CN107591540A - A kind of preparation method of biological fuel cell anode material - Google Patents
A kind of preparation method of biological fuel cell anode material Download PDFInfo
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- 239000010405 anode material Substances 0.000 title claims abstract description 33
- 239000000446 fuel Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 43
- 239000004744 fabric Substances 0.000 claims abstract description 42
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 34
- 239000002131 composite material Substances 0.000 claims abstract description 33
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 239000004088 foaming agent Substances 0.000 claims abstract description 20
- 239000003999 initiator Substances 0.000 claims abstract description 16
- 239000002356 single layer Substances 0.000 claims abstract description 9
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical group OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims abstract description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 42
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 42
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 34
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 21
- 235000010265 sodium sulphite Nutrition 0.000 claims description 21
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 18
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 150000007513 acids Chemical class 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 9
- 239000005457 ice water Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000002242 deionisation method Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003643 water by type Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 238000007781 pre-processing Methods 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 230000005611 electricity Effects 0.000 abstract description 11
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 8
- 229920000767 polyaniline Polymers 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 102000004190 Enzymes Human genes 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000010148 water-pollination Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000011942 biocatalyst Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000011712 cell development Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 210000003470 mitochondria Anatomy 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
Classifications
-
- 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
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Abstract
The present invention discloses a kind of preparation method of biological fuel cell anode material, with graphene and polyaniline-modified traditional anode material carbon cloth, single-layer graphene oxide is first modified with styrene sulfonic acid, then hydrophilic graphene is obtained with hydrazine hydrate reduction single-layer graphene oxide again, by hydrophilic graphene add containing aniline monomer, initiator, pore-foaming agent composite solution in, again by composite solution coated on the carbon cloth through hydrophilic pretreatment, composite solution reacts on carbon cloth, is then dried to obtain anode material.The biological fuel cell anode material that the present invention prepares has the advantages of biological attachment area is big, hydrophilicity is good, electric conductivity is strong, electricity generation performance is good.
Description
Technical field
The invention belongs to biological fuel cell field, and in particular to a kind of preparation side of biological fuel cell anode material
Method.
Background technology
Biological fuel cell is a kind of device that chemical energy is converted into electric energy using biocatalyst, utilizes micro- life
Thing metabolic process carries with the research and development for the biological fuel cell that electrode reaction is combined for production of renewable energy resources and offal treatment
A new way is supplied.Biological fuel cell is by the use of microorganism as reactive agent, by the chemical energy of fuel (organic substance)
Be converted into electric energy, it be it is a kind of using it is various biology be used as catalyst devices, conventional biocatalyst have microorganism, carefully
Born of the same parents' device (such as mitochondria) and enzyme, its type are determined by the species of biocatalyst.
Carrier of the anode of biological fuel cell as electricity production biological attachment, the adhesion amount of electricity production biology is not only influenceed, together
When have an effect on transmission of the electronics from microorganism to anode, on improve battery electricity generation performance have vital influence.It is high performance
Biological fuel cell anode requirement is easy to electricity-producing microorganism apposition growth, is easy to electron transmission, while require anode interior resistance
It is small, electric conductivity is strong, anode potential is stable.The electricity generation performances such as current traditional carbon paper, carbon cloth, graphite cake, soft graphite are general, work(
Rate problem becomes the bottleneck for influenceing biological fuel cell development.
The content of the invention
The present invention provides a kind of preparation method of biological fuel cell anode material, by changing to traditional carbon cloth anode
Property, prepare the anode material that biological attachment area is big, hydrophilicity is good, electric conductivity is strong, electricity generation performance is good.
