CN103872347A - Preparation method of porous nanofiber-based anode film of microbial fuel battery - Google Patents
Preparation method of porous nanofiber-based anode film of microbial fuel battery Download PDFInfo
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Abstract
The invention relates to a preparation method of a porous nanofiber-based anode film of a microbial fuel battery. Since polyaniline is good in bio-compatibility and electric conductivity and a nano fiber is high in specific surface area and high in surface activity, the polyaniline is polymerized onto a nano fiber film, which is activated through cyanuric chloride, in situ in a monomer manner to form the porous high-conductivity anode film of the microbial fuel battery. When the porous nanofiber-based anode film is applied to the microbial fuel battery, more electricity generation microorganisms can be adsorbed, the efficiency of the electricity generating microorganisms for generating electrons under an anaerobic condition through an oxygen-free breathing effect can be improved, and thus the output power density of the microbial fuel battery can be improved. The preparation method is simple in process, moderate in reaction conditions, low in production cost, free of pollution, suitable for preparation of a large-area microbial fuel battery anode material and favorable for application of the microbial fuel battery in a large scale.
Description
Technical field
The present invention relates to the preparation of a kind of microbiological fuel cell anode film
,particularly a preparation method for anode film for porous nano-fibre base microbe fuel cell, belongs to fuel cell technology field.
Background technology
Along with the rapid growth of population in the world, non-renewable resources are consumed in a large number as oil, coal, energy security and problem of environmental pollution become gradually restriction human kind sustainable development and affect the stable of society, but microbiological fuel cell has the function of electrogenesis and sewage disposal simultaneously, the mankind that appear as of microbiological fuel cell technology solve this great problem new thinking and method are provided.
The research of microbiological fuel cell technology starts from the eighties in last century, the device of a typical H type microbiological fuel cell is made up of electrogenesis microbe, anode, negative electrode, proton exchange membrane, microbiological fuel cell is that one utilizes microbe as catalyst, under anaerobic utilize anuerobic respiration that oxidation operation is decomposed and produces proton and electronics, proton reaches through amberplex the oxygen dissolving in negative electrode and negative electrode and reacts, and electronics is caught and passes to external circuit by anode material by microbe.Electronics can be supplied with external circuit electrical appliance at the mobile formation electric current of external circuit and use.Anode material has lower effect in microbiological fuel cell: provide microbial adhesion product and accept the electronics that Institute of Micro-biology catches and transmit the effect of electronics.The key factor that develops into the development of restriction micro-organisms fuel cell of anode material.Therefore the specific area, conductivity, the biocompatibility that improve microbiological fuel cell anode material become microbiological fuel cell important directions.
The more anode of microbial fuel cell material of current domestic research has: stainless steel cloth, graphite, carbon paper, carbon foam and it is carried out to modification.Chinese Patent Application No. CN 102324526 A, open day is on January 18th, 2012, invention and created name is: a kind of composite material anode of microbiological fuel cell and manufacture method, it relates to a kind of fuel cell composite material anode and manufacture method, low to solve microbiological fuel cell electricity generation ability, and to the low problem of organic pollutant removal rate in water body or sediment.Described anode is a kind of rolled-up stock, this anode comprises the first oven wire mesh blanket, the first nonmetal flaggy, the second oven wire mesh blanket, the second nonmetal flaggy and the 3rd oven wire mesh blanket, the second nonmetal flaggy is between the first oven wire mesh blanket and the second metal level silk screen layer, the second nonmetal flaggy is arranged between the second woven wire and the 3rd oven wire mesh blanket, a kind of method manufacture method key step of composite material anode of microbiological fuel cell is: one, woven wire is without specification etching, two, liquid phase plasma oozes carbo-nitriding, three, material compacting, four, liquid phase plasma carburizing, five, composite material reprocessing.The present invention is for the removal of microbiological fuel cell generating and water body sediment organic pollution.Its weak point is that the compatibility of this microbiological fuel cell anode film and microbe is poor, specific area is few compared with the micro organism quantity of subsection area absorption, so cause the shortcomings such as microbiological fuel cell output power density is low, current density is low.
