CN110165225A - A kind of modified anode nanometer composite material and preparation method of SMFC - Google Patents
A kind of modified anode nanometer composite material and preparation method of SMFC Download PDFInfo
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- CN110165225A CN110165225A CN201910431695.1A CN201910431695A CN110165225A CN 110165225 A CN110165225 A CN 110165225A CN 201910431695 A CN201910431695 A CN 201910431695A CN 110165225 A CN110165225 A CN 110165225A
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Abstract
The invention belongs to technical field of microbial fuel battery, more particularly to a kind of modified anode nanometer composite material and preparation method of SMFC, SMFC has biggish specific surface area with modified anode nanometer composite material, a large amount of attachment sites can be provided for electricity-producing microorganism, 1 supported in mesoporous, 4- dihydroxy anthraquinone can attract the enrichment of electricity-producing microorganism as electron medium, improve the electron transmission efficiency of electricity-producing microorganism, the modified anode nanometer composite material of SMFC, which is coated in electrode material surface, can significantly shorten the starting time of battery, improve the output voltage of battery, compared with naked carbon plate, nearly 100% is improved in the output voltage outside plus under 1000 Ω resistance using the microbiological fuel cell of modified carbon plate anode, simultaneously, electricity-producing microorganism can adhere in electrode surface rapidly, output Voltage increases rapidly and stablizes in 300mV or so.
Description
Technical field:
The invention belongs to technical field of microbial fuel battery, and in particular to a kind of modified anode nanometer composite wood of SMFC
Material and preparation method thereof.
Background technique:
SMFC (bottom sediment type microbiological fuel cell) will be aoxidized using the electricity-producing microorganism in bottom sediment
The electronics generated during organic matter is transferred to extracellular electrode along respiratory chain, occurs instead after being then passed to cathode with oxygen
It answers, constitutes entire circuit.Natural anaerobic environment in bottom sediment and the organic matter and minerals contained is produce electricity micro- life
The growth of object provides advantageous condition.Organic matter reserves in bottom sediment are huge and renewable, and SMFC's is long-term
Operation not will receive the limitation of fuel supply.The electrode material of SMFC is generally the inert materials such as graphite, ensure that the length of SMFC
Phase runs the constraint that not will receive battery material.Based on this, SMFC can provide electricity in situ steady in a long-term as underwater kit
The novel power supply of energy.
A kind of system of the modified anode of marine sediment microbiological fuel cell disclosed in Chinese patent 201410779536.8
Preparation Method is the following steps are included: it is 1.6cm, long 10cm, surface area 54cm that (1), which takes diameter,2Graphite rod as graphite anode,
Graphite surface is polished to smooth with 180,360,600,800 sand paper respectively；(2) with ferroso-ferric oxide, manganese sulfate, graphite powder,
Kaolin and six water nickel chlorides are that raw material makes Mn2++Fe3O4+Ni2+ graphite anode, wherein the partial size of graphite powder is 500 mesh, high
The partial size of ridge soil is 400 mesh；By ferroso-ferric oxide, manganese sulfate, graphite powder, kaolin and six water nickel chlorides respectively according to 6%,
3%, 58%, 30% and 2% mass ratio is mixed, and gross mass is 4 grams；(3) a certain amount of go is added after mixing
Ionized water is applied to four sides of graphite electrode, and graphite electrode, is then placed in Muffle furnace by dry 45min at a temperature of 80 DEG C,
In 380 DEG C~450 DEG C roasting temperature 48h；(4) aperture is made a call in the graphite one end pre-processed, conducting ring is added into hole
Oxygen resin in the epoxy resin that conducting wire exposed part inserts in the hole, but is to ensure that the exposed part of conducting wire cannot be with graphite
Matrix is in contact；(5) etc. after conductive epoxy resins have solidified, it is whether good that the link between electrode and conducting wire is tested with multimeter
It is good, then the remaining part of aperture is filled up with the epoxy resin of insulation, dries kept dry；(6) dose volume ratio be 5:2~
45% sulfuric acid of 5:3 and 36% concentrated nitric acid mixed solution；(7) the good graphite anode of pre-treatment is impregnated 30 in the solution
Minute, reaction temperature is 65 DEG C；(8) graphite anode handled well is removed, pure water impregnates repeatedly, until pH value does not become
Change；(9) cleaned modified graphite anode is put into air dry oven, 80 DEG C drying 12 hours；Chinese patent
