CN104201398A - Preparation and application of cathode catalyst for microbial fuel cell - Google Patents

Preparation and application of cathode catalyst for microbial fuel cell Download PDF

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Publication number
CN104201398A
CN104201398A CN201410418636.8A CN201410418636A CN104201398A CN 104201398 A CN104201398 A CN 104201398A CN 201410418636 A CN201410418636 A CN 201410418636A CN 104201398 A CN104201398 A CN 104201398A
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manganese dioxide
fuel cell
nano material
hours
cathode catalyst
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CN104201398B (en
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袁浩然
邓丽芳
陈勇
袁勇
周顺桂
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Guangzhou Institute of Energy Conversion of CAS
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Guangzhou Institute of Energy Conversion of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • 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 a preparation method of a cathode catalyst for a microbial fuel cell, the technology is simple, the cost is low, the reaction condition is mild, and an obtained product has the advantages of stable quality, good conductivity and higher catalytic electrochemical activity, and can be widely applied to the basic research in lithium ion battery, molecular sieve, microbial fuel cell cathode catalyst, super-capacitor and other related fields.

Description

A kind of preparation of microorganism fuel cell cathode catalyst and application thereof
Technical field:
The present invention relates to a kind of preparation and application thereof of microorganism fuel cell cathode catalyst.
Background technology:
The world today, energy problem is day by day serious, and the greenhouse effect that fossil fuel brings increasingly sharpen, and reproducible bioenergy has caused people's extensive concern day by day.Microbiological fuel cell is a kind ofly to utilize electrogenesis microbe the chemical energy in organic substance directly to be changed into the device of electric energy, it take organic substance as raw material is (as sewage, mud etc.), along with organic degraded, chemical energy in organic substance discharges, the electronics producing is by microorganism-capturing and be delivered to anode, and electronics arrives negative electrode through external circuit, generation current.The advantage of microbiological fuel cell is that raw material sources are extensive, carries out debirs processing in electrogenesis, low-cost and pollution-less, thereby become gradually study hotspot.
At present the principal element of restriction microbiological fuel cell application is its lower output power density, thereby the output power density that how to improve microbiological fuel cell is people's research emphasis.By improving battery structure, improve battery operation condition, change negative electrode and anode electrode material, selecting suitable cathode electronics acceptor, seed selection advantage electrogenesis bacterial strain etc., all can effectively improve the output power density of battery.And using oxygen cheap and easy to get, as electron acceptor, build air cathode microbial fuel cell, and by adding suitable cathod catalyst, improve the rate of reduction of oxygen, can increase substantially battery output power density, improve battery performance.Wherein, metal platinum (Pt) has high electrocatalytic active and chemical stability, is good oxygen reduction reaction (oxygen reduction reaction, ORR) catalyst, but expensive price limit its be widely used; Transition metal macrocyclic complexes, as pyrolysis FePC (pyr-FePc), durol Cobalt Porphyrin (CoTTMP) etc. has good catalytic activity, but its stability is not high, preparation process is complicated, practicality is not strong, and therefore adopting cheap metal oxide to replace precious metal is the important selection of oxidation-reduction electrode.Manganese dioxide has higher ORR catalytic activity and wide material sources, cheap, nontoxic, environmental friendliness, safety, be a kind of cathod catalyst relatively with application potential, be widely used in the fields such as molecular ion sieve, catalyst, electrochemical capacitor and energy reserve and converting system.
The preparation method of manganese dioxide has multiple, as: electrodeposition process, microemulsion method, hydro thermal method, oxidation-reduction method etc.The patent that wherein patent No. is 201310539372.7 discloses a kind of by adjusting the reaction time, prepares the method for different-shape nano manganese dioxide, and it is successfully applied to microbiological fuel cell in the identical situation of other conditions.But this manganese dioxide conductivity is poor, the material that the additional conductive doped performance of needs is good when as cathod catalyst, to improve its electric conductivity, should use more complicated.
