CN106257729A - Self-respiration type light helps microbial fuel cell and application thereof - Google Patents

Self-respiration type light helps microbial fuel cell and application thereof Download PDF

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CN106257729A
CN106257729A CN201510337590.1A CN201510337590A CN106257729A CN 106257729 A CN106257729 A CN 106257729A CN 201510337590 A CN201510337590 A CN 201510337590A CN 106257729 A CN106257729 A CN 106257729A
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anode
light
fuel cell
liquid storage
self
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李�灿
张丙青
施晶莹
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Dalian Institute of Chemical Physics of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/08—Fuel cells with aqueous electrolytes
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Materials Engineering (AREA)
  • Fuel Cell (AREA)

Abstract

The present invention relates to a kind of self-respiration type light and help microbial fuel cell, described fuel cell is excited by light and luminous energy and biomass energy is converted into electric energy, specifically includes optical window, liquid storage cylinder, seal washer, anode fixed plate, anode diffusion layer, membrane electrode, cathode gas diffusion layer, cathode collector plate, end plate；It is respectively equipped with packing ring sealing together in the inner side of anode fixed plate and cathode collector plate, it is provided with membrane electrode between two seal washers, membrane electrode is provided with cathode gas diffusion layer being positioned at cathode collector plate side, membrane electrode is provided with anode diffusion layer being positioned at anode fixed plate side, end plate it is provided with outside cathode collector plate, it is provided with liquid storage cylinder outside anode fixed plate, it is provided with seal washer between liquid storage cylinder and anode fixed plate, embedding optical window is hollowed out in the middle of liquid storage cylinder front, optical window is as the entrance port of light, liquid storage cylinder is internal places light anode and fuel solution, the invention provides one inexpensively, the green new way that solar energy and biomass energy are converted to electric energy.

Description

Self-respiration type light helps microbial fuel cell and application thereof
Technical field
The invention belongs to fuel cell field, be specifically related to a kind of self-respiration type light and help microbial fuel cell and application thereof, in institute The self-respiration type light stated helps in microbial fuel cell, luminous energy and biomass energy is converted into electric energy and discharges.
Background technology
The energy and environmental problem are human society existence and the two large problems of Faced In Sustainable Development.At present, countries in the world are main Energy system is mainly based upon oil, and coal etc. is containing C Fossil fuel, and energy is converted and mainly realized by heat engine process, Owing to being limited by Carnot cycle, not only transformation efficiency is low, causes serious energy waste, and produces substantial amounts of dust, CO2、 The harmful substance such as nitrogen oxides and oxysulfide and noise, the air thus caused, water quality, soil etc. pollute, seriously The development that threaten the living environment of the mankind, the energy and environment is faced with huge challenge.
Fuel cell, as a kind of novel electrochemical energy conversion device, the energy transition density high with it and environmental friendliness etc. Factor gets the attention.The chemical energy being stored in fuel and oxidant can be converted into electric energy by fuel cell, by Changing without heat energy in centre, do not limited by Carnot cycle, be that a kind of energy transformation ratio is high, noise is low, it is little, green to pollute The energy conversion device (Nature, 2011,414 (6861): 331.) of color.The kind of fuel cell has a lot, and it sets substantially Count as follows, it may be assumed that they all contain two electrodes (anode and a negative electrode), electrode has and can be used to accelerate electrochemistry The catalyst of reaction, carries the electrolyte of charging charge between electrode.It is fuel used includes fuel gas (H2, CO etc.) and Liquid fuel (Hydrocarbon such as methanol, formic acid) (Fuel Cells, 2001,1 (1), 5-39.).In this year, directly fire Material battery extensively receives because its fuel source and studies widely, it use various organic molecules as fuel, as methanol, Formic acid, formaldehyde, ethanol etc., these fuel sources enrich, easy to use, become the hot research of fuel cell.But, Direct fuel cell can not well realize at a lower temperature C-C key in organic molecule due to anode noble metal catalyst break Schizogenesis becomes CO2, thus limit biomass resource in nature utilization (Appl.Catal.B:Environ., 2010,97, 1-12).Another kind of important fuel cell biological fuel cell is by widely studied, because it can utilize general fuel cell institute Chemical energy is converted into electric energy as fuel by unavailable multiple natural organic matter, can be divided into microorganism according to the classification of catalyst Fuel cell and enzyme type fuel cell.But, the mass transport process of microbiological fuel cell is vulnerable to biomembrane obstruction and causes electric energy to turn Change efficiency to reduce, and the problem such as enzyme type fuel cell exists that output is low and service life is short, these factors limit biological combustion The development of material battery.
Photoelectrochemical cell employing light, at room temperature can be by H as driving force2O or oxidation operation, for the design of fuel cell Provide new thinking.1976, Bard etc. proposed a kind of representational photoelectrochemistrpool pool, and this chemical bath is with TiO2For light sun Pole, Pt are to electrode, on anode, water decomposition are generated O2, to O occurs on electrode2Reduction reaction, device is easy, and energy The work (J.Electrochem.Soc., 1976,123,1027-1030.) of persistence.In recent years, light helps biomass fuel The development of battery is based on photoelectrochemical cell, to be easier to oxidized biomass molecule as substrate, it is achieved luminous energy and life Material can be converted into the device of electric energy.Light helps the working mechanism of microbial fuel cell to be when semiconductor optical anode is prohibited by more than it When the light of bandwidth excites, electronics and hole in quasiconductor separate, and the few son in hole moves to semiconductor surface to be made in solution Biomass molecule generation oxidation reaction, light induced electron moves to electrode by external circuit, and electrode is being occurred O2Reduction anti- Should, the most whole System forming loop, produce electric energy.Therefore, compare with traditional direct alcohol fuel cell, Light helps microbial fuel cell at room temperature to operate, and solar energy can be utilized for driving force simultaneously, have broader practice Prospect (J.Hazard.Mater., 2011,185,575-590.).
