiments of the present invention, with reference to figure 7, hollow type cathode slot 310 can be hexahedron type, in hollow type the moon
2 air cathodes, 320,2 air cathodes 320 can be arranged on the side wall 311 of pole slot to be oppositely arranged, can also be adjacent
Setting.Other embodiments according to the present invention can also be at 4 of the hexahedron hollow type cathode slot 310 with reference to figure 8
4 air cathodes 320 are set on side wall 311.Other embodiment according to the present invention, with reference to figure 9, hollow type cathode slot
310 can be triangular prism-shaped, and 3 side walls in the triangular prism hollow type cathode slot 310 can be arranged in 3 air cathodes 320
On.
According to an embodiment of the invention, the material of anode 330 is not particularly limited, when the electro-chemical systems are bioelectrochemical
When system, as long as anode 330 is conducive to microorganism attachment.Specifically, anode 330 can be carbon brush, carbon cloth, carbon paper,
At least one of carbon felt, activated carbon and graphite.Specifically, may include a carbon brush in anode 330, can also be arranged more
Group carbon brush.Similarly, can be monolayer carbon cloth when anode is carbon cloth, or being spaced apart with diaphragm, with multilayer carbon
The combination of cloth.Thus, it is possible to further increase microorganism in the adhesive ability of anode, and the electro-chemical systems can be saved
Cost.
According to an embodiment of the invention, the concrete shape of anode 330 is not particularly limited, and when anode 330 is planar
When electrode, such as carbon paper or carbon cloth, electro-chemical systems 1000, which may further include, to be arranged in air cathode 320 and anode
Diaphragm (not shown) between 330.According to an embodiment of the invention, the specific material of diaphragm is not particularly limited, such as
Can be glass fibre, plastic wire, nylon cloth etc..The diaphragm can prevent from contacting hair between air cathode and anode as a result,
The vertical range between cathode and anode is further shortened in raw short circuit, improves electrode reaction efficiency, between intensifier electrode from
Son diffusion, while slowing down cathode pollutes rate.According to an embodiment of the invention, those skilled in the art can be according to practical feelings
Condition makes corresponding adjustment to electro-chemical systems according to the ... of the embodiment of the present invention, more suitable structure is selected to form electrochemistry
System, as long as meeting previously described feature according to the ... of the embodiment of the present invention.
According to an embodiment of the invention, the set-up mode of anode 330 and position are not particularly limited, for example, with reference to figure 7,
Anode 330 can be arranged between hollow type cathode slot 310 and shell 100.Electro-chemical systems are further improved as a result,
Using effect.According to an embodiment of the invention, with reference to figure 10, modularization electrode assembly 300 may further include anode and insert
Slot 360, anode 330 can also be arranged on the side wall of anode slot 360.According to an embodiment of the invention, anode slot 360 can
It is arranged with Wrap round hollow type cathode slot 310, anode slot 360 can be dismantled easily as a result, convenient for being carried out to electrode
It replaces.It, can be easily by multiple anodes by the way that anode slot 360 is arranged also, when system includes multiple anodes 330
330 are incorporated into the same electro-chemical systems, not only save space, are independent of each other between each anode, can also be according to reality
The water situation of processing adjusts the power (can be realized by increasing and decreasing number of electrodes) of whole system.Electricity is further improved as a result,
The using effect of chemical system 1000.
According to an embodiment of the invention, electro-chemical systems 1000 may further include multiple extrernal resistances 350, and extrernal resistance 350 is set
It sets between air cathode 320 and anode 330, and is electrically connected with air cathode 320 and anode 330.According to the present invention
Embodiment, total resistance value of multiple extrernal resistances 350 when electro-chemical systems 1000 are run is not particularly limited, for example, can be 0 Europe
Nurse, i.e. short circuit operation, or infinitely great, i.e. open running, or 2-1000 ohm.It further improves as a result,
The using effect of electro-chemical systems.
According to an embodiment of the invention, with reference to figure 11 and Figure 12, air cathode 320 may include multiple sub- cathodes 321.