In order to solve the above technical problems, the present invention adopts the following technical scheme that：
A kind of preparation method of biological fuel cell anode material, comprises the following steps：
S1. count in parts by weight, 5 parts of single-layer graphene oxides, 5~8 parts of styrene sulfonic acids and 100 parts of deionized waters are mixed
Close, 24h is stirred at room temperature, then add 5~7 parts of hydrazine hydrates, flow back 8~12h at 90~95 DEG C, then filtration washing,
Solid product is dried in vacuo, obtains hydrophilic graphene；
S2. count in parts by weight, by 5 parts of polystyrolsulfon acids, 0.3~0.9 part of hydrophilic graphene, 1~5 part of acrylic acid
Monomer, 30~40 parts of aniline monomers are added in reactor of the dress by the sulfonic acid solutions that 300 parts of pH value are 1~1.5, use ice-water bath
It is 0~5 DEG C to control temperature of reactor, with 400~500r/min rotating speed mechanical agitation, then adds 0.25~0.3 part of initiation
Agent, 1~3 part of pore-foaming agent, obtains composite solution；
S3. composite solution is uniformly coated on carbon cloth surfaces, 1~2h is reacted at room temperature, then at 55~60 DEG C
Drying, then alternately rinsed with deionization and acetone, finally obtain anode material.
Further, the carbon cloth is by pretreatment, preprocess method：Carbon cloth is immersed in ethanol or acetone soln
In, then 0.5~1h of ultrasonic vibration, then takes out and dries, be then placed in concentration be 20~30% hydrogen peroxide in immersion 6~
8h, rinsed and then dried standby with water.
Further, the composite solution is coated in carbon cloth surfaces in 15min.
Further, the pore-foaming agent is the quality of the mixture of sodium carbonate and sodium acid carbonate, sodium carbonate and sodium acid carbonate
Than for 1:0.5~1.3.
Further, the initiator is any one in ammonium persulfate, potassium peroxydisulfate, ammonium persulfate/sodium sulfite,
The molal weight of ammonium persulfate and sodium sulfite ratio is 1 in ammonium persulfate/sodium sulfite:0.1~0.3.
Beneficial effects of the present invention：
(1) present invention carrys out modification carbon cloth with hydrophilic graphene and polyaniline, and graphene has more compared with carbon cloth
Good biocompatibility and electric conductivity, and the specific surface area of graphene is bigger than carbon cloth, is more beneficial for the attachment surface of increase biology
Product, the present invention carry out hydrophilic treated to graphene so that graphene is evenly distributed in the solution, and aniline monomer of the present invention is in sulfonic acid
Lower polymerization, obtains partly sulfonated polyaniline, so as to increase the hydrophilic radical on polyaniline surface, strengthens the hydrophily of polyaniline, this
The carbon cloth of invention passes through hydrophilic pretreatment, improves the hydrophilicity of carbon cloth, therefore anode material hydrophilicity prepared by the present invention
It is good, be advantageous to the attachment and growth of biology.
(2) present invention adds pore-foaming agent in composite solution, and pore-foaming agent can produce gas during monomer polymerize
Body so that duct is formed in polymer, duct can increase the surface area of polymer, while can also increase the energy of adsorption of polymer
Power so that anode material can adhere to more biologies, while also improve fixed effect of the biology on anode material.
(3) contain acrylic acid in composite solution of the invention, be on the one hand used for the hydrophilicity for improving polymer, the opposing party
Face is advantageous to increase the viscosity and plasticity of composite solution so that combines more firmly between composite solution and carbon cloth, while also has
Beneficial to thickness of the control composite solution after carbon cloth surfaces shaping.
(4) carbon cloth of the invention, which applies, is covered with composite solution and reacts 1~2h at room temperature so that monomer polymerize, then 55
Drying is on the one hand to moisture removal at~60 DEG C, is on the other hand to decompose remnants sodium acid carbonate, reduces anode material
Impurity in material.
(5) the uncoated preceding temperature of composite solution of the present invention is 0~5 DEG C, and polymerization rate is slow, is coated in composite solution
The process of carbon cloth surfaces reserves time enough, and composite solution is coated in carbon cloth surfaces in 15min, avoids composite solution not
With regard to overreaction before coating, it is unfavorable for subsequent coated process, the sulfonic acid acidifying carbon cloth in composite solution is advantageous to further improve
The hydrophily of carbon cloth.
(6) the practical pore-foaming agent of the present invention is sodium carbonate and the mixture of sodium acid carbonate, can by both ratios come
Adjust speed caused by gas so that the hole of sufficient amount is formed when polyaniline is molded, gas generation is too fast easily to cause gas
Runaway, the duct of formation is excessive, forms excessive velocities easily causes duct to cave in, and gas produced then to be not easy to form hole slowly.