2005, Kaneko etc. was the most directly to propose the seminar that light helps microbial fuel cell to study, and they use nanometer many The TiO in hole2As light anode, using Pt as negative electrode, ammonia is carried out photo-electro chemical oxidation and produces H2With electric energy (Chem.Commun., 2005,1625-1627.).Subsequently, they are under this light helps the system of microbial fuel cell, with solar energy as driving force, Successfully the biomass such as alcohols, saccharide, cellulose, aminoacid, protein or biomass derivatives are changed into electric energy, at mark Under quasi-solar irradiation (AM 1.5G), during using methanol as fuel, obtaining open-circuit voltage (Voc) is 0.44V, short circuit current (Isc) For 0.31mA cm-2, power density (Pmax) is 0.037mW cm-2Battery performance (Electrochem.Commun., 2006, 8,336-340；J.Appl.Electrochem., 2007,37,1039-1046.), even, this light helps biomass fuel Material battery can also be urinated by photoelectrochemical degradation, refuse etc. produces electricity (Biosens.Bioelectron., 2007,23 (1), 140-143.).Lianos etc. have been also carried out more research in terms of light fuel cell, and they are at the extinction of light anode quasiconductor, The selection of electrolyte, the source of fuel, the aspect such as design of light fuel cell device has all carried out more systematic research (J. Hazard.Mater.,2011,185,575-590；J.Appl.Electrochem.,2012,42,737-743； Electrochim.Acta,2012,80,399-404；Appl.Catal.B:Environ.,2011,107,188-196； Catal.Today,2009,144,166-171.).They successively use the Degussa P25 of business, support Pt, RuO2、 The P25 of NiO, Ru doping P25 or in order to widen TiO2The extinction of electrode material, uses CdS or ZnS as the TiO of photosensitizer2 As light anode, investigate the light Electrooxidation Mechanism that biomass molecule is the most different, and also inquired into the moon Effect to battery discharge when sun the two poles of the earth exist chemistry bias, has investigated single pond, double ponds, and from breathe battery operation principle and Character, using biomass and derivative molecular glycerol, sorbitol, xylose, glucose and fructose etc. as substrate, successfully will too Sun can be changed into electric energy with the chemical energy of biomass reaction.But, they use light anode material compare limitation, all the time around TiO2, it is not extended to other quasiconductors.
The TiO of the different crystalline phase of the preparation such as Yan2Film light anode, uses glucose as fuel, finds that Anatase shows the highest Photoelectric current, with anatase TiO2For the glucose fuel cell of light anode under 350nm light excites, its battery peak power is 1.48μW cm-2(Chem.Commun.,2013,49,8632-8634.).Osterloh etc. are with TiO2For light anode, Portugal Grape sugar is as substrate, at solar simulation light (AM1.5,100mW cm-2Under), gained battery peak power is 0.57mW cm-2, This seminar uses WO simultaneously3As light anode, the maximum power of gained battery is 0.014mW cm-2(ChemSusChem, 2012,5,1482-1487.)。
As can be seen here, being currently used for light helps the semi-conducting material in microbial fuel cell mainly with TiO2It is main, WO3Also have Research, kind is the most less, and due to TiO2And WO3Gap is wider, limits absorption and the utilization of sunlight.Therefore, Explore the wider semiconductor catalyst of light absorption range helps the development of fuel cell the most helpful to light.
Summary of the invention
The problem existed for above-mentioned fuel cell, it is an object of the invention to provide a kind of self-respiration type light and helps biomass fuel electricity Pond and application thereof.
The technical scheme is that
A kind of self-respiration type light helps microbial fuel cell, including optical window, liquid storage cylinder, seal washer, anode fixed plate, anode Diffusion layer, membrane electrode, cathode gas diffusion layer, cathode collector plate, end plate；
It is respectively equipped with packing ring sealing together in the inner side of anode fixed plate and cathode collector plate, between two seal washers, is provided with membrane electrode, Membrane electrode is provided with cathode gas diffusion layer being positioned at cathode collector plate side, and membrane electrode is provided with anode being positioned at anode fixed plate side Diffusion layer, is provided with end plate outside cathode collector plate, be provided with liquid storage cylinder, between liquid storage cylinder and anode fixed plate outside anode fixed plate Being provided with seal washer, seal washer seals, and makes each parts of battery fasten and prevent fuel solution from revealing；Outside liquid storage cylinder Embedding optical window, optical window is as the entrance port of light, and liquid storage cylinder is internal places light anode and fuel solution, and described self-respiration type refers to combustion Material battery directly absorbs oxygen from air.
Cathode collector plate central authorities arrange multiple entrance and the circular channel I of product water discharge cathode gas diffusion layer, circle for air The collector section of shape passage I region composition cathode collector plate；Anode fixed plate central authorities arrange multiple between anode diffusion layer Carry out the circular channel II of electrolyte mass transfer, the mass transfer section of circular channel II region composition anode fixed plate；Seal washer and Hollow out in the middle of end plate, cut-out size and optical window, the collector section of cathode collector plate, the mass transfer section of anode fixed plate, the moon Pole gas diffusion layers, anode diffusion layer, membrane electrode in the same size；
Hollow out in the middle of seal washer and end plate, cut-out size and optical window, the collector section of cathode collector plate, anode fixed plate Mass transfer section, cathode gas diffusion layer, anode diffusion layer, membrane electrode in the same size；
Described liquid storage cylinder is a kind of recording quantity, the hollow chamber of five face seals, wherein, before in the middle of hollow out, the size hollowed out Consistent with optical window, liquid storage cylinder is arranged above with two through holes, be respectively used to light positive wire by and biomass fuel inject and anti- Answering gas to disengage, light anode is placed in liquid storage cylinder intracavity by through hole, and uses conductive silver glue and copper cash to connect formation Ohmic contact, Fix with epoxy resin and insulate.