As a result, by the way that multiple sub- cathodes 321 are arranged, the larger air cathode 320 of area, and air obtained can be easily prepared
320 profile pattern of cathode is high, functional, further improves the using effect of the electro-chemical systems.It is according to the present invention
The connection type of embodiment, multiple sub- cathodes 321 is not particularly limited, and multiple sub- cathodes 321 can connect can also be in parallel.By
This, the connection type of multiple sub- cathodes is various, can be combined as needed, to form air cathode 320, further carries
The high using effect of electro-chemical systems.
It should be noted that in practical application in industry, when making the larger air cathode of a bulk area, it is more difficult to ensure
The planarization and performance on its surface, therefore, air cathode 320 according to the ... of the embodiment of the present invention, by the way that multiple faces are arranged
The smaller sub- cathode 321 of product, and by its serial or parallel connection, can easily prepare large area and air of good performance is cloudy
Pole 320 is more conducive to the industrial applications of the electro-chemical systems 1000.According to a particular embodiment of the invention, for example, each
Air cathode may include the sub- cathode of multiple area equations of array arrangement.The area of every sub- cathode all more closes as a result,
Reason, can the simple, fast quality prepared and ensure catalyst layer.Multiple sub- cathodes are connected by simple serial or parallel connection
It connects, you can constitute whole air cathode, and every sub- cathode can have the moon for including diffusion layer as described previously
The structure of pole.Detailed description has been carried out before the concrete structure of cathode, details are not described herein.
According to an embodiment of the invention, when hollow type cathode slot 310 is formed by conductive material, multiple sub- cathodes
321 can be arranged directly on the side wall of hollow type cathode slot 310；According to an embodiment of the invention, when hollow type cathode is inserted
Slot 310 is when being formed by electrically non-conductive material, such as when being formed by plastics, and according to an embodiment of the invention, with reference to figure 11, air is cloudy
Pole 320 may further include conductive supporting frame 322, and multiple sub- cathodes 321 can be arranged on conductive supporting frame 322, conductive
Supporting rack 322 is electrically connected with anode 330.According to an embodiment of the invention, the material of conductive supporting frame 322 is not particularly limited,
As long as sub- cathode 321 can be made to be fixed and electrically conductive on its surface.For example, conductive supporting frame 322 can be stainless steel
Net.Thus, it is possible to which multiple sub- cathodes 321 is easily enabled to be electrically connected with anode 330, electro-chemical systems 1000 are further improved
Using effect.
According to an embodiment of the invention, when hollow type cathode slot 310 is formed by electrically non-conductive material, such as by plastics
When formation, according to an embodiment of the invention, with reference to figure 12, it can not also use conductive material to form conductive supporting frame, but pass through
The mode of conducting wire is set, realizes the in series or in parallel of multiple sub- cathodes 321：Air cathode 320 can also further comprise more
A conducting wire 323, multiple conducting wires 323 are corresponded with multiple sub- cathodes 321, and are electrically connected with anode 330.Thus, it is possible to will
Multiple sub- cathodes 321 are set up directly on the side wall 311 of hollow type cathode slot, then make each sub- cathode by multiple conducting wires
It is electrically connected with anode 330, simplifies preparation process, and further improve the using effect of electro-chemical systems 1000.
It should be noted that electro-chemical systems according to the ... of the embodiment of the present invention, concrete type are not particularly limited, as long as
Oxygen reduction reaction occurs for its cathode.Such as can be fuel cell, microbiological fuel cell, microorganism electrolysis cell or micro-
Biological desalination cell etc., and electro-chemical systems according to the ... of the embodiment of the present invention, application scenarios are very extensive, such as can use
In processing sanitary sewage, trade effluent etc., and the organic matter in sewage is electric energy by microorganism conversion by it, dirty eliminating
While dye, available energy is generated, low energy consumption and efficient.
The solution of the present invention is explained below in conjunction with embodiment.It will be understood to those of skill in the art that following
Embodiment is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.Particular technique or item are not specified in embodiment
Part, it is carried out according to technology or condition described in document in the art or according to product description.Agents useful for same or instrument
Production firm person is not specified in device, is that can purchase the conventional products obtained by market.
Embodiment 1：It prepares atom level and disperses Co catalyst
(1) configuration reaction solution A：0.01M CoCl2Solution, solvent are that volume ratio is 1:9 water/ethyl alcohol mixes solvent；
Prepare reducing agent solution B：The 5.0M N of the KOH containing 0.05M2H5OH hydrazine hydrate solutions；Formulation vehicle dispersion liquid C：2.5mg mL-1
N doping mesoporous carbon dispersion liquid.