Summary of the invention:
The preparation method who the object of this invention is to provide a kind of microorganism fuel cell cathode catalyst, compositing conducting performance and catalytic performance be higher manganese dioxide cathodes catalyst all.
The present invention is achieved by the following technical programs:
A microorganism fuel cell cathode catalyst, this catalyst has three-decker from inside to outside, comprises the nano-manganese dioxide layer of the outer load of carbon coating outside nano material of manganese dioxide layer, nano material of manganese dioxide layer and carbon coating.
The preparation method of described microorganism fuel cell cathode catalyst, comprises the following steps:
A, adopt hydrothermal synthesis method to make nano material of manganese dioxide: potassium permanganate is added in deionized water, the homogeneous solution that the concentration that stirs formation potassium permanganate is 0.3mol/L, then add manganese sulfate to stir and form uniform mixed solution, the mass ratio of described potassium permanganate and manganese sulfate is 5:2, then above-mentioned mixed solution is transferred in the high-temperature high-pressure reaction kettle that inner bag is polytetrafluoroethylene, under the temperature conditions of 140 ℃, react 2～18 hours, then be cooled to room temperature, after filtration, extremely neutral with deionized water rinsing, at 100 ℃ of air dryings, make nano material of manganese dioxide (MnO 2),
B, the nano material of manganese dioxide (MnO that 0.15g step a is obtained 2) be placed in 60～80ml 0.01mol/LH 2sO 4in solution, ultrasound suspending, adds 100 μ L pyrrole monomers and 40～60ml 0.01mol/LH fast 2sO 4the mixture of solution, is placed in ice bath and stirs filtration after 3～5 hours, filters gained solid and replaces cleaning until be dried 12 hours at 60 ℃ after neutrality with deionized water and ethanol, obtains having the nano material of manganese dioxide (MnO of carbon coating 2/ C);
C, the nano material of manganese dioxide with carbon coating of 50mg step b gained is placed in to the mixed liquor described in step a, repeating step a, obtains end product MnO 2/ C/MnO 2.
In step a and step c, the mixed solution reaction time is preferably 12～18 hours.
In step b, the increase of carbon coating realizes by first load pyrrole monomer, and the load of carbon coating need to be carried out in sour environment.
The present invention also protects the application of described catalyst, can be widely used in the association areas such as lithium ion battery, molecular sieve, microbiological fuel cell, super capacitor.
The present invention has the features such as technique is simple, cost is low, reaction condition is gentle, the constant product quality simultaneously obtaining, conduct electricity very well and to have higher catalytic electrochemical active, can be widely used in the fundamental research of lithium ion battery, molecular sieve, microorganism fuel cell cathode catalyst, super capacitor etc. and association area.
Accompanying drawing explanation:
Fig. 1 is three sandwich schematic diagrames of the application's end product;
Fig. 2 is the SEM figure of embodiment 1 gained end product;
Fig. 3 is the SEM figure of embodiment 2 gained end products;
Fig. 4 is the SEM figure of embodiment 3 gained end products;
Fig. 5 is the electrochemical catalysis performance map of embodiment 1～3 gained end product;
Fig. 6 is embodiment 1～3 gained end product electrogenesis design sketch during as microorganism fuel cell cathode catalyst.
Embodiment:
Below to further illustrate of the present invention, rather than limitation of the present invention.
Embodiment 1:
Potassium permanganate is added in deionized water, the homogeneous solution that the concentration that stirs formation potassium permanganate is 0.3mol/L, then add manganese sulfate to stir and form uniform mixed solution, the mass ratio of described potassium permanganate and manganese sulfate is 5:2, then above-mentioned mixed solution is transferred in the high-temperature high-pressure reaction kettle that inner bag is polytetrafluoroethylliner liner, under the temperature conditions of 140 ℃, react 2 hours, then be cooled to room temperature, after filtration, with deionized water rinsing, to neutral, in 100 ℃ of air, dry and obtain manganese dioxide nano flower.Subsequently, the above-mentioned manganese dioxide nano flower of 0.15g is placed in to 60ml 0.01mol/LH 2sO 4in solution, ultrasound suspending, adds 100 μ L pyrrole monomers and 40ml 0.01mol/LH fast 2sO 4the mixture of solution, is placed in ice bath and stirs filtration after 3 hours, and filtration gained solid deionized water and ethanol alternately cleaning to rear 60 ℃ of neutrality are dried to obtain MnO for 12 hours 2/ C.Then by 50mg MnO 2/ C solid is placed in the mixed liquor that potassium permanganate and manganese sulfate mass ratio are 5:2, transfer to subsequently in the high-temperature high-pressure reaction kettle that inner bag is polytetrafluoroethylliner liner, again under the temperature conditions of 140 ℃, react 2 hours, then be cooled to room temperature, filter, with deionized water rinsing, to neutral, finally in 100 ℃ of air, dry to obtain end product MnO 2/ C/MnO 2, its SEM figure as shown in Figure 2.