(7) when the present invention using ammonium persulfate/sodium sulfite is initiator, the amount of sodium sulfite can influence the speed reacted
Degree, sodium sulfite can excessively cause polymerisation too fast, be unfavorable for the coating of composite solution.
Embodiment
For ease of more fully understanding the present invention, it is illustrated by following instance, these examples belong to the protection of the present invention
Scope, but do not limit the scope of the invention.
Embodiment 1
A kind of preparation method of biological fuel cell anode material, comprises the following steps：
S1. count in parts by weight, 5 parts of single-layer graphene oxides, 5 parts of styrene sulfonic acids and 100 parts of deionized waters mixed,
24h is stirred at room temperature, then adds 5 parts of hydrazine hydrates, flow back 10h at 95 DEG C, then filtration washing, by solid product vacuum
Dry, obtain hydrophilic graphene；
S2. count in parts by weight, by 5 parts of polystyrolsulfon acids, 0.6 part of hydrophilic graphene, 3 parts of acrylic monomers, 30
Part aniline monomer is added in reactor of the dress by the sulfonic acid solutions that 300 parts of pH value are 1, controls the temperature of reactor to be with ice-water bath
2 DEG C, with 430r/min rotating speed mechanical agitation, 0.25 part of initiator is then added, 3 parts of pore-foaming agents, obtains composite solution；
S3. carbon cloth is immersed in ethanol or acetone soln, then ultrasonic vibration 1h, then takes out and dry, be then placed in
Concentration is to soak 7h in 25% hydrogen peroxide, is rinsed with water and then dries to obtain pretreatment carbon cloth.
S4., composite solution is uniformly coated on to pretreatment carbon cloth surfaces in 15min, reacts 1.5h at room temperature, so
Dry at 55 DEG C, then alternately rinsed with deionization and acetone afterwards, finally obtain anode material.
The pore-foaming agent is the mixture of sodium carbonate and sodium acid carbonate, and the mass ratio of sodium carbonate and sodium acid carbonate is 1:1.3.
The initiator is ammonium persulfate/sodium sulfite, ammonium persulfate and sodium sulfite in ammonium persulfate/sodium sulfite
Molal weight ratio is 1:0.1.
Embodiment 2
S1. count in parts by weight, 5 parts of single-layer graphene oxides, 8 parts of styrene sulfonic acids and 100 parts of deionized waters mixed,
24h is stirred at room temperature, then adds 7 parts of hydrazine hydrates, flow back 12h at 92 DEG C, then filtration washing, by solid product vacuum
Dry, obtain hydrophilic graphene；
S2. count in parts by weight, by 5 parts of polystyrolsulfon acids, 0.3 part of hydrophilic graphene, 5 parts of acrylic monomers, 35
Part aniline monomer is added in reactor of the dress by the sulfonic acid solutions that 300 parts of pH value are 1.5, and temperature of reactor is controlled with ice-water bath
For 5 DEG C, with 400r/min rotating speed mechanical agitation, 0.3 part of initiator is then added, 1 part of pore-foaming agent, obtains composite solution；
S3. carbon cloth is immersed in ethanol or acetone soln, then ultrasonic vibration 0.5h, then takes out and dry, Ran Houfang
Enter in the hydrogen peroxide that concentration is 30% and soak 6h, rinsed with water and then dry to obtain pretreatment carbon cloth.
S4., composite solution is uniformly coated on to pretreatment carbon cloth surfaces in 15min, reacts 1h at room temperature, then
Dry at 60 DEG C, then alternately rinsed with deionization and acetone, finally obtain anode material.
The pore-foaming agent is the mixture of sodium carbonate and sodium acid carbonate, and the mass ratio of sodium carbonate and sodium acid carbonate is 1:0.5.
The initiator is ammonium persulfate/sodium sulfite, ammonium persulfate and sodium sulfite in ammonium persulfate/sodium sulfite
Molal weight ratio is 1:0.3.
