CN104600331B - A kind of preparation method of microbiological fuel cell magnetic conductive bioceramic electrode - Google Patents

A kind of preparation method of microbiological fuel cell magnetic conductive bioceramic electrode Download PDF

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CN104600331B
CN104600331B CN201510063054.7A CN201510063054A CN104600331B CN 104600331 B CN104600331 B CN 104600331B CN 201510063054 A CN201510063054 A CN 201510063054A CN 104600331 B CN104600331 B CN 104600331B
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preparation
porous ceramic
coated
ceramic plate
coating
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CN104600331A (en
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成岳
谢文成
范小丰
盛丽平
刘小聪
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Jingdezhen Ceramic Institute
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88Processes of manufacture
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605Porous electrodes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8657Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88Processes of manufacture
    • H01M4/8825Methods for deposition of the catalytic active composition
    • H01M4/8828Coating with slurry or ink
    • H01M4/8839Painting
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Inert Electrodes (AREA)

Abstract

The present invention relates to the preparation method of a kind of microbiological fuel cell magnetic conductive bioceramic electrode, preparation including porous ceramic plate, the preparation of anode electrode, the preparation of cathode electrode, and utilize the advantage of porous ceramics and conduct electricity and the feature of biocompatibility, not only increase the surface area of electrode, and there is biomagnetism, be conducive to bio-film colonization and demoulding, improve biomembrane effect in the electrodes, and it is good to have water resistance, conduct electricity very well, permeability is good, synthesis low cost, the feature that Production Time is short, therefore there is wide market prospect.