Summary of the invention
For the problem of above-mentioned existence, the object of the present invention is to provide the preparation method of a kind of porous nano-fibre base microbe fuel cell anode film.To achieve these goals, the technical solution used in the present invention is:
A preparation method for anode film for porous nano-fibre base microbe fuel cell, described preparation method comprises the following steps:
A preparation monomer and sour mixed solution:
Described mixed solution is formulated by aniline monomer, acid and deionized water, wherein the concentration of aniline monomer is that the concentration of 0.005 g/ml ~ 1g/ml, acid is 0.5mol/L ~ 5mol/L, and acid is hydrochloric acid or sulfuric acid or nitric acid or phosphoric acid or DBSA or salicylic acid or wherein one of perchloric acid.
The mixed solution of b preparation initator and surfactant:
Described mixed solution is formulated by initator, surfactant and deionized water, wherein initiator concentration 0.01 g/ml ~ 0.5g/ml, surfactant concentration is 0.005g/ml ~ 0.5g/ml, described initator is ammonium persulfate or potassium permanganate or potassium bichromate or wherein one of ferric trichloride, and surfactant is dodecyl sodium sulfate or neopelex or polyethylene glycol or polyvinylpyrrolidone or wherein one of softex kw.
C nano fibrous membrane activation processing:
Nano fibrous membrane is placed in the 3 mol/L sodium hydroxide solutions of bath raio 1:30, controlling solution temperature is 30 DEG C, and constantly stir after 1h, take out nano fibrous membrane and blot surperficial solution with filter paper, take Cyanuric Chloride and 1 according to the ratio of 1:9, 4-dioxane, nano fibrous membrane is placed in to above-mentioned solution and constantly stirs at 30 DEG C, react after 2 h, taking out above-mentioned nano fibrous membrane filter paper blots, then use 1, the mixed solution washing of 4-dioxane and acetone, 1, 4-dioxane mass fraction is followed successively by 100%, 75%, 50%, 25%, 0%, wash and washed again after blotting with filter paper next time afterwards, each washing time 1 min ~ 5 min.
The home position polymerization reaction of d nano fibrous membrane:
Measure the solution of preparing in a step according to nano fibrous membrane bath raio for 1:20 ~ 1:200, nano fibrous membrane is immersed in above-mentioned solution in the backward above-mentioned solution of 5min ~ 30min to the solution that the b step of dropping equivalent dropwise joins and constantly stirs.After successive reaction 2 ~ 12h, the nano fibrous membrane that takes out electrically conductive polyaniline on in-situ polymerization through acetone, go after dried up washing, at 30 ~ 80 DEG C, dry and can obtain porous nano-fibre base microbe fuel cell anode film.
Described nano fibrous membrane is that spunlace non-woven cloth surface-coated has PVA-
co-PE nanofiber or needle punched non-woven fabrics surface-coated have PVA-
co-PE nanofiber or spun-bonded non-woven fabrics surface-coated have PVA-
co-PE nanofiber or melt spraying non-woven fabrics surface-coated have PVA-
co-PE nanofiber or heat seal nonwoven surface are coated with PVA-
co-PE nanofiber or loop bonding nonwoven surface are coated with PVA-
co-PE nanofiber.
Owing to adopting above technical scheme, because polyaniline has good biocompatibility and electric conductivity, simultaneously because nanofiber has high-specific surface area, high surface, the present invention adopts aniline monomer in-situ polymerization to the film of the nanofiber through Cyanuric Chloride activation, form porous, the microbiological fuel cell anode film of high conduction, thereby this porous nano-fibre base microbe fuel cell is applied in microbiological fuel cell and can adsorbs more electrogenesis microbe with anode film, improve electrogenesis microbe and under anaerobic produced electronic efficiency by anuerobic respiration, thereby can improve the output power density of microbiological fuel cell.Preparation method's technique of the present invention is simple simultaneously, reaction condition is gentleer, production cost is lower, the large-area anode of microbial fuel cell material of pollution-free applicable preparation, is conducive to microbiological fuel cell maximization application.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail:
A preparation method for anode film for porous nano-fibre base microbe fuel cell, described preparation method comprises the following steps:
A preparation monomer and sour mixed solution
Described mixed solution is formulated by aniline monomer, acid and deionized water, and wherein the concentration of aniline monomer is that the concentration of 0.005g/ml ~ 0.5g/ml, acid is 0.5mol/L ~ 5mol/L.Acid is hydrochloric acid or sulfuric acid or nitric acid or phosphoric acid or DBSA or salicylic acid or wherein one of perchloric acid, at room temperature first acid is added in deionized water, be mixed with sour solution then by the solution of aniline monomer acid adding, constantly stir and make aniline and hydrochloric acid fully react the salting liquid that forms aniline.