Embodiment 3
S1. count in parts by weight, 5 parts of single-layer graphene oxides, 6 parts of styrene sulfonic acids and 100 parts of deionized waters mixed,
24h is stirred at room temperature, then adds 6.5 parts of hydrazine hydrates, flow back 8h at 90 DEG C, and then filtration washing, true by solid product
Sky is dried, and obtains hydrophilic graphene；
S2. count in parts by weight, by 5 parts of polystyrolsulfon acids, 0.9 part of hydrophilic graphene, 1 part of acrylic monomers, 40
Part aniline monomer is added in reactor of the dress by the sulfonic acid solutions that 300 parts of pH value are 1.2, and temperature of reactor is controlled with ice-water bath
For 0 DEG C, with 500r/min rotating speed mechanical agitation, 0.28 part of initiator is then added, 2 parts of pore-foaming agents, obtains composite solution；
S3. carbon cloth is immersed in ethanol or acetone soln, then ultrasonic vibration 0.8h, then takes out and dry, Ran Houfang
Enter in the hydrogen peroxide that concentration is 20% and soak 8h, rinsed with water and then dry to obtain pretreatment carbon cloth.
S4., composite solution is uniformly coated on to pretreatment carbon cloth surfaces in 15min, reacts 2h at room temperature, then
Dry at 58 DEG C, then alternately rinsed with deionization and acetone, finally obtain anode material.
The pore-foaming agent is the mixture of sodium carbonate and sodium acid carbonate, and the mass ratio of sodium carbonate and sodium acid carbonate is 1:0.9.
The initiator is ammonium persulfate/sodium sulfite, ammonium persulfate and sodium sulfite in ammonium persulfate/sodium sulfite
Molal weight ratio is 1:0.2.
Embodiment 4
S1. count in parts by weight, 5 parts of single-layer graphene oxides, 5 parts of styrene sulfonic acids and 100 parts of deionized waters mixed,
24h is stirred at room temperature, then adds 6.8 parts of hydrazine hydrates, flow back 12h at 93 DEG C, and then filtration washing, true by solid product
Sky is dried, and obtains hydrophilic graphene；
S2. count in parts by weight, by 5 parts of polystyrolsulfon acids, 0.9 part of hydrophilic graphene, 1 part of acrylic monomers, 36
Part aniline monomer is added in reactor of the dress by the sulfonic acid solutions that 300 parts of pH value are 1, controls the temperature of reactor to be with ice-water bath
1 DEG C, with 500r/min rotating speed mechanical agitation, 0.27 part of initiator is then added, 2 parts of pore-foaming agents, obtains composite solution；
S3. carbon cloth is immersed in ethanol or acetone soln, then ultrasonic vibration 1h, then takes out and dry, be then placed in
Concentration is to soak 8h in 30% hydrogen peroxide, is rinsed with water and then dries to obtain pretreatment carbon cloth.
S4., composite solution is uniformly coated on to pretreatment carbon cloth surfaces in 15min, reacts 2h at room temperature, then
Dry at 59 DEG C, then alternately rinsed with deionization and acetone, finally obtain anode material.
The pore-foaming agent is the mixture of sodium carbonate and sodium acid carbonate, and the mass ratio of sodium carbonate and sodium acid carbonate is 1:0.4.
The initiator is ammonium persulfate.
Embodiment 5
S1. count in parts by weight, 5 parts of single-layer graphene oxides, 8 parts of styrene sulfonic acids and 100 parts of deionized waters mixed,
24h is stirred at room temperature, then adds 6.5 parts of hydrazine hydrates, flow back 11h at 95 DEG C, and then filtration washing, true by solid product
Sky is dried, and obtains hydrophilic graphene；
S2. count in parts by weight, by 5 parts of polystyrolsulfon acids, 0.8 part of hydrophilic graphene, 4 parts of acrylic monomers, 38
Part aniline monomer is added in reactor of the dress by the sulfonic acid solutions that 300 parts of pH value are 1, controls the temperature of reactor to be with ice-water bath
2 DEG C, with 400r/min rotating speed mechanical agitation, 0.28 part of initiator is then added, 3 parts of pore-foaming agents, obtains composite solution；
S3. carbon cloth is immersed in ethanol or acetone soln, then ultrasonic vibration 0.8h, then takes out and dry, Ran Houfang
Enter in the hydrogen peroxide that concentration is 30% and soak 8h, rinsed with water and then dry to obtain pretreatment carbon cloth.