Description

A kind of preparation method of microbiological fuel cell magnetic conductive bioceramic electrode
Technical field
The invention belongs to microbiological fuel cell field, be specifically related to a kind of microbiological fuel cell magnetic conductive biology pottery The preparation method of porcelain electrode.
Background technology
Microbiological fuel cell (MFC) is as a kind of novel biomass economy mode, by the catalytic action of microorganism Energy contained by organic acid and glucide is converted into electric energy, with biomass such as biodiesel, bio oxygen, alcohol fuels Land use systems is compared, and has its original advantage and feature, is the Optimum utilization mode of a kind of regenerative resource.
In MFC, the microorganism that anode mainly provides the place grown and acceptance to pass over for microorganism produces Electronics.Research shows that the material of anode is different, can affect the transmission of electronics on microorganism growth on model machine and anode.Negative electrode Being the deciding factor determining MFC electricity generation performance, the making of negative electrode needs catalyst, and therefore the research to it seems particularly Important, the best cathod catalyst of current effect is platinum.
Therefore the design of negative electrode is MFC development and a great challenge of application.The material being generally used as anode all may be used To be used as negative electrode, such as carbon cloth, carbon paper, carbon brush, graphite rod, black lead brush etc..But current electrode material is fragile, the most rotten Erosion, not acid-fast alkali-proof, bio-film colonization difficulty, easily by hole plug, ion-exchanging efficiency can be more and more lower, thus reduces whole The conversion efficiency of battery system.
Summary of the invention
The technical problem to be solved in the present invention is to provide one, and water resistance is good, conduct electricity very well, permeability is good, synthesis The preparation method of the microbiological fuel cell porous magnetic conductive biological ceramic electrode that low cost, Production Time are short.
For solving above technical problem, the technical scheme is that a kind of microbiological fuel cell magnetic conductive is raw The preparation method of thing ceramic electrode, it is characterised in that comprise the following steps:
The first step prepares porous ceramic plate: by weight percentage by clay 30%, quartz sand 30%, flyash 15%, resin 5%, Anhydrite 20% is poured into after in beaker, blended, pelletize, sieve, compressing, be dried, fire acquisition porous ceramic plate;
Second step prepares anode electrode: by graphite and nanometer Fe3O4After mixing, add a certain amount of water glass solution and stir Mix and uniformly prepare mixed coating, with hairbrush, mixed coating is coated in post-drying on the porous ceramic plate that the first step prepares;
3rd step prepares cathode electrode: include being coated with carbon based layer, coating diffusion layer, the preparation of coating catalytic layer, concrete work Skill is as follows:
(1) coating carbon based layer: first being cleaned up by the porous ceramic plate that the first step prepares, dry for standby, then by Quantitative hydrocarbon black powder loads in small beaker, and adds the PTFE solution that mass concentration is 40%, prepares white carbon black after stirring Molten slurry, then with paintbrush brush, molten for white carbon black slurry is uniformly coated on porous ceramic plate, after being coated with, little through natural air drying 2 Time, then porous ceramic plate is heated at a temperature of 370 DEG C 25 min, heat treatment takes out through naturally cooling to room temperature after completing;
(2) coating diffusion layer: be that 60% PTFE solution has been uniformly coated in previous step by paintbrush brush handle mass concentration It is coated with on the porous ceramic plate of carbon based layer side, at air through natural air drying, until PTFE layer becomes white completely, then will Porous ceramic plate heats 25 min at a temperature of 370 DEG C, repeats above step 3 times, makes PTFE layer be coated with 4 layers;
(3) coating catalytic layer: by nanometer Fe3O4Powder and powdered graphite mixing, after stirring with paintbrush brush, add matter Amount concentration is Nafion solution and the high-purity isopropanol of 5%, after stirring, with paintbrush brush coating catalytic layer equably in porous The opposite side of ceramic wafer PTFE layer, has been coated with rear natural air drying at least 24 hours.
The mesh number sieved in the described first step is 40 mesh.
Pressure compressing in the described first step is 20MPa.
The temperature being dried in the described first step is 70 DEG C.
The temperature fired in the described first step is 1250~1280 DEG C.
Graphite and nanometer Fe in described second step3O4Weight ratio be 5:3, the addition of described waterglass is graphite and receiving Rice Fe3O43 times of gross mass, the mass concentration of waterglass is 30%.
Drying temperature in described second step is 70 DEG C.
In (1) of described 3rd step, hydrocarbon black powder is 15% with the mass ratio of PTFE solution.
Nanometer Fe in (3) of described 3rd step3O4The mass ratio of powder and powdered graphite is 3:5.
In (3) of described 3rd step, the volume ratio of Nafion solution and high-purity isopropanol is 8:5.