(2) above-mentioned reaction solution A and support dispersion C are placed in cryogenic box, are cooled to subzero 60 DEG C and keep the temperature 30 points
Clock；It is controlled with syringe pump, by the above-mentioned CoCl of 5mL2Reaction solution A is with 0.125mL min-1Rate be added dropwise to the reproducibility of 20mL
In solution B；Above-mentioned mixing liquid the reaction was continued under the conditions of subzero 60 DEG C 2h, is mixed into the above-mentioned support dispersion C of 20mL later, after
Continuous stirring 3-5 hours.
(3) it is filtered using cryogenic vacuum and recycles the monatomic sample of cobalt of mesoporous carbon-loaded obtained in step (2)
And clean, later in natural drying at room temperature.
(4) sample prepared in step (3) is subjected to thermal activation, condition is：90min is warming up to 900 DEG C, keeps the temperature 60min,
Cooled to room temperature, gas condition are 500sccm high-purity argon gas, you can obtain heat-staple atom level dispersion Co catalyst.
Embodiment 2：Prepare the cathode for disperseing Co catalyst containing atom level
(1) diffusion layer is prepared：By the carbon black powders of 212mg and 705.5mg polytetrafluoroethylene (PTFE) binder, (mass fraction is
60%) it mixes, 1.4mL absolute ethyl alcohols is added, water bath sonicator 20 seconds, uniform stirring is to having sticking purees.By purees
It is placed on plastic board and is rolled repeatedly with idler wheel 2 times so that the mixing of diffusion layered material evenly, is then rolled to fid
Expect on stainless (steel) wire, suppress 10min at 4.5MPa with powder compressing machine, be then placed in 340 DEG C of Muffle furnaces and fire 20min,
Postcooling is taken out to room temperature.
(2) catalyst layer and cathode are prepared：The atom level dispersion Co catalyst prepared in 60mg embodiments 1 is weighed, is added
Enter 70 μ L polytetrafluoroethylene (PTFE) binders (mass fraction 60%), 388 μ L deionized waters, in agitated under sonication mixing 20s, then
It is uniformly applied on the stainless (steel) wire of diffusion layer, a piece of stainless (steel) wire (i.e. current collection layer) is covered on its upper side, together at 10MPa
10min is suppressed, dry 30min is then placed in 80 DEG C of baking ovens, postcooling is taken out to room temperature, is cut into the circle of a diameter of 3cm, i.e.,
The cathode for disperseing Co catalyst containing atom level has been made.
Embodiment 3：Make the electro-chemical systems for disperseing Co catalyst containing atom level
Reactor uses double chamber type configuration, the long 4cm in anode chamber, top centre position to be used for there are one the hole of a diameter of 1cm
Platinum electrode is placed as anode；The long 2cm of cathode chamber, it is intermediate there are one the hole of a diameter of 1cm, for placing reference electrode, two
Chamber is separated using cation-exchange membrane.The cathode for disperseing Co catalyst containing atom level prepared in titanium sheet and embodiment 2 is loaded onto,
Then it after being fixed with cathode baffle, is fixed with screw rod and screw tightening in reactor quadrangle, then reactor (i.e. electro-chemical systems)
It is completed.Electrolyte uses 50mM phosphate buffers.
Comparative example 1：Make the electro-chemical systems of the nanoparticle catalyst containing Co
Other production method reference implementation examples 3, the difference is that in cathode in the comparative example, catalyst is Co nanometers
Particle.
Comparative example 2：Make the electro-chemical systems of platiniferous C catalyst
Other production method reference implementation examples 3, the difference is that in cathode in the comparative example, catalyst is urged for platinum carbon
Agent.
Comparative example 3：Make the electro-chemical systems containing activated-carbon catalyst
Other production method reference implementation examples 3, the difference is that in cathode in the comparative example, catalyst is activated carbon
Catalyst.
