CN103199294B - Microfluid-based self-breathing photocatalytic film-free fuel battery - Google Patents
Microfluid-based self-breathing photocatalytic film-free fuel battery Download PDFInfo
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- CN103199294B CN103199294B CN201310085223.8A CN201310085223A CN103199294B CN 103199294 B CN103199294 B CN 103199294B CN 201310085223 A CN201310085223 A CN 201310085223A CN 103199294 B CN103199294 B CN 103199294B
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- microfluid
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- catholyte
- fuel battery
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- 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
Abstract
The invention relates to a microfluid-based self-breathing photocatalytic film-free fuel battery. The microfluid-based self-breathing photocatalytic film-free fuel battery is characterized in that conductive glass, a microfluid battery chip and a gas dispersing electrode form a main body of the micro-flow photocatalytic film-free fuel battery; the conductive glass is loaded with a titanium dioxide semiconductor nanorod serving as a photocatalyst; an anode conductor and a cathode conductor are used for leading out electric energy generated from the interior of the battery for external electric appliances to use; and organic waste water pollutant and anode electrolyte respectively flow in from an anode liquid inlet and a cathode liquid inlet. The microfluid-based self-breathing photocatalytic film-free fuel battery removes a proton exchange membrane required by a traditional photocatalytic fuel battery by a principle of laminated flow of microfluid laminar flow so as to simplify the battery structure and reduce the manufacturing cost; oxygen of air enters the battery chip through the gas dispersing electrode to participate in reaction without a special conveying device; and the waste water pollutant and the anode electrolyte are injected into the photocatalytic fuel battery chip through a micro-flow pump, and chemical energy of the organic pollutant is transformed into electric energy which is output outwards.
Description
[technical field]
The present invention relates to field of fuel cell technology, specifically, is that a kind of self-respiration type photocatalysis based on microfluid is without membrane cell.
[background technology]
Photic electrochemical reaction, is be that energy input impels electrochemical reaction to occur with luminous energy, makes the chemical energy be stored in chemical substance be that electric energy outwards exports.
Photochemical catalyst in photocatalytic fuel cell is when being subject to light radiation and irradiating, semiconductor light-catalyst is excited, and discharges electronics, produces hole simultaneously, the electronics of release and cavity energy and water react and produce strong oxidizing property free radical, thus can organic pollution in Decomposition Wastewater.Excite the electronics of generation can also be derived by external circuit, form electric current, power to external circuit electrical appliance.
Current photocatalytic fuel cell adopts body formula reactor to carry out batch processing, fuel and electrolyte is added in reactor and carries out photic electrochemical reaction, when running out of gas, then postcombustion.But the performance of current photocatalytic fuel cell also remains at low levels, and current density is about 1mA/cm
-2.Main cause is, the mass transfer in battery, transferring charge, and optical transport is subject to serious restriction, causes battery performance to be difficult to further raising.
Micro-fluidic technologies, due to its mass-and heat-transfer characteristic fast, is paid close attention to widely in recent years and is applied.Its laminar flow characteristics can be good at the physical and chemical process of control flow check body interface.
Gas-diffusion electrode, allows gas but stops liquid to pass through electrode.By using this type of electrode, can in electrochemical reaction process oxygen needed for continuous postreaction, allow photocatalytic fuel cell produce a respiration.At present, there is no the photocatalytic fuel cell report using gas-diffusion electrode design.
[summary of the invention]
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of self-respiration type photocatalysis based on microfluid without membrane cell; Object is micro-fluidic technologies to be applied in photocatalytic fuel cell, in order to break through the bottleneck of restriction photocatalytic fuel cell performance boost, accelerates material transferring charge, reduces luminous energy loss in the propagation direction.Meanwhile constantly supplement by the effect of gas-diffusion electrode the oxygen consumed, obtain efficient photocatalytic fuel cell reactor, and the long-time stability of retention.
The object of the invention is to be achieved through the following technical solutions:
A kind of self-respiration type photocatalysis based on microfluid is without membrane cell, it is characterized in that, load has titanium dioxide semiconductor nanometer rods to form microfluidic photocatalysis without membrane cell main body as the electro-conductive glass of photochemical catalyst and microfluid battery chip and gas-diffusion electrode, positive wire, the electric energy that inside battery produces by cathode wire is drawn for outside electrical appliance; Anolyte inlet connection, catholyte inlet connection is respectively used to organic wastewater and catholyte flows into, and discharge connection is used for effluent discharge.