The mixed solution of b preparation initator and surfactant
Described mixed solution is by initator, surfactant and deionized water are formulated, wherein initiator concentration 0.01 g/ml ~ 0.5g/ml, surfactant concentration is 0.005g/ml ~ 0.5g/ml, described initator is ammonium persulfate or potassium permanganate or potassium bichromate or wherein one of ferric trichloride, surfactant is dodecyl sodium sulfate or neopelex or polyethylene glycol or polyvinylpyrrolidone or wherein one of softex kw, in the deionized water of 60～80 DEG C, initator and surfactant are added wherein, constantly stir solution is mixed.
C nano fibrous membrane activation processing
Certain mass nano fibrous membrane is placed in the 3 mol/L sodium hydroxide solutions of quality bath raio 1:30, controlling reaction temperature is 30 DEG C, and constantly stir after 1h, take out nano fibrous membrane and blot surperficial solution with filter paper, according to Cyanuric Chloride and 1, 4-dioxane mass ratio is that 1:9 weighs, constantly stir Cyanuric Chloride is dissolved, nano fibrous membrane is placed in to the solution of above-mentioned preparation and constantly stirs at 30 DEG C, react after 2 h, taking out above-mentioned nano fibrous membrane filter paper blots, then use 1, the mixed solution washing of 4-dioxane and acetone, wherein 1, the mass fraction of 4-dioxane is followed successively by 100%, 75%, 50%, 25%, 0%, wash and washed again after blotting with filter paper next time afterwards, each washing time is 1min ~ 5min.
D home position polymerization reaction
To measure the solution of preparing in a step according to quality bath raio for 1:20 ~ 1:200 through the nano fibrous membrane after Cyanuric Chloride activation, nano fibrous membrane is immersed in above-mentioned solution, constantly stir and make nano fibrous membrane be treated in the backward above-mentioned solution of 5 min ~ 30 min the solution that the above-mentioned b step of dropping equivalent is dropwise joined and constantly stir by above-mentioned solution complete wetting.For making the polyaniline that nano fibrous membrane in situ Polymerization obtains more evenly need to be by nanofiber inversion membrane once every half an hour, after successive reaction 2 ~ 12h, take out with acetone and go dried up washing, at 30 ~ 80 DEG C, drying and can obtain porous nano-fibre base microbe fuel cell anode film.
Described nano fibrous membrane is that spunlace non-woven cloth surface-coated has PVA-
co-PE nanofiber or needle punched non-woven fabrics surface-coated have PVA-
co-PE nanofiber or spun-bonded non-woven fabrics surface-coated have PVA-
co-PE nanofiber or melt spraying non-woven fabrics surface-coated have PVA-
co-PE nanofiber or heat seal nonwoven surface are coated with PVA-
co-PE nanofiber or loop bonding nonwoven surface are coated with PVA-
co-PE nanofiber.
The application of porous nano-fibre base anode film in microbiological fuel cell: the reaction unit that the present invention adopts is by proton exchange membrane, negative and positive the two poles of the earth to be separated in the middle of H type microbial fuel cell unit, anolyte adopts the phosphate buffer solution of 0.05mol/L ~ 0.5mol/L, and organic substrates is that glucose, electrogenesis microbe adopt Escherichia coli.Catholyte adopts the above-mentioned phosphate buffer solution of same concentrations, the porous nano-fibre base microbe fuel cell anode film that anode material adopts the method to prepare, and negative electrode adopts platinum plate electrode, and reference electrode adopts saturated calomel electrode, passes into 15min N before test
2make system in anaerobic environment.The electrochemical property test of microorganism battery is to measure with the electrochemical workstation of three-electrode system.
This preparation method is the method that adopts in-situ polymerization, aniline monomer is aggregated on the film of the nanofiber activating through Cyanuric Chloride, due to polyaniline there is good biocompatibility and electric conductivity, simultaneously because nanofiber has high-specific surface area, high surface, so thereby this anode film material is applied in microbiological fuel cell and can adsorbs more electrogenesis microbe, improve electrogenesis microbe and under anaerobic produced the transmission efficiency of electronics by respiration, thereby can improve the output power density of microbiological fuel cell.Its preparation method is fairly simple, pollution-free simultaneously, and reaction condition is gentleer, and production cost is lower, is applicable to the large-area anode of microbial fuel cell material of preparation, is conducive to microbiological fuel cell maximization application.