S4., composite solution is uniformly coated on to pretreatment carbon cloth surfaces in 15min, reacts 2h at room temperature, then
Dry at 60 DEG C, then alternately rinsed with deionization and acetone, finally obtain anode material.
The pore-foaming agent is the mixture of sodium carbonate and sodium acid carbonate, and the mass ratio of sodium carbonate and sodium acid carbonate is 1:0.5.
The initiator is potassium peroxydisulfate.
Comparative example 1
S1. count in parts by weight, by 5 parts of polystyrolsulfon acids, 0.3 part of graphene, 5 parts of acrylic monomers, 35 parts of aniline
Monomer is added in reactor of the dress by the hydrochloric acid solution that 300 parts of pH value are 1.5, and it is 5 DEG C to control temperature of reactor with ice-water bath,
With 400r/min rotating speed mechanical agitation, 0.3 part of initiator is then added, 1 part of pore-foaming agent, obtains composite solution；
S2. composite solution is uniformly coated on carbon cloth surfaces in 15min, reacts 1h at room temperature, then at 60 DEG C
Lower drying, then alternately rinsed with deionization and acetone, finally obtain anode material.
The pore-foaming agent is the mixture of sodium carbonate and sodium acid carbonate, and the mass ratio of sodium carbonate and sodium acid carbonate is 1:0.5.
The initiator is ammonium persulfate/sodium sulfite, ammonium persulfate and sodium sulfite in ammonium persulfate/sodium sulfite
Molal weight ratio is 1:0.3.
Comparative example 2
Comparative example 2 in place of the difference of embodiment 2 with being：S2. count in parts by weight, by 5 parts of polystyrolsulfon acids, 0.3
Part hydrophilic graphene, 5 parts of acrylic monomers, it is 1.5 sulfonic acid solutions that 35 parts of aniline monomers, which are added to dress by 300 parts of pH value,
In reactor, it is 5 DEG C to control temperature of reactor with ice-water bath, with 400r/min rotating speed mechanical agitation, then adds 0.3 part and draws
Agent is sent out, obtains composite solution；
The anode material being prepared using embodiment 1~5 and comparative example 1~2 is anode, using stainless steel and iron silk screen as the moon
Pole, tested after biological stable fuel cell with galvanostatic method, the maximum power density and open circuit electricity of test biology fuel cell
Pressure, test data are as shown in the table.
The difference of comparative example 1 and embodiment 2 is that carbon cloth, graphene and the polyaniline of comparative example 1 are all without hydrophilic place
Reason, understood according to the contrast of the test data of comparative example 1 and embodiment 2, electricity of the hydrophily to biological fuel cell anode material
Performance has a significant effect, and the good anode material of hydrophily has more preferable electricity generation performance；According to comparative example 2 and embodiment 2
Test data contrast understands that the surface area of pore-foaming agent increase anode material is advantageous to strengthen the electricity generation performance of anode material.
Protection scope of the present invention is not limited merely to above-described embodiment, and all technical schemes for belonging under thinking of the present invention are equal
Belong to protection scope of the present invention.It should be pointed out that for those skilled in the art, the present invention is not being departed from
Some improvements and modifications under the premise of principle, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (5)
1. a kind of preparation method of biological fuel cell anode material, it is characterised in that comprise the following steps：
S1. count in parts by weight, 5 parts of single-layer graphene oxides, 5~8 parts of styrene sulfonic acids and 100 parts of deionized waters mixed,
24h is stirred at room temperature, then adds 5~7 parts of hydrazine hydrates, flow back 8~12h at 90~95 DEG C, then filtration washing, will be solid
Body product vacuum is dried, and obtains hydrophilic graphene；
S2. count in parts by weight, by 5 parts of polystyrolsulfon acids, 0.3~0.9 part of hydrophilic graphene, 1~5 part of acrylic acid list
Body, 30~40 parts of aniline monomers are added in reactor of the dress by the sulfonic acid solutions that 300 parts of pH value are 1~1.5, with ice-water bath control
Temperature of reactor processed is 0~5 DEG C, with 400~500r/min rotating speed mechanical agitation, then adds 0.25~0.3 part of initiator,
1~3 part of pore-foaming agent, obtains composite solution；
S3. composite solution is uniformly coated on carbon cloth surfaces, reacts 1~2h at room temperature, then dried at 55~60 DEG C,
Alternately rinsed with deionization and acetone again, finally obtain anode material.