Liquid storage cylinder, seal washer, cathode collector plate, anode fixed plate, the edge of end plate are uniformly arranged identical multiple fixing hole, After assembling, fixing hole can be overlapping, makes to be screwed this light and helps microbial fuel cell, screw to obtain a kind of no liquid after screwing tight The self-respiration type light leaked outside helps microbial fuel cell assembly.
Under normal conditions, described fixing hole is the through hole of more than four, prepares in fuel cell process actual, according to specifically Requirement, number and size to fixing hole are configured；Preferably number is 4, particular location be liquid storage cylinder, seal washer, Cathode collector plate, anode fixed plate, the corner at end plate edge.
Described membrane electrode includes PEM and is sprayed at the cathod catalyst of PEM one side, and described cathod catalyst is Pt/C, platinum black, the preparation method of membrane electrode is: formed in aqueous isopropanol by the cathod catalyst ultrasonic disperse of certain mass Slurry, is coated in the side of PEM with spray gun by pulp spraying, forms membrane electrode, and in membrane electrode, the carrying capacity of metal is 0.5～2mg cm-2。
The material of described smooth anode is type n semiconductor material.
Described smooth anode includes bulk material BiVO4、Fe2O3、WO3、TiO2、CdS、Ta2O5、Ta3N5Etc. N-type quasiconductor；
Carry out on the basis of bulk material or be not modified or modify, method that is modified or that modify be a. doped metallic elements and/ Or b. is compound, sensitization, Supported oxide promoter；
Metallic element includes in W, Mo, Ta, Zr, Si, Ti, La, Fe, Sr, Zn, Ag, Pt, Ru, In, Rh, Cr One or more；
It is 0.01%～10% that the doping of metallic element accounts for the 0%～20% of light anode gross mass, preferably doping scope；
Described oxide promoter is NiO, Ni (OH)2、NiOOH、Fe(OH)3、FeOOH、Mn(OH)2、Cu(OH)2In One or more；
Oxide promoter accounts for the 0%～10% of light anode gross mass, preferably loading 0.01%～2%.
The preparation method of light anode is set forth below, but described preparation method is not limiting as the preparation side of smooth anode used in the present invention Method and kind.
BiVO4The preparation of light anode: potentiostatic electrodeposition method.By Bi (NO3)3And VOSO4.xH2O is made into electrolyte, with sodium acetate and Nitre acid for adjusting pH, to 4.7, deposits 20～60min under 1.8～2.1V current potentials, and the electrode deposited is roasting 1h at 500 DEG C, In 1M KOH solution, soak 10～15min after roasting be purified.
W-BiVO4The preparation of light anode: add 0.1～10mM Na in above-mentioned electrolyte2WO3.2H2O, other synthesis steps are not Become.
Fe2O3The preparation of light anode: chemical baths.0.01～0.5mol/L FeCl3Solution, the NH of 0.3mol/L2CONH2Mixed Together in the beaker of 100mL, FTO is disposed vertically in beaker along walls of beaker, be then placed in baking oven 100 DEG C of heating 1～ 6h.After having reacted, take out FTO electrode, now on FTO, overgrow with saffron FeOOH film, then in Muffle furnace 500 DEG C Annealing 3h, obtains Fe2O3Electrode.
The Fe of Ti doping2O3The preparation of electrode: FeOOH film obtained above, at 0.01～1mol/L TiCl4Middle dipping 1～30min, Then 500 DEG C of annealing 3h in Muffle furnace, obtain the Fe of Ti doping2O3Electrode.
WO3The preparation of electrode, by spin coating WO on FTO3Presoma carries out the method synthesis annealed again.Specific as follows: by WCl6 It is dissolved in the mixed solvent of acetone and ether (1:3～3:1), makes WCl6Concentration be 0.01-1mol/L；FTO is put Putting on spin coating instrument, drip the above-mentioned precursor liquid of 200ul, under 1000 rotating speeds, spin coating 30s, obtains thin electrolyte film, in 70 DEG C of baking ovens Dry, then 500 DEG C of annealing 2h in Muffle furnace, obtain WO3Electrode.
TiO2The preparation of electrode, by electrochemical oxidation titanium sheet, the method synthesis of re-annealing.By titanium sheet and Pt sheet (to electrode) Being placed in electrolyte, at room temperature apply 20-60V constant voltage and carry out electrochemical oxidation 2-80min, anode oxidation process terminates After, remove external voltage, take out sample, the most slightly rinse surface with ethanol and deionized water, dry up.Then, by this electrode Being placed in Muffle furnace, be warming up to 450 DEG C with the speed of 2 DEG C/min, then anneal at 450 DEG C 30-200min, obtains TiO2 Electrode.
Cathode gas diffusion layer is carbon paper or carbon cloth, for conventional cathode gas diffusion layer, can also be able to make by oneself with commodity purchasing；
Anode diffusion layer is carbon paper or carbon cloth, for conventional anode diffusion layer, can also be able to make by oneself with commodity purchasing；
Hollowing out inside the internal structure of liquid storage cylinder, both-side opening, outside inlay optical window, and light anode is placed in inside liquid storage cylinder and hollows out place, Light anode uses conductive silver glue and copper cash to connect and forms Ohmic contact, and fixes with epoxy resin and insulate.