A kind of specific preparation step of the preparation method of anode of microbial fuel cell material disclosed in 201810941639.8 are as follows: (1)
According to parts by weight, 5~10 parts of graphene oxides are successively taken, 5~10 parts of thionyl chlorides, 5~10 parts of propargyl alcohols, 5~10 parts poly-
Styrene, first by graphene oxide and thionyl chloride heating reflux reaction for 24 hours after, after filtration washing is dry, then add with propargyl alcohol
Hot back flow reaction for 24 hours, after filtration washing is dry, obtains the graphene oxide of alkynyl, then by the graphene oxide of alkynyl and
Polystyrene reactant obtains Polystyrene graphene oxide；(2) carbon nanotube is mixed with water 1:10~1:20 in mass ratio
Ultrasound, is subsequently added into 0.3~0.5 times of carbon nanotube mass of polyamine, and heating stirring mixing is subsequently added into carbomer, stirs
Reaction, filtering are dry to get modified carbon nano-tube；(3) according to parts by weight, 5~10 parts of Polystyrene oxidations are successively taken
After graphene, 3~5 parts of modified carbon nano-tubes, 5~10 parts of compounding metal salt solutions and 3~5 parts of Nano metal powders are stirred,
PH to 8.0 is adjusted with urea liquid, then through 1~2h of hydro-thermal reaction, then uses hydrogen reducing, filtering and is dried washing, and microorganism is obtained
Dye cell anode material；A kind of modified pomelo peel foamy carbon Microbial fuel electricity disclosed in Chinese patent 201610173102.2
The specific preparation step of the preparation method of pond anode material are as follows: (1) take 2~3 shaddock peelings, prune pomelo peel surface Huang with knife
Color wax coat obtains the skin flesh of white sponge structure, is packed into gauze bag after impregnating 3~5h with deionized water, vacantly tangles yarn
Cloth bag drips the moisture in skin flesh naturally, takes out pomelo peel-flesh when dripping again without water droplet in gauze bag, is put into baking oven 105
Dry 2~3h at~110 DEG C；(2) pomelo peel after above-mentioned drying is put into high temperature carbonization furnace, nitrogen displacement is passed through into furnace
Wherein all air out, and 100 DEG C of 30~40min of pre- charing are first warming up to 8 DEG C/min rate program under nitrogen protection, then
800~900 DEG C are warming up to 5 DEG C/min rate, keeps the temperature after carbonizing 1~2h to its cooled to room temperature, obtains shaddock ped foam
Carbon；(3) shaddock ped foamy carbon obtained above is put into airslide disintegrating mill and smashes it through 200 mesh standard sieves, then will be after sieving
Foam carbon dust injects diameter for 1~2cm, in the cylindrical die of a height of 5~6cm, moves into high temperature sintering furnace in 500~600
Demoulding after 2~3h of sintering, obtains cylindrical foam carbon electrode at DEG C, spare；(4) 400~500g tourmaline is weighed, superfine powder is used
Grinding machine carries out grinding and crossing 900~1000 mesh standard sieves, by solid-to-liquid ratio is that 1:50 pours into concentration and is by obtained tourmaline powder
In 0.5mol/L hydrochloric acid solution, after 20~30min is impregnated in stirring, with deionized water filtering and washing 3~5 times；(5) by 100~
Ultra-fine tourmaline powder and 5~8g polyvinyl butyral after 120g washing pour into 2~3L acetone, are put into ultrasonic disperse machine
In 10~20min handled with 200~300W power ultrasonic disperse, then be placed on magnetic stirrer, continue stirring 20~for 24 hours,
Obtain mixing tourmaline powder suspension；(6) tourmaline powder suspension obtained above is poured into 5L beaker as electrolysis
Liquid is anode with platinized platinum, and spare cylindrical foam carbon electrode is cathode, apply 50 in positive and negative interpolar using electrophoretic deposition~
The electric field of 70V/cm, 1~2h of electrophoretic deposition；(7) after depositing, the foam carbon electrode after depositing tourmaline is taken out, is put into true
After the dry 8~10h of empty drier, tube type resistance furnace is moved into, with 1000~1200 DEG C of 1~2h of high temperature sintering under argon atmosphere
It comes out of the stove, up to modified pomelo peel foamy carbon anode of microbial fuel cell material after cooled to room temperature；Above-mentioned patented method
The anode material or conductivity of preparation are significantly improved or electric conductivity significantly improves, but the output of the SMFC of its preparation
Power is very low, and operation stability is undesirable, and as the key position of SMFC, anode is both the existence place of electricity-producing microorganism,
It plays again by the key effect of electronics transfer to external circuit, biocompatibility, specific surface area and the conduction of anode simultaneously
Rate etc. all largely affects the output power of SMFC.Therefore, it is necessary to urgent to develop more excellent performance of sun
Pole material promotes the performance of SMFC.