Electricity generation performance is tested
Air cathode performance is evaluated using chrono-amperometric voltammetry
Using the electro-chemical systems made in chrono-amperometric voltammetric determination embodiment 3 and comparative example 1-3 cathode also
Primary current.Open circuit measures after 3 hours since onset potential 0.2V (reference electrode Ag/AgCl), and one is measured every 0.1V
Group, destination potential are -0.4V (reference electrode Ag/AgCl), the current value stablized under each group of potential are taken, with active cathodic face
Product 7cm2Conversion is current density (current density i=U/ (RA), U are output voltage, and R is outer resistance value, and A is cathode area).Ginseng
Figure 13 is examined, under 0.2V to -0.4V same potentials, the reduction current of the cathode of the dispersion Co catalyst containing atom level is higher than to be received containing Co
The cathode of rice grain, platinum carbon and activated carbon.By taking -0.4V as an example, the air cathode that Co catalyst is disperseed containing atom level obtains
Highest current density 26A/m2, and the current density of platinum carbon air cathode is only 16A/m2, it will be apparent that, implemented according to the present invention
The cathode for disperseing Co catalyst containing atom level of example has electric property more superior than the traditional electrode being widely used at present.
Embodiment 4：Make the microbiological fuel cell for disperseing Co catalyst containing atom level
Using carbon brush as anode, attachment anaerobism produces electricity bacterium, and anode material 450 DEG C of calcining 30min in Muffle furnace are carried out
Pretreatment.Reactor uses single chamber type configuration, thickness 4cm, among top position there are two the hole of a diameter of 6mm side by side,
One is used to place anode carbon brush, another is for placing reference electrode；O-ring and gasket are used between cavity and anode and cathode baffle
Sealing is fixed, and is loaded onto the air cathode for disperseing Co catalyst containing atom level prepared in titanium sheet and embodiment 2, is then kept off with cathode
After plate is fixed, fixed with screw rod and screw tightening in reactor quadrangle, then reactor (i.e. microbiological fuel cell) is completed.
For inoculation source using the anode of microbial fuel cell water outlet of normal operation, matrix is 50mM phosphate buffered saline concentration
For 1g/L sodium acetates, 12.5mL/L minerals and 5mL/L vitamins is added.
Comparative example 4：Make the microbiological fuel cell of the nanoparticle catalyst containing Co
Its production method reference implementation example 4, the difference is that in air cathode in the comparative example, catalyst is received for Co
Rice grain.
Comparative example 5：Make the microbiological fuel cell of platiniferous C catalyst
Its production method reference implementation example 5, the difference is that in air cathode in the comparative example, catalyst is platinum carbon
Catalyst.
Comparative example 6：Make the microbiological fuel cell containing activated-carbon catalyst
Its production method reference implementation example 6, the difference is that in air cathode in the comparative example, catalyst is activity
Pd/carbon catalyst.
Electricity generation performance is tested
Polarization curve is measured using extrernal resistance method is changed
The microbiological fuel cell made in embodiment 4 and comparative example 4-6 is measured using quick change extrernal resistance method
Polarization curve replaces external resistance in the short time that is, in a cycle of operation and reaches stable, and reactor replaces 1g/L sodium acetates
After matrix, stablize under 5000 Ω extrernal resistances one hour, record output voltage and anode potential, then reduces dispatch from foreign news agency every 20min
Resistance, makes external resistance be followed successively by 1000 Ω, 500 Ω, 300 Ω, 200 Ω, 100 Ω, 50 Ω, 30 Ω, 20 Ω, 10 Ω, 5 Ω, 2 Ω,
And the output voltage stablized under the resistance and anode potential are recorded in real time, can be calculated under each external resistance according to data
Power density P=Ui, wherein current density i=U/ (RA), U are output voltage, and R is outer resistance value, and A is cathode area.With electric current
Density i is abscissa, and area power density P is ordinate, draws out area power density curve, as illustrated in FIG. 14.From figure
In as can be seen that containing atom level disperse Co catalyst microbiological fuel cell cathode maximum power density be 2500mW/m2
The maximum power density of left and right, Co nano particle air cathodes is 2100mW/m2Left and right, the maximum power of active carbon air cathode
Density is 1600mW/m2The maximum power density of left and right, platinum carbon air cathode is 1500mW/m2Left and right, it is obvious that, contain atom level
The maximum power density for disperseing the microbiological fuel cell of Co catalyst is micro- higher than nano particle containing Co, platinum carbon and activated carbon
Biological fuel cell.