Liquid storage cylinder (1) uses has certain mechanical strength, easily processing and the material of resistance to certain corrosion, preferably politef (PTFE), polymethyl methacrylate (PMMA), rustless steel, optical window (2) as the entrance port of light, uses printing opacity good Material, is preferably quartz, glass, lucite；Seal washer (3) uses the material with certain mechanical strength, elastic strength Material, preferably silica gel, PTFE；Anode fixed plate (5) uses has certain mechanical strength, easily processing and the material of resistance to certain corrosion Material, preferably epoxy resin, PMMA, rustless steel, graphite cake, it is easy that cathode collector plate (4) employing has certain mechanical strength Process resistance to certain corrosion and the good material of electric conductivity, the preferably printed circuit board (PCB) of plated surface Au-Ag-Pt, graphite cake, Metallic plate；End plate (9) uses has certain mechanical strength and the material of easily processing, preferably epoxy resin, PMMA, rustless steel, Graphite cake；Cathode gas diffusion layer (6) uses carbon paper or carbon cloth, and anode diffusion layer (7) uses carbon paper or carbon cloth.
Described fuel solution refers to comprise the solution of biomass fuel, and described biomass fuel includes cellulose, starch, Fructus Vitis viniferae Sugar, cellobiose, lactose, glycerol, ethylene glycol, methanol, ethanol, formaldehyde, formic acid, acetic acid and their derivant, Be preferably glucose, cellobiose, glycerol, methanol, or from the organic molecule in waste water, refuse, preferably ammonia, Carbamide, phenols；Described solution be sodium borate buffer solution, phosphate buffered solution, Tris buffer solution, metabisulfite solution, Sodium hydroxide solution, sulfuric acid solution, pH scope is 1～14.
Light source irradiates self-respiration type light and helps the optical window of microbial fuel cell, and light path passes through optical window direct light anode front or the back side, Luminous energy and biomass energy being converted into electric energy discharge, the light source of described light includes xenon lamp, xenon-mercury lamp, iodine-tungsten lamp, solar energy Simulator and sunlight.
Described fuel cell is that a kind of miniature self-respiration type light helps microbial fuel cell, and structure is as described above, can make A kind of microstructure, wherein, circular channel I that cathode collector plate and anode fixed plate central authorities offer and the Kong Zhi of circular channel II Footpath is 1～6mm, and perforated area accounts for the 30～70% of catalysis active area；Preferably bore dia is 4mm, and perforated area accounts for urges Change the 50% of active area.
Self-respiration type light of the present invention helps microbial fuel cell at small-power power, new forms of energy or alternative energy source, sewage Application in reason equipment, sensor.
Self-respiration type light of the present invention helps the assembling of microbial fuel cell and discharge process as follows: by liquid storage cylinder, sealing gasket Circle, anode fixed plate, seal washer, anode diffusion layer, membrane electrode, cathode diffusion layer, seal washer, cathode collector plate, End plate is screwed successively；Then in liquid storage cylinder, put into light anode, inject the solution containing biomass fuel；By light anode Negative and positive pole with cathode collector plate is respectively connected to test system, carries out battery discharge test.
The present invention, compared with known fuel cell system, has the advantage that
1, help in microbial fuel cell at self-respiration type light of the present invention, utilize photo-excited semiconductor light anode to produce electronics And hole, biomass fuel is aoxidized by hole, and oxygen, by directly absorbing from air from breathing pattern, reduces at negative electrode Reaction, light anode excites the electronics of generation to derive via external circuits, releases electricity, and biomass fuel of the present invention is originated Extensively, can be some natural biomass and derivant thereof, including glucose, cellobiose, glycerol, ethylene glycol, methanol, Ethanol etc., it is also possible to be the organic molecule in waste water or refuse, such as ammonia, carbamide, phenols etc., the present invention utilizes nature to enrich Solar energy and biomass energy be converted into electric energy, and transformation process cleaning, do not result in the pollution of environment.
2, institute's light anode material is semiconductor oxide materials, such as TiO2、WO3、Fe2O3、BiVO4Deng, compare traditional expensive For metal eelctro-catalyst, in nature, abundance is big, cheap, excites the C-C of the lower Organic substance fuel that can effectively rupture at light Key, is provided that higher open-circuit voltage.
3, negative electrode uses self-respiration type to be emptied electrode, and air is directed through cathode gas diffusion layer and uniformly assigns to cathode catalysis layer, because of This is battery oxygen supply without using any other auxiliary device, is greatly simplified battery structure.
4, simple to operate, it is not necessary to can to run under harsh working condition, room temperature.
Accompanying drawing explanation
Fig. 1 is the structural representation that self-respiration type light helps microbial fuel cell device, wherein, 1 be liquid storage cylinder, 2 for optical window, 3 be seal washer, 4 for cathode collector plate, 5 for anode fixed plate, 6 for cathode gas diffusion layer, 7 for anode diffusion layer, 8 For membrane electrode, 9 be end plate, 10 for light anode, 11 for fixing hole, 12 for circular channel I, 13 for circular channel II, 14 For through hole I, 15 be through hole II；
Fig. 2 is BiVO4And W-BiVO4The XRD figure of light anode: W-BiVO4Maintain BiVO4Monoclinic phase structure；
Fig. 3 is BiVO4And W-BiVO4The SEM figure of light anode: electrode is made up of interconnective approximate sphericity granule, mixes W W-BiVO4Maintain BiVO4The pattern of electrode；
Fig. 4 is BiVO4And W-BiVO4Photoelectric current test result after the test result of light anode photoelectricity oxidizing glucose: W doping Apparently higher than plain BiVO4Photoelectric current；
Fig. 5 is BiVO4And W-BiVO4Light anode is in self-respiration type light helps microbial fuel cell device, at AM1.5G 100 mW/cm2Solar simulator is the cell discharge performance curve chart under light conditions with glucose solution as fuel；
Fig. 6 is BiVO4And W-BiVO4Light anode, in self-respiration type light helps microbial fuel cell device, in visible ray light intensity is 350mW cm–2Cell discharge performance curve chart with glucose solution as fuel under the conditions of Xe lamp (λ > 420nm)；
Fig. 7 is W-BiVO4The test figure of the biomass such as light anode light electroxidation glycerol, methanol, cellobiose；
Fig. 8 is W-BiVO4Light anode is in self-respiration type light helps microbial fuel cell device, at AM1.5G 100mW/cm2Too Sun energy simulator is the cell discharge performance curve chart under light conditions with glycerol, methanol, cellobiose solution as fuel；
Fig. 9 is W-BiVO4Light anode in self-respiration type light helps microbial fuel cell device under the conditions of dark-state with glucose solution Cell discharge performance curve chart for fuel；
Figure 10 is Fe2O3Electrode or the Fe of Ti doping2O3Light anode in self-respiration type light helps microbial fuel cell device, AM1.5G 100mW/cm2Solar simulator is the cell discharge performance curve chart under light conditions with glucose solution as fuel；
Figure 11 is WO3Light anode is in self-respiration type light helps microbial fuel cell device, at AM1.5G 100mW/cm2The sun Energy simulator is the cell discharge performance curve chart under light conditions with glucose solution as fuel；
Figure 12 is TiO2Light anode is in self-respiration type light helps microbial fuel cell device, at AM1.5G 100mW/cm2The sun Energy simulator is the cell discharge performance curve chart under light conditions with methanol solution as fuel.