The present invention utilizes porous ceramics to have the feature of conduction and biocompatibility, not only increases the surface area of electrode, And there is biomagnetism, and beneficially bio-film colonization and demoulding, improve biomembrane effect in the electrodes, and have waterproof Performance is good, conducts electricity very well, and permeability is good, synthesizes low cost, and the feature that Production Time is short, before therefore having wide market Scape.
Accompanying drawing explanation
Fig. 1 multiporous biological conductivity ceramics air cathode electrode schematic diagram.
Detailed description of the invention
Embodiment 1
The preparation method of a kind of microbiological fuel cell magnetic conductive bioceramic electrode, comprises the following steps:
The first step prepares porous ceramic plate: by weight percentage by clay 30%, quartz sand 30%, flyash 15%, resin 5%, Anhydrite 20% is poured into after in beaker, blended, pelletize, cross 40 mesh sieves, 20MPa compressing, 70 DEG C be dried, 1260 DEG C fire Obtain porous ceramic plate;
Second step prepares anode electrode: by 2.5g graphite and 1.5g nanometer Fe3O4After mixing, add the mass concentration of 12g It is the water glass solution of 30% the prepared mixed coating that stirs, with hairbrush, mixed coating is coated in the porous that the first step prepares In 70 DEG C of drying after on ceramic wafer;
3rd step prepares cathode electrode: include being coated with carbon based layer, coating diffusion layer, the preparation of coating catalytic layer, concrete work Skill is as follows:
(1) coating carbon based layer: first cleaned up by the porous ceramic plate that the first step prepares, dry for standby, then will The hydrocarbon black powder of 3.0g loads in small beaker, and adds the PTFE solution that 20g mass concentration is 40%, prepares charcoal after stirring Black molten slurry, then with paintbrush brush, molten for white carbon black slurry is uniformly coated on porous ceramic plate, after being coated with, through natural air drying 2 Hour, then porous ceramic plate is heated at a temperature of 370 DEG C 25 min, heat treatment takes out through naturally cooling to room after completing Temperature;
(2) coating diffusion layer: be that 60% PTFE solution has been uniformly coated in previous step by paintbrush brush handle mass concentration It is coated with on the porous ceramic plate of carbon based layer side, at air through natural air drying, until PTFE layer becomes white completely, then will Porous ceramic plate heats 25 min at a temperature of 370 DEG C, repeats above step 3 times, makes PTFE layer be coated with 4 layers;
(3) coating catalytic layer: by 1.5g nanometer Fe3O4Powder and the mixing of 2.5 g powdered graphites, stir with paintbrush brush After, add Nafion solution and 25ml high-purity isopropanol that 40ml mass concentration is 5%, after stirring, with paintbrush brush equably Coating catalytic layer, in the opposite side of porous ceramic plate PTFE layer, has been coated with rear natural air drying at least 24 hours.
Embodiment 2
The preparation method of a kind of microbiological fuel cell magnetic conductive bioceramic electrode, comprises the following steps:
The first step prepares porous ceramic plate: by weight percentage by clay 30%, quartz sand 30%, flyash 15%, resin 5%, Anhydrite 20% is poured into after in beaker, blended, pelletize, cross 40 mesh sieves, 20MPa compressing, 70 DEG C be dried, 1280 DEG C fire Obtain porous ceramic plate;
Second step prepares anode electrode: by 2.0g graphite and 1.2g nanometer Fe3O4After mixing, add the mass concentration of 9.6g It is the water glass solution of 30% the prepared mixed coating that stirs, with hairbrush, mixed coating is coated in the porous that the first step prepares In 70 DEG C of drying after on ceramic wafer;
3rd step prepares cathode electrode: include being coated with carbon based layer, coating diffusion layer, the preparation of coating catalytic layer, concrete work Skill is as follows:
(1) coating carbon based layer: first cleaned up by the porous ceramic plate that the first step prepares, dry for standby, then will The hydrocarbon black powder of 4.5g loads in small beaker, and adds the PTFE solution that 30 g mass concentrations are 40%, prepares after stirring The molten slurry of white carbon black, then with paintbrush brush, molten for white carbon black slurry is uniformly coated on porous ceramic plate, after being coated with, through natural air drying 2 Individual hour, then porous ceramic plate heating at a temperature of 370 DEG C 25 min, heat treatment takes out through naturally cooling to room after completing Temperature;
(2) coating diffusion layer: be that 60% PTFE solution has been uniformly coated in previous step by paintbrush brush handle mass concentration It is coated with on the porous ceramic plate of carbon based layer side, at air through natural air drying, until PTFE layer becomes white completely, then will Porous ceramic plate heats 25 min at a temperature of 370 DEG C, repeats above step 3 times, makes PTFE layer be coated with 4 layers;
(3) coating catalytic layer: by 1.2g nanometer Fe3O4Powder and the mixing of 2.0g powdered graphite, stir with paintbrush brush After, add Nafion solution and 40ml high-purity isopropanol that 64ml mass concentration is 5%, after stirring, with paintbrush brush equably Coating catalytic layer, in the opposite side of porous ceramic plate PTFE layer, has been coated with rear natural air drying at least 24 hours.