Specific embodiment
embodiment 1
The mixed solution of a preparation aniline monomer and hydrochloric acid
Described mixed solution monomer is formulated by aniline, hydrochloric acid and deionized water, and wherein the concentration of aniline monomer is 0.005g/ml, and the concentration of hydrochloric acid is 0.5mol/L.At room temperature first acid is added in deionized water, be mixed with sour solution and then aniline monomer added in sour solution, constantly stir and make aniline and hydrochloric acid fully react the salting liquid that forms aniline.
The mixed solution of b preparation ammonium persulfate and dodecyl sodium sulfate
Described mixed solution is formulated by ammonium persulfate, dodecyl sodium sulfate and deionized water, wherein initiator ammonium persulfate concentration 0.01g/ml, and surfactant dodecyl sodium sulfate concentration is 0.005g/ml.In the deionized water of 60～80 DEG C, initiator ammonium persulfate and surfactant dodecyl sodium sulfate are added wherein, constantly stir solution is mixed.
C nano fibrous membrane activation processing
Certain mass nano fibrous membrane is placed in the 3 mol/L sodium hydroxide solutions of quality bath raio 1:30, controlling reaction temperature is 30 DEG C, and constantly stir after 1 h, take out nano fibrous membrane and blot surperficial solution with filter paper, according to Cyanuric Chloride and 1, 4-dioxane mass ratio is that 1:9 weighs, constantly stir and make Cyanuric Chloride be dissolved in 1, in 4-dioxane, nano fibrous membrane is placed in to above-mentioned solution and disconnected stirring at 30 DEG C, react after 2 h, taking out above-mentioned nano fibrous membrane filter paper blots, then use 1, the mixed solution washing of 4-dioxane and acetone, wherein 1, 4-dioxane mass fraction is followed successively by 100%, 75%, 50%, 25%, 0%, wash and washed again after blotting with filter paper next time afterwards, each washing time is 1min ~ 5min.
D home position polymerization reaction
By through the nano fibrous membrane after Cyanuric Chloride activation according to quality bath raio the solution for preparing in 1:20 measures above-mentioned a step, nano fibrous membrane is immersed in above-mentioned solution, constantly stir and make nano fibrous membrane be treated in the backward above-mentioned solution of 5min ~ 30min the solution that the b step of dropping equivalent is dropwise joined and constantly stir by above-mentioned solution complete wetting.For making the polyaniline that nano fibrous membrane in situ Polymerization obtains more evenly need to be by nanofiber inversion membrane once every half an hour, after successive reaction 2 ~ 12h, take out with acetone and go dried up washing, at 30 ~ 80 DEG C, drying and can obtain porous nano-fibre base microbe fuel cell anode film.
Described nano fibrous membrane is that spunlace non-woven cloth surface-coated has PVA-
co-PE nanofiber.
embodiment 2
The mixed solution of a preparation aniline monomer and sulfuric acid
Described mixed solution is formulated by aniline monomer, sulfuric acid and deionized water, and wherein the concentration of aniline monomer is 0.5 g/ml, and the concentration of sulfuric acid is 5mol/L.At room temperature first sulfuric acid is added in deionized water, then the solution that is mixed with sulfuric acid add aniline monomer in the solution of sulfuric acid, constantly stirs and make aniline and sulfuric acid fully react the salting liquid that forms aniline.
The mixed solution of b preparation potassium permanganate and neopelex
Described mixed solution is formulated by potassium permanganate, neopelex and deionized water.Wherein initator potassium permanganate concentration 0.5g/ml, surfactant neopelex concentration is 0.5g/ml.In the deionized water of 60～80 DEG C, initator potassium permanganate and surfactant neopelex are added wherein, constantly stir solution is mixed.
C nano fibrous membrane activation processing
Certain mass nano fibrous membrane is placed in the 3mol/L sodium hydroxide solution of quality bath raio 1:30, controlling reaction temperature is 30 DEG C, and constantly stir after 1 h, take out nano fibrous membrane and blot surperficial solution with filter paper, according to Cyanuric Chloride and 1, 4-dioxane mass ratio is that 1:9 weighs, constantly stir and make Cyanuric Chloride be dissolved in 1, in 4-dioxane, nano fibrous membrane is placed in to above-mentioned solution and vibration at 30 DEG C, after reaction 2h, taking out above-mentioned nano fibrous membrane filter paper blots, then use 1, the mixed solution washing of 4-dioxane and acetone, wherein 1, 4-dioxane mass fraction is followed successively by 100%, 75%, 50%, 25%, 0%, wash and washed again after blotting with filter paper next time afterwards, each washing time is 1min ~ 5min.