Described microfluid photocatalysis uses organic wastewater as fuel from breathing without membrane cell, uses mineral salt as electrolyte, is electric energy processing the chemical energy in organic substance while waste water.
Described battery chip being arranged width is 2mm, and the degree of depth is 1mm, and length is the fluid channel of 10mm, and the gas-diffusion electrode for being made up of the carbon paper being loaded with platinum catalyst on the downside of fluid channel, upside is titanium dioxide semiconductor nanometer rods light-catalyzed reaction catalyst.
Described battery chip is by two pieces of micro-channel chip substrate I, and chip substrate II combines, and the microfluid in battery chip is upper and lower layering Laminar Flow, effectively can be kept the Laminar Flow of upper lower leaf in passage by this kind of practical structures.
Described chip substrate I has two through holes and two sections of grooves, leading portion (close entrance is leading portion) is groove, and back segment is groove; Front hole is anolyte ingate, and metapore is outlet opening.
Described chip substrate II has three through holes and three sections of grooves, two sections, front and back are groove, and interlude is groove; Front hole is anolyte ingate, and interstitial hole is catholyte ingate, and metapore is outlet opening.
Described anolyte entrance, catholyte entrance is connected with battery chip substrate II, junction epoxy sealing.
Described outlet is connected with battery chip substrate II, junction epoxy sealing.
Described positive wire is connected with photocatalysis load glass, and junction uses carbon slurry to be connected with silver slurry.
Described cathode wire is connected with carbon paper electrode, and junction uses carbon slurry to be connected with silver slurry.
Prepare microchannel chip, use microfluidic pump drive fluid, make fuel and electrolyte in microchannel, keep the flow regime of parallel laminar flow.There is light-catalyzed reaction and oxidation reaction on photocatalyst layer surface in anolyte, catholyte, at the gas-diffusion electrode place that load is made up of the carbon paper of platinum catalyst, reduction reaction occurs.Anode photochemical catalyst adopts titanium dioxide nano-rod, is synthesized on electro-conductive glass by hydro thermal method.Due to the material diffusion of microfluid and charge transfer path short, resistance is little, can realize supplementing and the discharge of product, therefore, it is possible to greatly improve battery performance of fuel fast.Due to the characteristic of anolyte and catholyte laminar flow, without the need to introducing physical boundary (such as proton exchange membrane), only relying on and controlling fluid flowing and can well control two fluids interface, simplifying battery structure, reduce manufacturing cost.
The present invention uses a kind of typical Wastewater Pollutant (as methylene blue) as fuel, and adopt natural mineral matter salt (as sodium sulphate) as electrolyte, water is as solution carrier.When photochemical catalyst excites by illumination, produce electronics and hole at the anode place of photocatalyst glass, oxidation reaction occur:
TiO
2+hv→TiO
2(e
-+h
+)
Electronics forms electric current by external circuit and arrives negative electrode, at gas-diffusion electrode place, reduction reaction occurs:
e
-+O
2+H
+→H
2O
Proton (H
+) be transferred to negative electrode by the electrolyte in microchannel by anode.
Beneficial effect of the present invention is as follows:
The present invention is based on microfluidic technology, break through traditional photocatalytic fuel cell restriction bottleneck, greatly improve photocatalytic fuel cell performance.Meanwhile, utilize microfluidic layer stream laminar flow principle, remove the proton exchange membrane needed in traditional photocatalytic fuel cell, reach simplification battery structure, reduce the object of manufacturing cost.In addition, the oxygen in air enters to participate in reaction in battery chip by gas-diffusion electrode, and without the need to special conveying device.Organic wastewater and catholyte will inject photocatalytic fuel cell chip by miniflow pump, under illumination condition, the chemical energy be stored in chemical substance is converted to electric energy and outwards export.
Structure of the present invention is simple, with low cost, easily manufactured, easy and simple to handle, and performance improves more than 75% compared with the body formula photocatalytic fuel cell developed at present.
[accompanying drawing explanation]
Fig. 1 is the structural representation of this microfluid photocatalysis without membrane cell.
Fig. 2 is the sectional view of this microfluid photocatalysis without membrane cell.
Being labeled as in accompanying drawing: 1, photocatalyst glass; 2, battery chip; 3, substrate I; 4, substrate II; 5, positive wire; 6, cathode wire; 7, anolyte inlet connection; 8, catholyte inlet connection; 9, discharge connection; 10, gas-diffusion electrode; 11, catholyte; 12, fluid interface; 13, anolyte.