Embodiment 2
Potassium permanganate is added in deionized water, the homogeneous solution that the concentration that stirs formation potassium permanganate is 0.3mol/L, then add manganese sulfate to stir and form uniform mixed solution, the mass ratio of described potassium permanganate and manganese sulfate is 5:2, then above-mentioned mixed solution is transferred in the high-temperature high-pressure reaction kettle that inner bag is polytetrafluoroethylliner liner, under the temperature conditions of 140 ℃, react 12 hours, then be cooled to room temperature, after filtration, extremely neutral with deionized water rinsing, in 100 ℃ of air, dry and obtain having nanotube and nanometer rods and mix the manganese dioxide of pattern (nanometer rods accounts for 60%, nanotube accounts for 40%).Subsequently, the above-mentioned nano material of manganese dioxide of 0.15g is placed in to 60ml 0.01mol/LH 2sO 4in solution, ultrasound suspending, adds 100 μ L pyrrole monomer and 40ml0.01mol/LH fast 2sO 4the mixture of solution, is placed in ice bath and stirs filtration after 3 hours, and filtration gained solid deionized water and ethanol alternately cleaning to rear 60 ℃ of neutrality are dried to obtain MnO for 12 hours 2/ C.Then by 50mg MnO 2/ C solid is placed in the mixed liquor that potassium permanganate and manganese sulfate mass ratio are 5:2, transfer to subsequently in the high-temperature high-pressure reaction kettle that inner bag is polytetrafluoroethylliner liner, again under the temperature conditions of 140 ℃, react 12 hours, then be cooled to room temperature, filter, with deionized water rinsing, to neutral, finally in 100 ℃ of air, dry to obtain end product MnO 2/ C/MnO 2, its SEM figure is as Fig. 3.
Embodiment 3
Potassium permanganate is added in deionized water, the homogeneous solution that the concentration that stirs formation potassium permanganate is 0.3mol/L, then add manganese sulfate to stir and form uniform mixed solution, the mass ratio of described potassium permanganate and manganese sulfate is 5:2, then above-mentioned mixed solution is transferred in the high-temperature high-pressure reaction kettle that inner bag is polytetrafluoroethylliner liner, under the temperature conditions of 140 ℃, react 18 hours, then be cooled to room temperature, after filtration, with deionized water rinsing, to neutral, in 100 ℃ of air, dry and obtain manganese dioxide nano-rod.Subsequently, the above-mentioned manganese dioxide nano of 0.15g is placed in to 60ml 0.01mol/LH 2sO 4in solution, ultrasound suspending, adds 100 μ L pyrrole monomers and 40ml 0.01mol/LH fast 2sO 4the mixture of solution, is placed in ice bath and stirs filtration after 3 hours, and filtration gained solid deionized water and ethanol alternately cleaning to rear 60 ℃ of neutrality are dried to obtain MnO for 12 hours 2/ C.Then by 50mg MnO 2/ C solid is placed in the mixed liquor that potassium permanganate and manganese sulfate mass ratio are 5:2, transfer to subsequently in the high-temperature high-pressure reaction kettle that inner bag is polytetrafluoroethylliner liner, again under the temperature conditions of 140 ℃, react 18 hours, then be cooled to room temperature, filter, with deionized water rinsing, to neutral, finally in 100 ℃ of air, dry to obtain end product MnO 2/ C/MnO 2, its SEM figure is as Fig. 4.
Embodiment 4
The end product of embodiment 1,2,3 gained (structure is as shown in Figure 1) is respectively used to microorganism fuel cell cathode catalyst, carries out the research of microbiological fuel cell electrogenesis and various electrochemical Characterization,
Result shows, end product performance the best that embodiment 2 is synthetic, and this kind of material has the strongest chemical property (as shown in Figure 5), in-0.25 position, has significant redox peak, and this also illustrates that this material has stronger catalytic action.And when this material is used for microbiological fuel cell electrogenesis, battery has the highest output voltage of 0.52V, compare and using three sandwich materials of embodiment 1 and embodiment 3 as the battery of cathod catalyst, output voltage exceeds respectively 0.15V and 0.07V (as shown in Figure 6).