Detailed description of the invention
In order to further illustrate the present invention, enumerate following example in conjunction with the accompanying drawings, but it is not limiting as institute of the present invention Scope of protection.
Embodiment 1
Be illustrated in figure 1 a kind of self-respiration type light and help microbial fuel cell, including liquid storage cylinder 1, optical window 2, seal washer 3, Cathode collector plate 4, anode fixed plate 5, cathode gas diffusion layer 6, anode diffusion layer 7, membrane electrode 8, end plate 9, light anode 10。
Specifically, the inner side of anode fixed plate 5 and cathode collector plate 4 is respectively equipped with packing ring 3 sealing together, two seal washers 3 Between be provided with membrane electrode 8, membrane electrode 8 is provided with cathode gas diffusion layer 6 being positioned at cathode collector plate 4 side, and membrane electrode 8 is in place It is provided with anode diffusion layer 7 in anode fixed plate 5 side, outside cathode collector plate 4, is provided with end plate 9；Set outside anode fixed plate 5 Having liquid storage cylinder 1, be provided with seal washer 3 between liquid storage cylinder 1 and anode fixed plate 5, liquid storage cylinder 1 opposite side embeds optical window 2, storage Sap cavity 1 is internal places light anode 10；Liquid storage cylinder 1, seal washer 3, cathode collector plate 4, anode fixed plate 5, end plate 9 Edge is uniformly provided with multiple fixing hole 11, is preferably provided with 4 fixing holes 11, and described fixing hole 11 is circular；Cathode collector plate 4 are provided with, in central authorities, the circular channel I 12 that multiple air and current are logical, the collector section of this passage area composition cathode collector plate 4, Enter for air and product water discharges cathode gas diffusion layer 6；Anode fixed plate 5 is provided with the circle of multiple electrolyte circulation in central authorities Shape passage II 13, the mass transfer section of this passage area composition anode fixed plate 5, for the mass transfer with anode diffusion layer 7；Cloudy Circular channel I that pole collector plate 4 and anode fixed plate 5 central authorities offer and a diameter of 4mm of circular channel II, at liquid storage cylinder 1 Top central authorities have the through hole I 14 that light positive wire passes through, and have the through hole II of fuel and gas in liquid storage cylinder 1 tip edge 15, inject for fuel and reacting gas disengages, be fuel solution in liquid storage cylinder 1；Membrane electrode 8 includes PEM and spraying In the cathod catalyst of PEM one side, the preparation method of membrane electrode is in aqueous isopropanol by cathod catalyst ultrasonic disperse Middle formation slurry, is coated in the side of PEM with spray gun by pulp spraying, forms membrane electrode, and the carrying capacity of Pt metal is 0.5～2mg cm-2, liquid storage cylinder 1, seal washer 3, end plate 9 length and width consistent, such as 5.7cm × 5.7cm, liquid storage cylinder 1, seal washer 3 and end plate 9 central authorities be provided with the opening portion hollowed out, the size of opening with optical window 2, the collector section of cathode collector plate 4, sun The mass transfer section of pole fixed plate 5, cathode gas diffusion layer 6, anode diffusion layer 7, membrane electrode 8 in the same size, for 2.0cm × 2.0cm, for making each parts of battery fasten and prevent fuel solution from revealing, critical piece adds colloid packing ring, i.e. seal washer 3 points It is not placed between cathode collector plate 4 and the inner side of anode fixed plate 5 and anode fixed plate 5 and liquid storage cylinder 1, seals, And surrounding to open four holes for screw stays.
Liquid storage cylinder 1 uses politef (PTFE) material, and optical window 2, as the entrance port of light, uses quartz material, anode Fixed plate 5 uses epoxide resin material, cathode collector plate 4 to use epoxy resin fiberglass material printed circuit board (PCB), and at electricity Plate surface, road scribbles anticorrosive coat, and anticorrosive coat is Ag, is made by brushing method, and end plate 9 uses stainless steel material, cathode gas Diffusion layer 6 uses hydrophobicity carbon paper, anode diffusion layer 7 to use hydrophilic carbon paper, light anode 10 to use conductive silver glue and copper cash even Connect formation Ohmic contact, and fix with epoxy resin and insulate.