D home position polymerization reaction
To measure the solution of preparing in a step according to quality bath raio for 1:30 through the nano fibrous membrane after Cyanuric Chloride activation, nano fibrous membrane is immersed in above-mentioned solution, constantly stir and make nano fibrous membrane be treated in the backward above-mentioned solution of 5min ~ 30min the solution that the b step of dropping equivalent is dropwise joined and constantly stir by above-mentioned solution complete wetting.For making the polyaniline that nano fibrous membrane in situ Polymerization obtains more evenly need to be by nanofiber inversion membrane once every half an hour, after successive reaction 2 ~ 12 h, take out with acetone and go dried up washing, at 30 ~ 80 DEG C, drying and can obtain porous nano-fibre base microbe fuel cell anode film.
Described nano fibrous membrane is that needle punched non-woven fabrics surface-coated has PVA-
co-PE nanofiber.
embodiment 3
The mixed solution of a preparation aniline monomer and nitric acid
Described mixed solution is formulated by aniline monomer, nitric acid and deionized water, and wherein the concentration of aniline monomer is 0.1g/ml, and the concentration of nitric acid is 1mol/L.At room temperature first acid is added in deionized water, be mixed with sour solution and then aniline monomer added in sour solution, constantly stir and make aniline and hydrochloric acid fully react the salting liquid that forms aniline.
The mixed solution of b preparation potassium bichromate and polyethylene glycol
Described mixed solution is that potassium bichromate, polyethylene glycol and deionized water are formulated.Wherein initator potassium bichromate concentration 0.01g/ml, surfactant polyethylene concentration is 0.1g/ml.In the deionized water of 60～80 DEG C, initator potassium bichromate and surfactant polyethylene are added wherein, constantly stir solution is mixed.
C nano fibrous membrane activation processing
Certain mass nano fibrous membrane is placed in the 3mol/L sodium hydroxide solution of quality bath raio 1:30, controlling reaction temperature is 30 DEG C, and constantly stir after 1h, take out nano fibrous membrane and blot surperficial solution with filter paper, according to Cyanuric Chloride and 1, 4-dioxane mass ratio is that 1:9 weighs, constantly stir and make Cyanuric Chloride be dissolved in 1, in 4-dioxane, nano fibrous membrane is placed in to above-mentioned solution and constantly stirs at 30 DEG C, react after 2 h, taking out above-mentioned nano fibrous membrane filter paper blots, then use 1, the mixed solution washing of 4-dioxane and acetone, wherein 1, 4-dioxane mass fraction is followed successively by 100%, 75%, 50%, 25%, 0%, wash and washed again after blotting with filter paper next time afterwards, each washing time is 1min ~ 5min.
D home position polymerization reaction
To measure the solution of preparing in a step according to quality bath raio for 1:100 through the nano fibrous membrane after Cyanuric Chloride activation, nano fibrous membrane is immersed in above-mentioned solution, constantly stir and make nano fibrous membrane be treated in the backward above-mentioned solution of 5 min ~ 30 min the solution that the b step of dropping equivalent is dropwise joined and constantly stir by above-mentioned solution complete wetting.For making the polyaniline that nano fibrous membrane in situ Polymerization obtains more evenly need to be by nanofiber inversion membrane once every half an hour, after successive reaction 2 ~ 12 h, take out with acetone and go dried up washing, at 30 ~ 80 DEG C, drying and can obtain porous nano-fibre base microbe fuel cell anode film.
Described nano fibrous membrane is that spun-bonded non-woven fabrics surface-coated has PVA-
co-PE nanofiber.
embodiment 4
The mixed solution of a preparation aniline monomer and phosphoric acid
Described mixed solution is formulated by aniline monomer, phosphoric acid and deionized water, and wherein the concentration of aniline monomer is 0.02 g/ml, and the concentration of phosphoric acid is 2mol/L.At room temperature first phosphoric acid is added in deionized water, then the solution that is mixed with phosphoric acid add aniline monomer in the solution of phosphoric acid, constantly stirs and make aniline and phosphoric acid fully react the salting liquid that forms aniline.