[embodiment]
Below provide a kind of self-respiration type photocatalysis based on microfluid of the present invention without the embodiment of membrane cell.
Embodiment 1
In FIG, photocatalyst electro-conductive glass 1 and battery chip 2 form the main body of this microfluid photocatalysis without membrane cell.Substrate I3 is carved with two sections of grooves and two through holes, leading portion is groove (long 16mm, wide 2mm, dark 0.4mm), back segment is groove (long 17mm, wide 2mm, dark 0.5mm), groove formation anode inlet bonding with photocatalyst glass runner, the groove of groove and substrate II4, electro-conductive glass and gas-diffusion electrode 10 bonding formation battery fluid channel.Substrate II is carved with three sections of grooves and three holes, two sections, front and back (arrival end is front, and the port of export is rear) is groove (front segment length 8mm, wide 2mm, dark 0.4mm; Rear segment length 7mm, wide 2mm, dark 0.4mm), interlude is groove (long 10mm, wide 2mm, dark 0.5mm), leading portion groove and substrate I bottom surface bonding formation catholyte entrance channel, the groove of interlude groove and substrate I, electro-conductive glass, the bonding formation microchannel of diffusion electrode, back segment groove formation outlet flow bonding with substrate I bottom surface.As shown in Figure 2, the front hole of substrate I and the front hole of substrate II form anolyte entrance, and are connected to solidify glue with anolyte inlet connection 7, and the metapore of substrate I and the metapore of substrate II form waste liquid outlet, and are connected to solidify glue with discharge connection 9.The interstitial hole of substrate II and the bottom surface of substrate I form catholyte entrance, and are connected to solidify glue with catholyte inlet connection 8.Anolyte 13 and catholyte 11 take overs from anode inlet respectively and cathode inlet is taken over and flowed into, and present lower leaf and flow in battery microchannel.Due to minute yardstick Laminar Flow and diffusion control, the interface of anolyte and catholyte can form a narrow liquid interface 12 automatically, plays the effect preventing catholyte from mixing with anolyte, as shown in Figure 2.Waste liquid flows out from outlet.
Between photocatalyst electro-conductive glass and battery chip, between chip substrate I and chip substrate II, between gas-diffusion electrode and chip substrate II.
Positive wire 5 is drawn from photocatalyst electro-conductive glass place, and to derive light induced electron, electronics is imported negative electrode and participates in reduction reaction by cathode wire 6.Use carbon to starch between wire with electrode to be connected with silver slurry.
Organic pollution (fuel) and catholyte enter battery from anolyte entrance and catholyte entrance respectively, and outlet is used for effluent discharge.
Air diffuses into battery chip from gas-diffusion electrode.
Cell operation is: use microfluidic pump that fuel and catholyte are injected battery from anolyte entrance and catholyte entrance respectively, fuel and catholyte flow through anode and cathode inlet runner respectively, in the parallel flowing of battery fluid channel place natural layering, simultaneously, positive wire is connected by external loading (electrical appliance) with cathode wire, forms electronic loop.There is oxidation reaction and reduction reaction at photocatalyst electro-conductive glass and gas-diffusion electrode place respectively, outwards export electric energy.Reacted waste liquid, through outlet flow, gets rid of battery from outlet.
Following characteristics is embodied in operating process of the present invention:
(1) microfluidic design is used, make organic pollution and electrolyte in microchannel, keep the flow regime of parallel laminar flow, by the adjustment of flow velocity, effectively can suppress the mixing between two fluids, thus prevent organic pollution from diffusing to cell cathode, cause parasite current and reduce cell integrated output.
(2) design of gas-diffusion electrode is used, can be effective in reaction system supplemental oxygen fast, improve electrochemical reaction efficiency.
(3) use microchannel design, significantly reduce the resistance to mass tranfer in reaction system and characteristic length, thus reduce the transmission loss of organic substance between electrolyte flow to electrode surface.
With 0.03mmol/L methylene blue for fuel, 0.1mol/L sulfuric acid is electrolyte is example, and this photocatalysis microfluidic can produce 1.65mA/cm from breathing without membrane cell
2electric current, under bibliographical information same operation condition, adopt the photocatalytic fuel cell current density value 0.94mA/cm of body formula reactor
2.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise; can also make some improvements and modifications, these improvements and modifications also should be considered within the scope of protection of the present invention.