Embodiment 2
BiVO4And W-BiVO4The preparation of light anode:
BiVO4Electrode or W-BiVO4The synthesis step of electrode is as follows:
BiVO4The preparation of light anode: potentiostatic electrodeposition method synthesizes.202mL water adds the dense HNO of 11mL mass percent 65%3, Claim 8.75mmol VOSO4.xH2O is dissolved in above-mentioned solution, adds 1.2133g Bi (NO3)3.5H2O, 52g anhydrous sodium acetate Regulation pH to about 5.1, then adds nitric acid and adjusts pH to 4.7.With above-mentioned solution as electrolyte, make electrode with Pt sheet, FTO makees working electrode, and saturated calomel electrode SCE is reference electrode, under the conditions of 70 DEG C of constant temperature water baths, by CHI760D electrification Learn work station controlling potential 1.855V vs.SCE, deposition 40min and take out cleaning, 500 DEG C of roasting 1h in atmosphere, rise Temperature 2 DEG C/min of speed, finally soaks 15min with the KOH of 1mol/L, removes V2O5Impurity, described FTO is doping The SiO of fluorine2Transparent conducting glass.
W adulterates BiVO4The preparation of light anode: add 1mmol/L Na in above-mentioned electrolyte2WO3.2H2O, other synthesis steps Constant.
BiVO4And W-BiVO4The XRD spectra result of light anode is shown in Fig. 2, W-BiVO4Do not change BiVO4Crystalline phase, maintain BiVO4Monoclinic phase structure.
Embodiment 3
BiVO4And W-BiVO4The morphology characterization of light anode:
BiVO4Electrode is made up of interconnective approximate sphericity granule, mixes the W-BiVO of W4Maintain BiVO4The pattern of electrode, Result is shown in Fig. 3.
Embodiment 4
BiVO4And W-BiVO4Light anode photoelectricity oxidizing glucose:
With the sodium borate buffer solution of 0.2mol/L pH=9 as blank electrolyte solution, sodium borate buffer solution adds 0.1 The glucose of mol/L is fuel solution, with BiVO4And W-BiVO4Electrode is that light anode, Pt sheet are for electrode, saturated calomel Electrode SCE is reference electrode, with AM1.5G 100mW/cm2Solar simulator is light source, and light is from the electrode back side i.e. FTO Side is incident, and test result is shown in Fig. 4, W doping BiVO4After photoelectric current apparently higher than plain BiVO4Photoelectric current.
Sodium borate buffer solution compound method of the present invention is, by molten to 2.4856g boric acid and 15.3319g sodium tetraborate Xie Hou, constant volume to 1L, i.e. obtain the sodium borate buffer solution of 0.2mol/L pH=9.
Embodiment 5
Battery assembles and test:
When battery is installed, four screws are each passed through liquid storage cylinder 1, the most successively set upper sealing washer 3, anode fixed plate 5, Second seal washer 3, being placed in anode fixed plate 5 by anode diffusion layer 7, membrane electrode 8 is placed in without the one side of catalyst again On anode diffusion layer 7, cathode gas diffusion layer 6 is placed in membrane electrode 8 surface of cathod catalyst, then puts the 3rd sealing Packing ring 3, cathode collector plate 4 and end plate 9, finally put the nut of fastening screw, screw means fixed, make each member in tight In conjunction with.Then in liquid storage cylinder 1, light anode 10 is put into, in liquid storage cylinder 1 upper end by the duct I 14 of liquid storage cylinder 1 upper end During duct II 15 injects, 5mL contains 0.1mol/L glucose fuel, the sodium borate buffer solution of pH=9, by the wire of light anode It is connected with the electrode wires of the wire being welded on cathode collector plate current-carrying part one jiao with Dutch IviumStat electrochemical workstation, beats Open AM1.5G 100mW/cm2Solar simulator light source, light path, through the FTO face of optical window 2 direct light anode 10, opens work Make station test system, carry out battery discharge test.Test curve such as Fig. 5, test result such as table 1.
Fuel battery performance under table 1, AM1.5G with glucose as fuel
Under AM1.5G light source, best battery performance be open-circuit voltage be 0.92V, short circuit current is 1.65mA cm-2, Power density is 0.40mW cm–2。
The process of battery discharge is: illumination makes light anode 10 excite generation electronics and hole, and hole is by the oxidized on surface；Matter Son enters membrane electrode 8 PEM via anode diffusion layer 7, and then enters membrane electrode 8 cathode catalysis layer, and oxygen is via hole 12, by directly absorbing from air from breathing pattern, enter the cathode catalysis layer of membrane electrode 8 by cathode gas diffusion layer 6, Reduction reaction occurs on the cathode catalysis layer of membrane electrode 8, and light anode 10 excites the electronics of generation to derive via external circuits, puts Go out electricity.
Photoelectric transformation efficiency computational methods are:
Embodiment 6
Similar embodiment 5, difference is that it is 350mW cm that light source changes into light intensity–2Xe lamp (λ > 420nm) can See the cell discharge performance under optical condition, curve chart such as Fig. 6, test result such as table 2.
Fuel battery performance under table 2, visible ray with glucose as fuel
Embodiment 7
W-BiVO4The biomass such as light anode light electroxidation glycerol, methanol, cellobiose:
Similar embodiment 4, difference is to change the dobell's solution containing glucose into the boron of glycerol, methanol, cellobiose Acid sodium solution.Test result such as Fig. 7.
Embodiment 8
With glycerol, methanol, the cellobiose solution battery performance test as fuel:
Similar embodiment 5, difference is glucose fuel changes into glycerol, methanol, cellobiose fuel.Test result See Fig. 8, test result such as table 3.
Fuel battery performance under table 3, AM1.5G with glycerol, cellobiose, methanol as fuel
Embodiment 9
The performance test under battery dark-state with glucose solution as fuel:
Similar embodiment 5, difference is to be not added with illumination, and test result is shown in Fig. 9, and the maximum power density obtained only has 0.4 μ W cm-2, less nearly 1000 times than power density during illumination, illustrate that this battery is dependent on the microbial fuel cell of optical drive.