Summary of the invention:
It is an object of the invention to overcome disadvantage of the existing technology, it is compound with modified anode nanometer to design a kind of SMFC
Material and preparation method thereof shortens the starting time of microbiological fuel cell, improves the output voltage of microbiological fuel cell, be
The promotion of microbiological fuel cell performance provides new thinking.
To achieve the goals above, SMFC of the present invention is reduction-oxidation graphite with modified anode nanometer composite material
Alkene/titanium dioxide/1,4- dihydroxy anthraquinone composite material；Its main structure includes titanium dioxide microballoon sphere, mesoporous and 1,4- dihydroxy
Base anthraquinone and redox graphene；Several mesoporous, mesoporous inside are provided on the titanium dioxide microballoon sphere that diameter is 400nm
Filled with Isosorbide-5-Nitrae-dihydroxy anthraquinone, titanium dioxide microballoon sphere is coated with one layer of redox graphene.
The modified anode nanometer composite material of SMFC of the present invention can with binder (Nafion) to set ratio
It is coated on the surface of carbon-based material or metal_based material after example mixing, is used to prepare SMFC with modified anode.
The technical process of the modified anode nanometer composite material and preparation method thereof of SMFC of the present invention includes sol-gel
Method prepares meso-porous titanium dioxide titanium precursors, is heated to reflux in graphene oxide water solution, carries out hydro-thermal in ethanol water
Reaction, high-temperature calcination and negative pressure support 1,4- dihydroxy anthraquinone totally five steps under an inert atmosphere:
(1) sol-gel method prepares meso-porous titanium dioxide titanium precursors: 4mL tetra-n-butyl titanate is added to 200mL second two
In alcohol, mixed solution is formed with the revolving speed stirring 6-24h of 400rpm at room temperature, mixed solution is added to and is gone containing 1-2mL
In the 340mL acetone of ionized water, 2h is stirred with the revolving speed of 600rpm, white precipitate is collected by centrifugation；
(2) be heated to reflux in graphene oxide water solution: the white precipitate for taking 0.5g step (1) to obtain be added to containing
In the 100mL deionized water of 0.125-0.05g graphene oxide, flow back 4h at 90 DEG C, and gray precipitate is collected by centrifugation；
(3) hydro-thermal reaction is carried out in ethanol water: by the gray precipitate that step (2) obtains be scattered in 20mL ethyl alcohol and
In the mixed solution of 10mL deionized water composition, for 24 hours, black precipitate is collected by centrifugation in hydro-thermal reaction under the conditions of 180 DEG C；
(4) high-temperature calcination under an inert atmosphere: under nitrogen atmosphere, 400 DEG C of calcining black precipitate 4h, obtain graphene/
Titanium dioxide composite nano material；
(5) negative pressure supports 1,4- dihydroxy anthraquinone: the graphene for taking 0.2g step (4) to obtain/titanium dioxide composite Nano
Material is scattered in 50mL and contains in the ethyl alcohol of supersaturated Isosorbide-5-Nitrae-dihydroxy anthraquinone, is then transferred to the vacuum that vacuum degree is 50mbar
In drying box, 15min is stood, is taken out, washing and drying wash repeatedly and 3 times dry, obtain being supported with Isosorbide-5-Nitrae-dihydroxy anthraquinone
Graphene/titanium dioxide composite nano material.