Claims (3)

1. a microorganism fuel cell cathode catalyst, is characterized in that, this catalyst has three-decker from inside to outside, comprises the nano-manganese dioxide layer of the outer load of carbon coating outside nano material of manganese dioxide layer, nano material of manganese dioxide layer and carbon coating.
2. a preparation method for microorganism fuel cell cathode catalyst, is characterized in that, comprises the following steps:
A, potassium permanganate is added in deionized water, the homogeneous solution that the concentration that stirs formation potassium permanganate is 0.3mol/L, then add manganese sulfate to stir and form uniform mixed solution, the mass ratio of described potassium permanganate and manganese sulfate is 5:2, then above-mentioned mixed solution is transferred in the high-temperature high-pressure reaction kettle that inner bag is polytetrafluoroethylene, under the temperature conditions of 140 ℃, react 2～18 hours, then be cooled to room temperature, after filtration, with deionized water rinsing, to neutral, at 100 ℃ of air dryings, make nano material of manganese dioxide;
B, the nano material of manganese dioxide that 0.15g step a is obtained are placed in 60～80ml 0.01mol/LH 2sO 4in solution, ultrasound suspending, adds 100 μ L pyrrole monomers and 40ml～60ml 0.01mol/LH fast 2sO 4the mixture of solution, is placed in ice bath and stirs filtration after 3～5 hours, filters gained solid and replaces cleaning until be dried 12 hours at 60 ℃ after neutrality with deionized water and ethanol, obtains having the nano material of manganese dioxide of carbon coating;
C, the nano material of manganese dioxide with carbon coating of 50mg step b gained is placed in to the mixed liquor described in step a, repeating step a, obtains end product.
3. the preparation method of microorganism fuel cell cathode catalyst according to claim 2, is characterized in that, in step a and step c, the mixed solution reaction time is 12～18 hours.
CN201410418636.8A 2014-08-22 2014-08-22 The preparation of a kind of microorganism fuel cell cathode catalyst and application thereof Active CN104201398B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106972179A (en) * 2017-04-11 2017-07-21 广州道动新能源有限公司 Composite catalyst and its preparation method and application
CN115072838A (en) * 2022-07-08 2022-09-20 重庆大学 Novel method for generating electricity by treating landfill leachate mixed shale gas flowback wastewater through single-chamber microbial fuel cell

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CN103553137A (en) * 2013-11-04 2014-02-05 中国科学院广州能源研究所 Method for preparing nano manganese dioxides with different appearances by hydrothermal synthesis process
CN103887522A (en) * 2014-04-05 2014-06-25 南开大学 Preparation method of activated carbon air cathode of manganese dioxide modified microbial fuel cell

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* Cited by examiner, † Cited by third party
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CN101928040A (en) * 2010-06-29 2010-12-29 北京科技大学 Preparation method of manganese dioxide of super capacitor electrode material
CN103553137A (en) * 2013-11-04 2014-02-05 中国科学院广州能源研究所 Method for preparing nano manganese dioxides with different appearances by hydrothermal synthesis process
CN103887522A (en) * 2014-04-05 2014-06-25 南开大学 Preparation method of activated carbon air cathode of manganese dioxide modified microbial fuel cell

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Title
QI LI ET AL: ""Design and synthesis of MnO2/Mn/MnO2 sandwich-structured nanotube arrays with high supercapacitive performance for electrochemical energy storage"", 《NANO LETTERS》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106972179A (en) * 2017-04-11 2017-07-21 广州道动新能源有限公司 Composite catalyst and its preparation method and application
CN115072838A (en) * 2022-07-08 2022-09-20 重庆大学 Novel method for generating electricity by treating landfill leachate mixed shale gas flowback wastewater through single-chamber microbial fuel cell

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