A kind of 2. preparation method of biological fuel cell anode material according to claim 1, it is characterised in that the carbon
By pre-processing, preprocess method is cloth：Carbon cloth is immersed in ethanol or acetone soln, then 0.5~1h of ultrasonic vibration, so
Take out and dry afterwards, be then placed in the hydrogen peroxide that concentration is 20~30% and soak 6~8h, rinsed and then dried standby with water.
3. the preparation method of a kind of biological fuel cell anode material according to claim 1, it is characterised in that described multiple
Close solution and carbon cloth surfaces are coated in 15min.
A kind of 4. preparation method of biological fuel cell anode material according to claim 1, it is characterised in that the cause
Hole agent is the mixture of sodium carbonate and sodium acid carbonate, and the mass ratio of sodium carbonate and sodium acid carbonate is 1:0.5~1.3.
5. the preparation method of a kind of biological fuel cell anode material according to claim 1, it is characterised in that described to draw
Hair agent is ammonium persulfate, potassium peroxydisulfate, any one in ammonium persulfate/sodium sulfite, over cure in ammonium persulfate/sodium sulfite
The molal weight ratio of sour ammonium and sodium sulfite is 1:0.1~0.3.
Priority Applications (1)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110943230A (en) * | 2019-11-21 | 2020-03-31 | 南京师范大学 | A kind of microbial fuel cell anode and preparation method thereof |
| CN114725404A (en) * | 2022-04-22 | 2022-07-08 | 福州大学 | Biocompatible microbial fuel cell composite anode material and preparation method thereof |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1264321A (en) * | 1997-05-13 | 2000-08-23 | 普渡研究基金会 | Hydrogel composites and superporous hydrogel composites having fast swelling, high mechanical strenght, and superabsorbent properties |
| CN1488331A (en) * | 2003-08-13 | 2004-04-14 | 复旦大学 | A superporous hydrogel composite, its preparation method and its application in pharmacy |
| CN1757662A (en) * | 2005-07-07 | 2006-04-12 | 复旦大学 | Interpenetrating network polymer type super porous aquogel, its prepn. method and application |
| CN1768920A (en) * | 2005-10-20 | 2006-05-10 | 北京科技大学 | A method for preparing temperature-controlled instant-release microcapsules for preparing porous hydrogels |
| CN102030984A (en) * | 2010-11-26 | 2011-04-27 | 中国人民解放军国防科学技术大学 | Preparation method of water-soluble self-doped polyaniline (PANI) electrochromic material |
| CN102225985A (en) * | 2011-04-20 | 2011-10-26 | 黎明职业大学 | A kind of preparation method of macroporous sodium carboxymethyl cellulose graft copolymer with rapid swelling adsorption performance |
| CN102432875A (en) * | 2011-09-19 | 2012-05-02 | 中国科学院长春应用化学研究所 | Aqueous polyaniline and preparation method thereof |
| CN102492296A (en) * | 2011-11-25 | 2012-06-13 | 江南大学 | Synthesis method of water dispersible polyaniline/graphene composite material |
| CN103214670A (en) * | 2013-03-05 | 2013-07-24 | 中国科学院长春应用化学研究所 | Aqueous polyaniline hollow microballoon and preparation method thereof |
| CN104098766A (en) * | 2013-04-12 | 2014-10-15 | 中国石油化工股份有限公司 | Method for preparing polyaniline by using organic polysulfonic acid |
| CN104211053A (en) * | 2014-09-04 | 2014-12-17 | 济宁利特纳米技术有限责任公司 | Preparation method of modified graphene aqueous dispersion |