Compared with prior art, the present invention SMFC has biggish specific surface area, energy with modified anode nanometer composite material
Enough provide a large amount of attachment sites for electricity-producing microorganism, it is mesoporous in Isosorbide-5-Nitrae-dihydroxy anthraquinone for supporting can be inhaled as electron medium
The enrichment for drawing electricity-producing microorganism improves the electron transmission efficiency of electricity-producing microorganism, by the modified anode nanometer composite material of SMFC
The starting time that battery can significantly be shortened coated in electrode material surface, the output voltage of battery is improved, compared with naked carbon plate,
Nearly 100% is improved in the output voltage outside plus under 1000 Ω resistance using the microbiological fuel cell of modified carbon plate anode, together
When, electricity-producing microorganism can adhere in electrode surface rapidly, and output voltage increases rapidly and stablizes in 300mV or so.
Detailed description of the invention:
Fig. 1 is the main structure schematic illustration of the modified anode nanometer composite material of SMFC of the present invention.
Fig. 2 is the scanning electron microscope (SEM) photograph of graphene/titanium dioxide composite nano material of the present invention.
Fig. 3 is the nitrogen adsorption desorption curve graph of graphene/titanium dioxide composite nano material of the present invention.
Fig. 4 is the sodium-chloride water solution that 1,4- dihydroxy anthraquinone of the present invention is 3.5% in mass percent concentration
In releasing curve diagram.
Fig. 5 is modified carbon plate of the present invention and naked carbon plate in the output voltage curve figure outside plus under 1000 Ω resistance.
Specific embodiment:
It is described further by way of example and in conjunction with the accompanying drawings.
Embodiment 1:
The present embodiment is related to the SMFC release and characterization of the 1,4- dihydroxy anthraquinone in modified anode nanometer composite material:
The sodium-chloride water solution that 20mL mass percent concentration is 3.5% is dispersed with modified anode nanometer composite material by 50mgSMFC
In, 6 absorbance values of primary frequency test are tested with 2h, scanning range 200-900nm draws 1 according to test result,
The standard curve of 4- dihydroxy anthraquinone, and then convert and obtain SMFC Isosorbide-5-Nitrae-dihydroxy anthraquinone in modified anode nanometer composite material
Release profiles, show that the modified anode nanometer composite material of SMFC can support Isosorbide-5-Nitrae-dihydroxy anthraquinone and slow release, 1,
4- dihydroxy anthraquinone can be improved the electron transmission efficiency between electricity-producing microorganism and electrode as electron medium.
Embodiment 2:
The present embodiment is related to SMFC and prepares bottom sediment type microbiological fuel cell with modified anode nanometer composite material
The method of modified anode, comprising the following steps:
(1) taking length is 3cm, width 3cm, is highly the carbon plate of 0.5cm as anode, respectively with 800 mesh, 1000
Mesh, 1200 mesh sand paper be polishing to smooth surface, be cleaned by ultrasonic 30min；
(2) in every 25mgSMFC with 25 μ L Nafion aqueous solutions being added in modified anode nanometer composite material and 125 μ L are gone
Ionized water is mixed evenly, and ultrasonic disperse is until form homogeneous slurry；
(3) with fine, soft fur brush by slurries with 5mg/cm2Amount be uniformly coated on the surface of carbon plate anode, place at room temperature for 24 hours
It is dry, obtain the modified anode of bottom sediment type microbiological fuel cell.
Embodiment 3:
The present embodiment is related to the establishment and performance test of bottom sediment type microbiological fuel cell, and bottom sediment type is micro-
Biological fuel cell is made of ooze and seawater, and lower section is the ooze that height is 20cm, modification carbon plate sun prepared by embodiment 2
Pole is placed at ooze depth 10cm, and top is the natural sea-water that height is 10cm, and cathode is placed in natural sea-water, and cathode is
The carbon fiber brush of length 5cm；After bottom sediment type microbiological fuel cell is completed, outer plus 1000 Ω between anode and cathode
External resistance, with data collection system record bottom sediment type microbiological fuel cell both ends output voltage, with naked carbon plate
The bottom sediment type microbiological fuel cell of anode preparation is control group, is compared, as shown in figure 5, modified carbon plate anode
The output voltage of the bottom sediment type microbiological fuel cell of preparation increases rapidly and stablizes in 300mV or so, reaches most
The time of big voltage is 50h, the bottom sediment type microbiological fuel cell of naked carbon plate anode preparation reach maximum voltage when
Between be 70h, and the more naked carbon plate anode of output voltage of the bottom sediment type microbiological fuel cell of modified carbon plate anode preparation
The output voltage of the bottom sediment type microbiological fuel cell of preparation improves nearly 100%.