In summary, the catalytic performance of atom level dispersion Co catalyst is good, and catalytic efficiency is higher, is disperseed using atom level
The electro-chemical systems and microbiological fuel cell of Co catalyst all have preferable electricity generation performance.
Operation stability is tested
The microbiological fuel cell made to embodiment 4 and comparative example 5 carries out operation stability test, i.e., certain
Under the conditions of external resistance, output voltage U of the test battery when running different time, and calculate battery operation difference according to data
Current density value i (i=U/ (RA), U are output voltage, and R is outer resistance value, and A is cathode area) when the time, such as test respectively
Under the conditions of the external resistance of 50 Ω of battery, operation 50h, 100h, 150h, 200h, 250h, 300h, 350h, 400h, 450h,
Output voltage when 500h, 550h, 600h, 650h and 700h, in order to further prove to disperse Co catalyst containing atom level
The stability of electricity generation performance of microbial fuel cell, the microbiological fuel cell of platiniferous C catalyst, will be empty after running 200h
The biomembrane of gas cathode surface strikes off, and continues to test its output voltage in different time later, and calculate its current density
Value, test result are as illustrated in FIG. 15.It can be seen from the figure that disperseing the Microbial fuel electricity of Co catalyst containing atom level
Pond, electricity generation performance is highly stable, changes little with the variation of cell runtime, and after running 700h, electric current is close
Angle value is still relatively stable, is compared when with starting, almost without decline.And containing the microbiological fuel cell of platinum carbon catalyst,
With the increase of cell runtime, electricity generation performance reduction is obvious, and after running 700h, electricity generation performance is only when originating
65%.After striking off the biomembrane of cathode, the electricity generation performance of the microbiological fuel cell of platiniferous C catalyst increases, explanation
The air cathode of platiniferous C catalyst is easily contaminated, hinders it and is contacted with air, hinders the oxygen reduction reaction of cathode, and
Capacity of decomposition of the anode to organic matter is reduced, the reduction of battery electricity generation performance is in turn resulted in.And containing atom level dispersion Co catalysis
On the air cathode of agent, microorganism is not easy to assemble, and contamination resistance is strong, and electricity generation performance is relatively stable, good cycle.Comparison
It is found that the catalytic performance of atom level dispersion Co catalyst is good, and stability is very high, disperses Co catalyst containing atom level
The electricity production stability of microbiological fuel cell is preferable.
Embodiment 5：Make the electro-chemical systems containing 2 air cathodes
Other production methods are a difference in that the electrode of the electro-chemical systems uses modularization electrode assembly with embodiment 3,
With reference to figure 7, hollow type cathode slot 310 is hexahedron type, and 2 air cathodes 320 are placed on the two of hollow type cathode slot 310
On a side wall, wherein disperse urging for Co catalyst containing atom level containing what is prepared as described in Example 2 in air cathode 320
Agent layer, 310 centre of hollow type cathode slot are full of air, are inserted into the reaction compartment 200 full of matrix；It again will be each
The carbon brush anode 330 that air cathode 320 produces electricity bacterium with attachment anaerobism is connect with conducting wire, and connects extrernal resistance 350, you can is made and is contained
The electro-chemical systems of 2 air cathodes.
Embodiment 6：Make the electro-chemical systems containing 3 air cathodes
Other production methods are with embodiment 5, with reference to figure 9, the difference is that hollow type cathode slot 310 used is trigone
Column type, 3 air cathodes 320 are placed on three side walls of hollow type cathode slot 310, wherein are contained in air cathode 320
What is prepared as described in Example 2 disperses the catalyst layer of Co catalyst containing atom level.
Embodiment 7：Make the electro-chemical systems containing 4 air cathodes
Other production methods are with embodiment 4, with reference to figure 8, the difference is that 4 air cathodes 320 are placed on hollow type
On four side walls of cathode slot 310, wherein contain the fraction containing atom prepared as described in Example 2 in air cathode 320
Dissipate the catalyst layer of Co catalyst.
In the description of the present invention, the orientation or positional relationship of the instructions such as term "upper", "lower" is based on ... shown in the drawings
Orientation or positional relationship is merely for convenience of the description present invention rather than requires the present invention must be with specific azimuth configuration and behaviour
Make, therefore is not considered as limiting the invention.