Claims (5)
1. one kind based on the self-respiration type photocatalysis of microfluid without membrane cell, it is characterized in that, load has titanium dioxide semiconductor nanometer rods to form self-respiration type photocatalysis without membrane cell main body as the electro-conductive glass of photochemical catalyst and microfluid battery chip and gas-diffusion electrode, and the electric energy that inside battery produces by positive wire, cathode wire is drawn for outside electrical appliance; Anolyte inlet connection, catholyte inlet connection are respectively used to organic wastewater and catholyte flows into, and discharge connection is used for effluent discharge;
Described self-respiration type photocatalysis uses organic wastewater as fuel without membrane cell, uses mineral salt as electrolyte, is electric energy while process waste water by the chemical energy in organic substance;
Described battery chip being arranged width is 2mm, and the degree of depth is 1mm, and length is the fluid channel of 10mm, the gas-diffusion electrode for being made up of the carbon paper being loaded with platinum catalyst on the downside of fluid channel, and upside is titanium dioxide semiconductor nanometer rods light-catalyzed reaction catalyst;
Described battery chip is by two pieces of micro-channel chip substrates I, and chip substrate II combines, and the microfluid in battery chip is upper and lower layering Laminar Flow, effectively can be kept the Laminar Flow of upper lower leaf in passage by this kind of practical structures;
Described chip substrate I has two through holes and two sections of grooves, leading portion is groove, and back segment is groove; Front hole is anolyte ingate, and metapore is outlet opening;
Described chip substrate II has three through holes and three sections of grooves, two sections, front and back are groove, and interlude is groove; Front hole is anolyte ingate, and interstitial hole is catholyte ingate, and metapore is outlet opening;
Prepare microfluid battery chip, use microfluidic pump drive fluid, make organic wastewater and electrolyte in microchannel, keep the flow regime of parallel laminar flow; There is light-catalyzed reaction and oxidation reaction on photocatalyst layer surface in anolyte, catholyte, at the gas-diffusion electrode place that load is made up of the carbon paper of platinum catalyst, reduction reaction occurs; Anode photochemical catalyst adopts titanium dioxide nano-rod, is synthesized on electro-conductive glass by hydro thermal method.
2. the self-respiration type photocatalysis based on microfluid as claimed in claim 1 is without membrane cell, and it is characterized in that, described anolyte entrance, catholyte entrance is connected with battery chip substrate II, junction epoxy sealing.
3. the self-respiration type photocatalysis based on microfluid as claimed in claim 1 is without membrane cell, and it is characterized in that, described outlet is connected with battery chip substrate II, junction epoxy sealing.
4. the self-respiration type photocatalysis based on microfluid as claimed in claim 1 is without membrane cell, and it is characterized in that, described positive wire is connected with photocatalysis load glass, and junction uses carbon slurry to be connected with silver slurry.
5. the self-respiration type photocatalysis based on microfluid as claimed in claim 1 is without membrane cell, and it is characterized in that, described cathode wire is connected with carbon paper electrode, and junction uses carbon slurry to be connected with silver slurry.
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| CN201310085223.8A CN103199294B (en) | 2013-03-15 | 2013-03-15 | Microfluid-based self-breathing photocatalytic film-free fuel battery |
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| CN103199294B true CN103199294B (en) | 2015-06-24 |
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Cited By (1)
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| CN104993164B (en) * | 2015-05-25 | 2017-07-11 | 重庆大学 | Photocatalytic reduction of carbon oxide and photocatalytic fuel cell coupling electricity production system |
| CN106169632B (en) * | 2016-06-22 | 2018-12-18 | 重庆大学 | Visible light photocatalysis fuel cell based on membrane electrode and preparation method thereof |
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| US20050084737A1 (en) * | 2003-10-20 | 2005-04-21 | Wine David W. | Fuel cells having cross directional laminar flowstreams |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101084364A (en) * | 2004-11-19 | 2007-12-05 | 康奈尔研究基金会（有限公司） | Planar membraneless microchannel fuel cell |
| CN101299463A (en) * | 2008-06-06 | 2008-11-05 | 北京大学 | Light fuel cell |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108682885A (en) * | 2018-04-08 | 2018-10-19 | 江苏理工学院 | A kind of design method of microfluid fuel cell porous electrode geometric dimension |
| CN108682885B (en) * | 2018-04-08 | 2021-05-18 | 江苏理工学院 | Design method for geometric dimension of porous electrode of microfluid fuel cell |
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