| CN104448155A (en) * | 2014-11-19 | 2015-03-25 | 山东诺尔生物科技有限公司 | Preparation method of high-diffusivity water-absorbent resin |
| CN106398206A (en) * | 2016-09-09 | 2017-02-15 | 武汉大学 | Preparation methods of oxidized graphene/polyaniline/titanium dioxide nanocomposite and polyaniline nanometer anticorrosive paint |
| CN106941179A (en) * | 2017-03-20 | 2017-07-11 | 哈尔滨工业大学 | A kind of preparation of graphene Polyaniline-modified carbon cloth electrode material and the method for accelerating biological anode domestication |
-
2017
- 2017-08-27 CN CN201710746438.8A patent/CN107591540A/en active Pending
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1264321A (en) * | 1997-05-13 | 2000-08-23 | 普渡研究基金会 | Hydrogel composites and superporous hydrogel composites having fast swelling, high mechanical strenght, and superabsorbent properties |
| CN1488331A (en) * | 2003-08-13 | 2004-04-14 | 复旦大学 | A superporous hydrogel composite, its preparation method and its application in pharmacy |
| CN1757662A (en) * | 2005-07-07 | 2006-04-12 | 复旦大学 | Interpenetrating network polymer type super porous aquogel, its prepn. method and application |
| CN1768920A (en) * | 2005-10-20 | 2006-05-10 | 北京科技大学 | A method for preparing temperature-controlled instant-release microcapsules for preparing porous hydrogels |
| CN102030984A (en) * | 2010-11-26 | 2011-04-27 | 中国人民解放军国防科学技术大学 | Preparation method of water-soluble self-doped polyaniline (PANI) electrochromic material |
| CN102225985A (en) * | 2011-04-20 | 2011-10-26 | 黎明职业大学 | A kind of preparation method of macroporous sodium carboxymethyl cellulose graft copolymer with rapid swelling adsorption performance |
| CN102432875A (en) * | 2011-09-19 | 2012-05-02 | 中国科学院长春应用化学研究所 | Aqueous polyaniline and preparation method thereof |
| CN102492296A (en) * | 2011-11-25 | 2012-06-13 | 江南大学 | Synthesis method of water dispersible polyaniline/graphene composite material |
| CN103214670A (en) * | 2013-03-05 | 2013-07-24 | 中国科学院长春应用化学研究所 | Aqueous polyaniline hollow microballoon and preparation method thereof |
| CN104098766A (en) * | 2013-04-12 | 2014-10-15 | 中国石油化工股份有限公司 | Method for preparing polyaniline by using organic polysulfonic acid |
| CN104211053A (en) * | 2014-09-04 | 2014-12-17 | 济宁利特纳米技术有限责任公司 | Preparation method of modified graphene aqueous dispersion |
| CN104448155A (en) * | 2014-11-19 | 2015-03-25 | 山东诺尔生物科技有限公司 | Preparation method of high-diffusivity water-absorbent resin |
| CN106398206A (en) * | 2016-09-09 | 2017-02-15 | 武汉大学 | Preparation methods of oxidized graphene/polyaniline/titanium dioxide nanocomposite and polyaniline nanometer anticorrosive paint |
| CN106941179A (en) * | 2017-03-20 | 2017-07-11 | 哈尔滨工业大学 | A kind of preparation of graphene Polyaniline-modified carbon cloth electrode material and the method for accelerating biological anode domestication |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110943230A (en) * | 2019-11-21 | 2020-03-31 | 南京师范大学 | A kind of microbial fuel cell anode and preparation method thereof |
| CN114725404A (en) * | 2022-04-22 | 2022-07-08 | 福州大学 | Biocompatible microbial fuel cell composite anode material and preparation method thereof |
| CN114725404B (en) * | 2022-04-22 | 2023-09-01 | 福州大学 | Biocompatible microbial fuel cell composite anode material and preparation method thereof |
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