The mixed solution of b preparation ferric trichloride and polyvinylpyrrolidone
Described mixed solution is that ferric trichloride, polyvinylpyrrolidone and deionized water are formulated, wherein initator ferric trichloride concentration 0.025 g/ml, and surfactant polyvinylpyrrolidone concentration is 0.01g/ml.In the deionized water of 60～80 DEG C, initator ferric trichloride and surfactant polyvinylpyrrolidone are added wherein, constantly stir solution is mixed.
C nano fibrous membrane activation processing
Certain mass nano fibrous membrane is placed in the 3mol/L sodium hydroxide solution of quality bath raio 1:30, controlling reaction temperature is 30 DEG C, and constantly stir after 1 h, take out nano fibrous membrane and blot surperficial solution with filter paper, according to Cyanuric Chloride and 1, 4-dioxane mass ratio is that 1:9 weighs, constantly stir and make Cyanuric Chloride be dissolved in 1, in 4-dioxane, nano fibrous membrane is placed in to above-mentioned solution and constantly stirs at 30 DEG C, react after 2 h, taking out above-mentioned nano fibrous membrane filter paper blots, then use 1, the mixed solution washing of 4-dioxane and acetone, wherein 1, 4-dioxane mass fraction is followed successively by 100%, 75%, 50%, 25%, 0%, wash and washed again after blotting with filter paper next time afterwards, each washing time is 1min ~ 5min.
D home position polymerization reaction
To measure the solution of preparing in a step according to quality bath raio for 1:150 through the nano fibrous membrane after Cyanuric Chloride activation, nano fibrous membrane is immersed in above-mentioned solution, constantly stir and make nano fibrous membrane be treated in the backward above-mentioned solution of 5min ~ 30min the solution that the b step of dropping equivalent is dropwise joined and constantly stir by above-mentioned solution complete wetting.For making the polyaniline that nano fibrous membrane in situ Polymerization obtains more evenly need to be by nanofiber inversion membrane once every half an hour, after successive reaction 2 ~ 12h, take out with acetone and go dried up washing, at 30 ~ 80 DEG C, drying and can obtain porous nano-fibre base microbe fuel cell anode film.
Described nano fibrous membrane is that needle punched non-woven fabrics surface-coated has PVA-
co-PE nanofiber.
embodiment 5
The mixed solution of a preparation aniline monomer and DBSA
Described mixed solution is formulated by aniline monomer, DBSA and deionized water, and wherein the concentration of aniline monomer is 0.03g/ml, and the concentration of DBSA is 3mol/L.At room temperature first DBSA is added in deionized water, then the solution that is mixed with DBSA add aniline monomer in the solution of DBSA, constantly stirs and make aniline and DBSA fully react the salting liquid that forms aniline.
The mixed solution of b preparation ammonium persulfate and softex kw
Described mixed solution is formulated by ammonium persulfate, softex kw and deionized water.Wherein initiator ammonium persulfate concentration 0.35g/ml, surfactant softex kw concentration is 0.3g/ml.In the deionized water of 60～80 DEG C, initiator ammonium persulfate and surfactant softex kw are added wherein, constantly stir solution is mixed.
C nano fibrous membrane activation processing
Certain mass nano fibrous membrane is placed in the 3mol/L sodium hydroxide solution of quality bath raio 1:30, controlling reaction temperature is 30 DEG C, and constantly stir after 1h, take out nano fibrous membrane and blot surperficial solution with filter paper, according to Cyanuric Chloride and 1, 4-dioxane mass ratio is that 1:9 weighs, constantly stir and make Cyanuric Chloride be dissolved in 1, in 4-dioxane, nano fibrous membrane is placed in to above-mentioned solution and constantly stirs at 30 DEG C, after reaction 2h, taking out above-mentioned nano fibrous membrane filter paper blots, then use 1, the mixed solution washing of 4-dioxane and acetone, wherein 1, 4-dioxane mass fraction is followed successively by 100%, 75%, 50%, 25%, 0%, wash and washed again after blotting with filter paper next time afterwards, each washing time is 1 min ~ 5 min.
D home position polymerization reaction
To measure the solution of preparing in a step according to quality bath raio for 1:200 through the nano fibrous membrane after Cyanuric Chloride activation, nano fibrous membrane is immersed in above-mentioned solution, constantly stir and make nano fibrous membrane be treated in the backward above-mentioned solution of 5min ~ 30min the solution that the b step of dropping equivalent is dropwise joined and constantly stir by above-mentioned solution complete wetting.For making the polyaniline that nano fibrous membrane in situ Polymerization obtains more evenly need to be by nanofiber inversion membrane once every half an hour, after successive reaction 2 ~ 12h, take out with acetone and go dried up washing, at 30 ~ 80 DEG C, drying and can obtain porous nano-fibre base microbe fuel cell anode film.