In the description of this specification, the description of reference term " one embodiment ", " another embodiment " etc. means to tie
The embodiment particular features, structures, materials, or characteristics described are closed to be included at least one embodiment of the present invention.At this
In specification, a schematic expression of the above terms does not necessarily refer to the same embodiment or example.Moreover, the tool of description
Body characteristics, structure, material or feature may be combined in any suitable manner in any one or more of the embodiments or examples.This
Outside, without conflicting with each other, those skilled in the art by different embodiments described in this specification or can show
The feature of example and different embodiments or examples is combined.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changes, replacing and modification.
Claims (14)
1. a kind of cathode, which is characterized in that including：
Current collection layer；And
Catalyst layer, the catalyst layer are arranged on the current collection layer, and the catalyst layer includes that atom level dispersed metal is urged
Agent.
2. cathode according to claim 1, which is characterized in that further comprise：
Diffusion layer, the diffusion layer, which is arranged, urges in side of the current collection layer far from the catalyst layer, or setting described
Side of the agent layer far from the current collection layer.
3. cathode according to claim 1, which is characterized in that the atom level dispersed metal catalyst include carrier and
The active metal of load on the carrier, the active metal includes at least one of Fe, Co and Ni.
4. cathode according to claim 1, which is characterized in that the atom level dispersed metal catalyst is in low temperature environment
Lower preparation.
5. a kind of battery, which is characterized in that including：
Claim 1-4 any one of them cathodes；And
Anode, the anode are electrically connected with the cathode.
6. battery according to claim 5, which is characterized in that for the battery when extrernal resistance is 50 ohm, power density is not
Less than 2000mW/m2。
7. battery according to claim 5, which is characterized in that current density of the battery after running 500 hours
Decaying is no more than 5%.
8. a kind of electro-chemical systems, which is characterized in that including：
Shell limits reaction compartment in the shell；And
Modularization electrode assembly, the modularization electrode assembly are arranged in the reaction compartment, the modularization electrode assembly
Further comprise：
Hollow type cathode slot, the hollow type cathode slot include：Multiple air cathodes, the multiple air cathode setting exist
On the side wall of the hollow type cathode slot, the air cathode includes claim 1-4 any one of them catalyst layers；
Anode, the anode are electrically connected with the air cathode.
9. electro-chemical systems according to claim 8, which is characterized in that the hollow type cathode slot includes multiple described
Side wall and bottom surface, multiple side walls and the bottom surface limit hollow space inside the hollow type cathode slot,
The side wall is close to the side of the hollow space and atmosphere.
10. electro-chemical systems according to claim 8, which is characterized in that the anode is arranged in the hollow type cathode
Between slot and the shell.
11. electro-chemical systems according to claim 8, which is characterized in that the modularization electrode assembly further comprises：
Anode slot, the anode are arranged on the side wall of the anode slot.
12. electro-chemical systems according to claim 8, which is characterized in that the air cathode includes multiple sub- cathodes；
Optionally, multiple sub- cathodes are in parallel or series；
Optionally, the air cathode further comprises that conductive supporting frame, the multiple sub- cathode are set up directly on the conduction
On supporting rack, the conductive supporting frame is electrically connected with the anode；
Optionally, the air cathode further comprises that multiple conducting wires, the multiple conducting wire are a pair of with the multiple sub- cathode one
It should connect, and the multiple conducting wire is electrically connected with the anode.
13. electro-chemical systems according to claim 8, which is characterized in that the anode is carbon brush, carbon cloth, carbon paper, carbon
At least one of felt, activated carbon, graphite.
14. electro-chemical systems according to claim 8, which is characterized in that the anode is plane-shape electrode, the electrochemistry
System further comprises：Diaphragm, the diaphragm are arranged between the air cathode and the anode.
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| PCT/CN2018/114155 WO2019200895A1 (en) | 2018-04-17 | 2018-11-06 | Single-atom air cathode, battery, electrochemical system and bioelectrochemical system |
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| WO2021062906A1 (en) * | 2019-09-30 | 2021-04-08 | 华中师范大学 | Electrode used for degrading gas-phase organic pollutant, preparation method therefor, and device for degrading gas-phase organic pollutant |
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