Claims (5)
1. a kind of modified anode nanometer composite material of SMFC, it is characterised in that be redox graphene/titanium dioxide/Isosorbide-5-Nitrae-
Dihydroxy anthraquinone composite material.
2. the modified anode nanometer composite material of SMFC according to claim 1, it is characterised in that main structure includes two
Titania microsphere, mesoporous and 1,4- dihydroxy anthraquinone and redox graphene；It is set on the titanium dioxide microballoon sphere that diameter is 400nm
It is mesoporous to be equipped with several, mesoporous inside is filled with Isosorbide-5-Nitrae-dihydroxy anthraquinone, and titanium dioxide microballoon sphere is coated with oxygen reduction
Graphite alkene.
3. the modified anode nanometer composite material of SMFC according to claim 1, it is characterised in that can with binder
It is coated on the surface of carbon-based material or metal_based material after mixing, is used to prepare SMFC with modified anode.
4. a kind of modified anode nanometer composite material and preparation method thereof of SMFC, it is characterised in that technical process includes sol-gel
Method prepares meso-porous titanium dioxide titanium precursors, is heated to reflux in graphene oxide water solution, carries out hydro-thermal in ethanol water
Reaction, high-temperature calcination and negative pressure support 1,4- dihydroxy anthraquinone totally five steps under an inert atmosphere.
5. the modified anode nanometer composite material and preparation method thereof of SMFC according to claim 4, it is characterised in that technique mistake
Journey are as follows:
(1) sol-gel method prepares meso-porous titanium dioxide titanium precursors: 4mL tetra-n-butyl titanate is added to 200mL ethylene glycol
In, mixed solution is formed with the revolving speed of 400rpm stirring 6-24h at room temperature, by mixed solution be added to containing 1-2mL go from
In the 340mL acetone of sub- water, 2h is stirred with the revolving speed of 600rpm, white precipitate is collected by centrifugation；
(2) be heated to reflux in graphene oxide water solution: the white precipitate for taking 0.5g step (1) to obtain be added to containing
In the 100mL deionized water of 0.125-0.05g graphene oxide, flow back 4h at 90 DEG C, and gray precipitate is collected by centrifugation；
(3) hydro-thermal reaction is carried out in ethanol water: dispersing 20mL ethyl alcohol and 10mL for the gray precipitate that step (2) obtains
In the mixed solution of deionized water composition, for 24 hours, black precipitate is collected by centrifugation in hydro-thermal reaction under the conditions of 180 DEG C；
(4) high-temperature calcination under an inert atmosphere: under nitrogen atmosphere, 400 DEG C of calcining black precipitate 4h obtain graphene/dioxy
Change titanium composite nano materials；
(5) negative pressure supports 1,4- dihydroxy anthraquinone: the graphene/titanium dioxide composite nano material for taking 0.2g step (4) to obtain
It is scattered in 50mL to contain in the ethyl alcohol of supersaturated Isosorbide-5-Nitrae-dihydroxy anthraquinone, is then transferred to the vacuum drying that vacuum degree is 50mbar
In case, 15min is stood, is taken out, washing and drying wash repeatedly and 3 times dry, obtain being supported with Isosorbide-5-Nitrae-dihydroxy anthraquinone stone
Black alkene/titanium dioxide composite nano material.
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| CN115159665A (en) * | 2022-09-09 | 2022-10-11 | 太原理工大学 | Device for removing heavy metal ions in coking sludge |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115159665A (en) * | 2022-09-09 | 2022-10-11 | 太原理工大学 | Device for removing heavy metal ions in coking sludge |
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