Described nano fibrous membrane is that melt spraying non-woven fabrics surface-coated has PVA-
co-PE nanofiber.
embodiment 6
A preparation aniline and salicylic mixed solution
Described mixed solution is formulated by aniline monomer, salicylic acid and deionized water, and wherein the concentration of aniline monomer is 0.2 g/ml, and salicylic concentration is 1 mol/L.At room temperature first acid is added in deionized water, be mixed with salicylic solution and then aniline monomer added in salicylic solution, constantly stir and make aniline and salicylic acid fully react the salting liquid that forms aniline.
The mixed solution of b preparation ferric trichloride and softex kw
Described mixed solution is that ferric trichloride, softex kw and deionized water are formulated, and wherein initator ferric trichloride concentration is 0.035g/ml, and surfactant softex kw concentration is 0.075g/ml.In the deionized water of 60～80 DEG C, initator ferric trichloride and surfactant softex kw are added wherein, constantly stir solution is mixed.
C nano fibrous membrane activation processing
Certain mass nano fibrous membrane is placed in the 3mol/L sodium hydroxide solution of quality bath raio 1:30, controlling reaction temperature is 30 DEG C, and constantly stir after 1h, take out nano fibrous membrane and blot surperficial solution with filter paper, according to Cyanuric Chloride and 1, 4-dioxane mass ratio is that 1:9 weighs, constantly stir and make Cyanuric Chloride be dissolved in 1, in 4-dioxane, nano fibrous membrane is placed in to above-mentioned solution and constantly stirs at 30 DEG C, after reaction 2h, taking out above-mentioned nano fibrous membrane filter paper blots, then use 1, the mixed solution washing of 4-dioxane and acetone, wherein 1, 4-dioxane mass fraction is followed successively by 100%, 75%, 50%, 25%, 0%, wash and washed again after blotting with filter paper next time afterwards, each washing time is 1min ~ 5min.
D home position polymerization reaction
To measure the solution of preparing in a step according to quality bath raio for 1:50 through the nano fibrous membrane after Cyanuric Chloride activation, nano fibrous membrane is immersed in above-mentioned solution, constantly stir and make nano fibrous membrane be treated in the backward above-mentioned solution of 5min ~ 30min the solution that the b step of dropping equivalent is dropwise joined and constantly stir by above-mentioned solution complete wetting.For making the polyaniline that nano fibrous membrane in situ Polymerization obtains more evenly need to be by nanofiber inversion membrane once every half an hour, after successive reaction 2 ~ 12h, take out with acetone and go dried up washing, at 30 ~ 80 DEG C, drying and can obtain porous nano-fibre base microbe fuel cell anode film.
Described nano fibrous membrane is that heat seal nonwoven surface is coated with PVA-
co-PE nanofiber.
embodiment 7
The mixed solution of a preparation aniline monomer and perchloric acid
Described mixed solution is made up of aniline monomer, perchloric acid and deionized water, and wherein the concentration of aniline monomer is 0.15 g/ml, and the concentration of perchloric acid is 2.5mol/L.At room temperature first perchloric acid is added in deionized water, then the solution that is mixed with perchloric acid add aniline monomer in the solution of perchloric acid, constantly stirs and make aniline and perchloric acid fully react the salting liquid that forms aniline.
The mixed solution of b preparation ferric trichloride and dodecyl sodium sulfate
Described mixed solution is ferric trichloride, dodecyl sodium sulfate and deionized water composition, the wherein concentration 0.01g/ml of initator ferric trichloride, surfactant dodecyl sodium sulfate 0.1g/ml.In the deionized water of 60～80 DEG C, initator ferric trichloride and surfactant dodecyl sodium sulfate are added wherein, constantly stir solution is mixed.
C nano fibrous membrane activation processing
Certain mass nano fibrous membrane is placed in the 3mol/L sodium hydroxide solution of quality bath raio 1:30, controlling reaction temperature is 30 DEG C, and constantly stir after 1h, take out nano fibrous membrane and blot surperficial solution with filter paper, according to Cyanuric Chloride and 1, 4-dioxane mass ratio is that 1:9 weighs, constantly stir and make Cyanuric Chloride be dissolved in 1, in 4-dioxane, nano fibrous membrane is placed in to above-mentioned solution and constantly stirs at 30 DEG C, after reaction 2h, taking out above-mentioned nano fibrous membrane filter paper blots, then use 1, the mixed solution washing of 4-dioxane and acetone, wherein 1, 4-dioxane mass fraction is followed successively by 100%, 75%, 50%, 25%, 0%, wash and washed again after blotting with filter paper next time afterwards, each washing time is 1min ~ 5min.