Embodiment 10
Fe2O3Electrode or the Fe of Ti doping2O3The preparation of electrode, is closed by the method in chemical baths film forming roasting again on FTO Become.
Fe2O3Preparing of electrode is specific as follows: 0.2mol/L FeCl3Solution, the NH of 0.3mol/L2CONH2It is mixed in 100mL Beaker in, FTO is disposed vertically in beaker along walls of beaker, is then placed in baking oven 100 DEG C of heating 4h.After having reacted, Take out FTO electrode, now on FTO, overgrow with saffron FeOOH film, in Muffle furnace after 500 DEG C of annealing 3h, then 750 DEG C Carry out double annealing 15min, obtain Fe2O3Electrode.The Fe of Ti doping2O3The preparation of electrode: FeOOH film obtained above, At 0.1mol/L TiCl4Middle dipping 5min, then 500 DEG C of annealing 3h in Muffle furnace, then 750 DEG C carry out double annealing 15min, Obtain the Fe of Ti doping2O3Electrode.
Embodiment 11
WO3The preparation of electrode, by spin coating WO on FTO3Presoma carries out the method synthesis annealed again.Specific as follows: by WCl6 It is dissolved in the mixed solvent of acetone and ether (3:2), makes WCl6Concentration be 0.1mol/L；FTO is placed on spin coating On instrument, dripping the above-mentioned precursor liquid of 200ul, under 1000 rotating speeds, spin coating 30s, obtains thin electrolyte film, dries in 70 DEG C of baking ovens, then In Muffle furnace, 500 DEG C of annealing 2h, obtain WO3Electrode.
Embodiment 12
TiO2The preparation of electrode, by electrochemical oxidation titanium sheet, the method synthesis of re-annealing.Specific as follows:
The preparation of electrolyte: add ammonium fluoride and the water of 2wt% that mass fraction is 0.4wt% in ethylene glycol solution.
Titanium sheet and Pt sheet (to electrode) are placed in electrolyte, at room temperature apply 40V constant voltage and carry out electrochemical oxidation 10min, After anode oxidation process terminates, remove external voltage, take out sample, the most slightly rinse surface with ethanol and deionized water, dry up. Then, being placed in Muffle furnace by this electrode, be warming up to 450 DEG C with the speed of 2 DEG C/min, then anneal at 450 DEG C 30min, Obtain TiO2Electrode.
Embodiment 13
With Fe2O3Electrode or the Fe of Ti doping2O3Electrode is light anode, the battery performance test with glucose solution as fuel:
Similar embodiment 5, difference is BiVO4Or W-BiVO4Electrode changes Fe into2O3Electrode or the Fe of Ti doping2O3Electricity Pole, changes by the sodium borate buffer solution that electrolyte is pH=9 as the sodium hydroxide solution of pH=13 into.Test result is shown in Figure 10.Knot Opinion is: the Fe adulterated by Ti2O3Light anode, the self-respiration type light with glucose solution as fuel helps the performance of biomass fuel Relatively body Fe2O3Electrode is significantly improved, and short circuit current is by 0.52mA cm-2Bring up to 1.40mA cm-2, power density by 0.057mW cm-2Bring up to 0.143mW cm-2。
Embodiment 14
With WO3Electrode is light anode, the battery performance test with glucose solution as fuel:
Similar embodiment 5, difference is BiVO4Or W-BiVO4Electrode changes WO into3Electrode, is pH=9's by electrolyte Sodium borate buffer solution changes the phosphate buffer solution of pH=7 into.Test result is shown in Figure 11.It is concluded that with WO3Electrode is light anode, Battery performance with glucose solution as fuel is, open-circuit voltage is 0.65V, and short circuit current is by 1.28mA cm-2, power is close For 0.15mW cm-2。
Embodiment 15
With TiO2Electrode is light anode, the battery performance test with methanol solution as fuel:
Similar embodiment 5, difference is BiVO4Or W-BiVO4Electrode changes TiO into2Electrode, is pH=9 by electrolyte Sodium borate buffer solution change the sodium hydroxide solution of pH=13 into, change glucose fuel into methanol fuel.Test result is shown in figure 12.It is concluded that with TiO2Electrode is light anode, and the battery performance with methanol solution as fuel is, open-circuit voltage is 1.20V, Short circuit current is by 0.35mA cm-2, power is close for 0.13mW cm-2。

Claims (10)

1. a self-respiration type light helps microbial fuel cell, it is characterised in that: described self-respiration type light helps microbial fuel cell Including optical window (2), liquid storage cylinder (1), seal washer (3), anode fixed plate (5), anode diffusion layer (7), membrane electrode (8), Cathode gas diffusion layer (6), cathode collector plate (4), end plate (9)；
It is respectively equipped with packing ring sealing together (3), two seal washers in the inner side of anode fixed plate (5) and cathode collector plate (4) (3) being provided with membrane electrode (8) between, membrane electrode (8) is provided with cathode gas diffusion layer (6) being positioned at cathode collector plate (4) side, Membrane electrode (8) is provided with anode diffusion layer (7) being positioned at anode fixed plate (5) side, and cathode collector plate (4) outside is provided with end Plate (9), anode fixed plate (5) outside is provided with liquid storage cylinder (1), is provided with close between liquid storage cylinder (1) and anode fixed plate (5) Seal washer (3), hollows out embedding optical window (2) in the middle of liquid storage cylinder (1) front, optical window (2) is as the entrance port of light, liquid storage cylinder (1) intracavity places light anode (10) and fuel solution, and described self-respiration type refers to that fuel cell directly absorbs oxygen from air.