Claims (10)

1. the microbiological fuel cell preparation method of magnetic conductive bioceramic electrode, it is characterised in that include following step Rapid:
The first step prepares porous ceramic plate: by weight percentage by clay 30%, quartz sand 30%, flyash 15%, resin 5%, length Stone 20% is poured into after in beaker, blended, pelletize, sieve, compressing, be dried, fire acquisition porous ceramic plate;
Second step prepares anode electrode: by graphite and nanometer Fe3O4After mixing, add a certain amount of water glass solution and stir all Even prepared mixed coating, is coated in post-drying on the porous ceramic plate that the first step prepares with hairbrush by mixed coating;
3rd step prepares cathode electrode: including being coated with carbon based layer, coating diffusion layer, the preparation of coating catalytic layer, concrete technology is such as Under:
(1) coating carbon based layer: first being cleaned up by the porous ceramic plate that the first step prepares, dry for standby, then by a certain amount of Hydrocarbon black powder load in small beaker, and add the PTFE solution that mass concentration is 40%, after stirring, prepare the molten slurry of white carbon black, With paintbrush brush, molten for white carbon black slurry is uniformly coated on porous ceramic plate again, after being coated with, through natural air drying 2 hours, so After porous ceramic plate is heated 25 min at a temperature of 370 DEG C, heat treatment takes out through naturally cooling to room temperature after completing;
(2) coating diffusion layer: be that 60% PTFE solution is uniformly coated in previous step have been coated with by paintbrush brush handle mass concentration On the porous ceramic plate of carbon based layer side, at air through natural air drying, until PTFE layer becomes white completely, then by porous Ceramic wafer heats 25 min at a temperature of 370 DEG C, repeats above step 3 times, makes PTFE layer be coated with 4 layers;
(3) coating catalytic layer: by nanometer Fe3O4Powder and powdered graphite mixing, after stirring with paintbrush brush, add quality dense Degree is Nafion solution and the high-purity isopropanol of 5%, after stirring, with paintbrush brush coating catalytic layer equably in porous ceramics The opposite side of plate PTFE layer, has been coated with rear natural air drying at least 24 hours.
Preparation method the most according to claim 1, it is characterised in that the mesh number sieved in the described first step is 40 mesh.
Preparation method the most according to claim 1, it is characterised in that pressure compressing in the described first step is 20MPa。
Preparation method the most according to claim 1, it is characterised in that the temperature being dried in the described first step is 70 DEG C.
Preparation method the most according to claim 1, it is characterised in that the temperature fired in the described first step be 1250~ 1280℃。
Preparation method the most according to claim 1, it is characterised in that graphite and nanometer Fe in described second step3O4Quality Ratio is 5:3, and the addition of described waterglass is graphite and nanometer Fe3O4Gross mass 3 times, the mass concentration of waterglass is 30%.
Preparation method the most according to claim 1, it is characterised in that the drying temperature in described second step is 70 DEG C.
Preparation method the most according to claim 1, it is characterised in that the interpolation of hydrocarbon black powder in (1) of described 3rd step Amount is the 15% of PTFE solution quality.
Preparation method the most according to claim 1, it is characterised in that nanometer Fe in (3) of described 3rd step3O4Powder and The mass ratio of powdered graphite is 3:5.
Preparation method the most according to claim 1, it is characterised in that Nafion solution and height in (3) of described 3rd step The volume ratio of pure isopropanol is 8:5.
CN201510063054.7A 2015-02-08 2015-02-08 A kind of preparation method of microbiological fuel cell magnetic conductive bioceramic electrode Expired - Fee Related CN104600331B (en)

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CN108546146A (en) * 2018-04-10 2018-09-18 云南铝业股份有限公司 Metal fuel battery waterproof ventilative layer and preparation method thereof
CN110823755A (en) * 2019-11-19 2020-02-21 湖南博溥立材料科技有限公司 Method for detecting anti-oxidation performance of coating material of prebaked electrolytic aluminum anode

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Address after: 333001 Jiangxi city of Jingdezhen Province Pearl mountain new factory Tao Yang Road 27

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