D home position polymerization reaction
To measure the solution of preparing in a step according to quality bath raio for 1:100 through the nano fibrous membrane after Cyanuric Chloride activation, nano fibrous membrane is immersed in above-mentioned solution, constantly stir and make nano fibrous membrane be treated in the backward above-mentioned solution of 5min ~ 30min the solution that the b step of dropping equivalent is dropwise joined and constantly stir by above-mentioned solution complete wetting.For making the polyaniline that nano fibrous membrane in situ Polymerization obtains more evenly need to be by nanofiber inversion membrane once every half an hour, after successive reaction 2 ~ 12h, take out with acetone and go dried up washing, at 30 ~ 80 DEG C, drying and can obtain porous nano-fibre base microbe fuel cell anode film.
Described nano fibrous membrane is that loop bonding nonwoven surface is coated with PVA-
co-PE nanofiber.
Claims (2)
1. a preparation method for anode film for porous nano-fibre base microbe fuel cell, is characterized in that, described preparation method comprises the following steps:
A preparation monomer and sour mixed solution:
Described mixed solution is formulated by aniline monomer, acid and deionized water, wherein the concentration of aniline monomer is that the concentration of 0.005 g/ml ~ 0.5g/ml, acid is 0.5mol/L ~ 5mol/L, and acid is hydrochloric acid or sulfuric acid or nitric acid or phosphoric acid or DBSA or salicylic acid or wherein one of perchloric acid;
The mixed solution of b preparation initator and surfactant:
Described mixed solution is formulated by initator, surfactant and deionized water, wherein initiator concentration 0.01 g/ml ~ 0.5g/ml, surfactant concentration is 0.005g/ml ~ 0.5g/ml, described initator is ammonium persulfate or potassium permanganate or potassium bichromate or wherein one of ferric trichloride, and surfactant is dodecyl sodium sulfate or neopelex or polyethylene glycol or polyvinylpyrrolidone or wherein one of softex kw;
C nano fibrous membrane activation processing:
Nano fibrous membrane is placed in the 3 mol/L sodium hydroxide solutions of bath raio 1:30, controlling solution temperature is 30 DEG C, and constantly stir after 1h, take out nano fibrous membrane and blot surperficial solution with filter paper, take Cyanuric Chloride and 1 according to the ratio of 1:9, 4-dioxane, nano fibrous membrane is placed in to above-mentioned solution and constantly stirs at 30 DEG C, after reaction 2h, taking out above-mentioned nano fibrous membrane filter paper blots, then use 1, the mixed solution washing of 4-dioxane and acetone, 1, 4-dioxane mass fraction is followed successively by 100%, 75%, 50%, 25%, 0%, wash and washed again after blotting with filter paper next time afterwards, each washing time 1 min ~ 5 min,
The home position polymerization reaction of d nano fibrous membrane:
Measure the solution of preparing in a step according to nano fibrous membrane bath raio for 1:20 ~ 1:200, nano fibrous membrane is immersed in above-mentioned solution in the backward above-mentioned solution of 5 min ~ 30 min to the solution that the b step of dropping equivalent dropwise joins and constantly stirs; After successive reaction 2 ~ 12h, the nano fibrous membrane that takes out electrically conductive polyaniline on in-situ polymerization through acetone, go after dried up washing, at 30 ~ 80 DEG C, dry and can obtain porous nano-fibre base microbe fuel cell anode film.
2. the preparation method of anode film for a kind of porous nano-fibre base microbe fuel cell as claimed in claim 1, is characterized in that: described nano fibrous membrane is that spunlace non-woven cloth surface-coated has PVA-
co-PE nanofiber or needle punched non-woven fabrics surface-coated have PVA-
co-PE nanofiber or spun-bonded non-woven fabrics surface-coated have PVA-
co-PE nanofiber or melt spraying non-woven fabrics surface-coated have PVA-
co-PE nanofiber or heat seal nonwoven surface apply PVA-
co-PE nanofiber or loop bonding nonwoven surface are coated with PVA-
co-PE nanofiber.
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Application publication date: 20140618 |