Self-respiration type light the most according to claim 1 helps microbial fuel cell, it is characterised in that: cathode collector plate (4) Central authorities arrange multiple entrance and the circular channel I (12) of product water discharge cathode gas diffusion layer (6) for air, circular logical The collector section in road I (12) region composition cathode collector plate (4)；Anode fixed plate (5) central authorities arrange multiple for sun Carrying out the circular channel II (13) of electrolyte mass transfer between pole diffusion layer (7), circular channel II (13) region composition anode is solid Determine the mass transfer section of plate (5)；Hollow out in the middle of seal washer (3) and end plate (9), the size of cut-out and optical window (2), The collector section of cathode collector plate (4), the mass transfer section of anode fixed plate (5), cathode gas diffusion layer (6), anode expand Dissipate layer (7), membrane electrode (8) in the same size；
Described liquid storage cylinder (1) is a kind of recording quantity, the hollow chamber of five face seals, wherein, before in the middle of hollow out, hollow out Size is consistent with optical window (2), and liquid storage cylinder (1) is arranged above with two through holes (14,15), is respectively used to the logical of light positive wire Crossing and biomass fuel injects and reacting gas disengages, light anode (10) is placed in liquid storage cylinder intracavity by through hole, and employing is led Electricity elargol and copper cash connect formation Ohmic contact, fix with epoxy resin and insulate.
Self-respiration type light the most according to claim 1 helps microbial fuel cell, it is characterised in that: liquid storage cylinder (1), Seal washer (3), cathode collector plate (4), anode fixed plate (5), the edge of end plate (9) are uniformly arranged identical multiple fixing Hole (11), after assembling, fixing hole can be overlapping, makes to be screwed this light and helps microbial fuel cell, screw to obtain one after screwing tight The self-respiration type light that kind no liquid leaks outside helps microbial fuel cell assembly.
Self-respiration type light the most according to claim 1 helps microbial fuel cell, it is characterised in that:
Described membrane electrode (8) includes PEM and is sprayed at the cathod catalyst of PEM one side, described smooth anode (10) Material be type n semiconductor material.
Self-respiration type light the most according to claim 4 helps microbial fuel cell, it is characterised in that:
Described cathod catalyst is Pt/C, platinum black；
Described smooth anode includes bulk material BiVO4、Fe2O3、WO3、TiO2、CdS、Ta2O5、Ta3N5In one or both with On；
Carry out on the basis of bulk material or be not modified or modify, method that is modified or that modify be a. doped metallic elements and/ Or b. is compound, sensitization, Supported oxide promoter；
Metallic element includes in W, Mo, Ta, Zr, Si, Ti, La, Fe, Sr, Zn, Ag, Pt, Ru, In, Rh, Cr One or more；
The doping of metallic element accounts for the 0%～20% of light anode gross mass；
Described oxide promoter is NiO, Ni (OH)2、NiOOH、Fe(OH)3、FeOOH、Mn(OH)2、Cu(OH)2In One or more；
Oxide promoter accounts for the 0%～10% of light anode gross mass.
Self-respiration type light the most according to claim 1 helps microbial fuel cell, it is characterised in that: described fuel solution Referring to comprise the solution of biomass fuel, described biomass fuel includes cellulose, starch, glucose, cellobiose, breast In sugar, glycerol, ethylene glycol, methanol, ethanol, formaldehyde, formic acid, acetic acid and their derivant one or both with On, preferably one or more in glucose, cellobiose, glycerol, methanol, or from waste water, refuse Organic molecule, preferably one or more in ammonia, carbamide, phenols；Described solution be sodium borate buffer solution, Phosphate buffered solution, Tris buffer solution, metabisulfite solution, sodium hydroxide solution, sulfuric acid solution.
Self-respiration type light the most according to claim 1 helps microbial fuel cell, it is characterised in that: liquid storage cylinder (1) is adopted With having certain mechanical strength, easily processing and the material of resistance to certain corrosion, preferably politef (PTFE), polymethyl Acid methyl ester (PMMA), rustless steel, optical window (2), as the entrance port of light, uses the material that printing opacity is good, the most quartzy, Glass, lucite；Seal washer (3) uses the material with certain mechanical strength, elastic strength, preferably silica gel, PTFE； Anode fixed plate (5) uses has certain mechanical strength, easily processing and the material of resistance to certain corrosion, preferably epoxy resin, PMMA, Rustless steel, graphite cake, cathode collector plate (4) employing has certain mechanical strength and easily processes resistance to certain corrosion and electric conductivity Good material, the preferably printed circuit board (PCB) of plated surface Au-Ag-Pt, graphite cake, metallic plate；End plate (9) uses to be had Certain mechanical strength and the material of easily processing, preferably epoxy resin, PMMA, rustless steel, graphite cake；Cathode gas diffusion layer (6) using carbon paper or carbon cloth, anode diffusion layer (7) uses carbon paper or carbon cloth.
Self-respiration type light the most according to claim 1 helps microbial fuel cell, it is characterised in that: light source irradiates light and helps life The optical window (2) of biomass fuel battery, light path passes through optical window (2) direct light anode (10) front or the back side, by luminous energy and biology Characteristic energy changes is that electric energy discharges, and the light source of described light includes xenon lamp, xenon-mercury lamp, iodine-tungsten lamp, solar simulator and too Sunlight.
Self-respiration type light the most according to claim 1 helps microbial fuel cell, it is characterised in that: described fuel cell is A kind of miniature self-respiration type light helps microbial fuel cell.
10. the self-respiration type light described in claim 1-9 helps microbial fuel cell at small-power power, new forms of energy or to replace For the application in the energy, sewage disposal device, sensor.
CN201510337590.1A 2015-06-17 2015-06-17 Self-respiration type light helps microbial fuel cell and application thereof Pending CN106257729A (en)

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CN113130914A (en) * 2019-12-31 2021-07-16 大连大学 Lactose fuel cell and PtNPs/CuNPs/NiNPs/carbon cloth plastic electrode for constructing same
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