CN106207236B - A kind of photoelectricity composite fuel cell based on MEA electrode - Google Patents
A kind of photoelectricity composite fuel cell based on MEA electrode Download PDFInfo
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- CN106207236B CN106207236B CN201610737222.0A CN201610737222A CN106207236B CN 106207236 B CN106207236 B CN 106207236B CN 201610737222 A CN201610737222 A CN 201610737222A CN 106207236 B CN106207236 B CN 106207236B
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- fuel cell
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- photocatalysis
- anode film
- cathodic coating
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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
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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
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Abstract
The invention discloses a kind of photoelectricity composite fuel cells based on MEA electrode, including photocatalysis anode film, cathodic coating, proton exchange membrane；The photocatalysis anode film, cathodic coating are compressed on proton exchange membrane left and right sides respectively.The present invention significantly improves photoelectricity fuel cell output power, and by taking ethyl alcohol as an example, compared with prior art, output performance of the present invention obtains biggish improvement, is the highest photoelectricity fuel cell of output power in current report；Working life significantly improves；Photoelectricity composite fuel cell working life based on MEA electrode of the invention can achieve 45 days, relatively stable；The technology of the present invention is low in cost, is relatively suitble to industrialization production, and can integrally improve photoelectrocatalysis efficiency, small organic molecule exhaustive oxidation can be generated carbon dioxide based on photocatalysis.
Description
Technical field
The invention belongs to field of new energy technologies more particularly to a kind of photoelectricity composite fuel cells based on MEA electrode.
Background technique
Being constantly progressive for science and technology keeps the development of human society more and more rapider, and the demand of the energy is also increasing.Fossil
The energy is the main energy of current whole world consumption, however not only resource is limited but also dirty in use for conventional fossil fuel
Environment is contaminated, therefore it is extremely urgent to develop more clean renewable energy.New energy it is numerous varied, but these energy come
Source is all attributed to solar energy, and solar energy is inexhaustible as one kind, and the inexhaustible energy is a kind of optimal clean energy resource,
But the prior art still has limitation for the utilization of solar energy.Optical electro-chemistry fuel cell is based on photo-electrocatalytic technology, utilizes
The some small organic molecules of solar energy catalysis oxidation are constructed battery and are generated electricity by composite cathode, provide exploitation to people
Utilize solar energy new approaches.
Optical electro-chemistry fuel battery performance has close contact with electrode structure and battery structure.Optical electro-chemistry is fired at present
The anode catalyst for expecting battery, is generally fixed on electrically conducting transparent matrix by cladding process, is easy to fall off in the solution, and after
Phase removal process is relatively difficult, to reduce catalytic efficiency；On the other hand, in traditional optical electro-chemistry fuel cell, due to
Proton needs to transmit in the solution, causes the internal resistance of electrode big when liquor capacity is excessive, and proton transfer rate is low, causes output property
It can be low.In order to further increase optical electro-chemistry fuel battery performance, need to designing and construct new electrode structure.
Summary of the invention
The purpose of the present invention is to provide a kind of photoelectricity composite fuel cells based on MEA electrode, it is intended to solve current light
Electrochemical fuel cell output performance is very poor, and universality is very poor, without suitable electrode structure, causes the internal resistance of electrode big, matter
Sub- delivery rate is low, the inefficient problem of electro-catalysis.
The invention is realized in this way a kind of photoelectricity composite fuel cell based on MEA electrode, it should be based on MEA electrode
Photoelectricity composite fuel cell includes photocatalysis anode film, cathodic coating, proton exchange membrane；The photocatalysis anode film, cathodic coating point
It is not compressed on proton exchange membrane left and right sides.
The photoelectricity composite fuel cell based on MEA electrode further includes shell, bolt, anode chamber, cathode chamber；The sun
Pole room and cathode chamber are bolted in shell；The photocatalysis anode film is located in anode chamber；The cathodic coating is located at
In cathode chamber.
The photocatalysis anode film includes uniformly coating TiO2Carbon cloth.
The photoelectricity composite fuel cell preparation method based on MEA electrode the following steps are included:
The preparation of MEA electrode: the preparation of the MEA electrode includes the preparation of photocatalysis anode film and the preparation of cathodic coating；
Obtained photocatalysis anode film and cathodic coating are assembled, are added one between photocatalysis anode film and cathodic coating
Nafion film is opened, under the conditions of 180 DEG C, 5MPa~9MPa, hot pressing 1.5 hours, then the PTFE film of anode is removed, in quality
Than making photocatalysis anode film, cathodic coating and Catalytic Layer protonation in the dilute sulfuric acid for 5% again, it is made three-in-one group of membrane electrode
Part；It is assembled into battery with two pieces of PTFE clamping plates, the PTFE containing quartz window is placed on the one side of photocatalysis anode film.
Photocatalysis anode film the preparation method comprises the following steps:
Weigh it is nonmetallic modifying after TiO2Nano particle 40mg, the volume ratio that water and ethyl alcohol is added is the mixture of 1:1,
Ultrasonic disperse 15 minutes, the nafion solution of 50mg 5% is then added, 10mg ammonium oxalate continues ultrasonic vibration 45 minutes；It is mixed
5cm is applied to after closing uniformly2PTFE film, 70 DEG C of dryings in air dry oven, obtains photocatalysis anode film；
Cathodic coating the preparation method comprises the following steps:
It weighs 40mg XC-72 carbon dust, is added the mixture that the volume ratio of water and ethyl alcohol is 1:1, ultrasonic disperse 15 minutes,
The nafion solution of 100mg 5% is added, 10mg ammonium oxalate continues ultrasonic disperse 45 minutes；It is coated in 5cm after mixing2
On the front and back sides of carbon cloth, 70 DEG C of dryings, obtain cathodic coating in air dry oven.
Present invention catalysis oxidation chemical substance under the auxiliary of sunlight, including small organic molecule, biological substance, Yi Jishui
Middle organic pollutant etc., by matching suitable cathode, composition battery is produced electricl energy, and the present invention can not only degrade having in water
Machine pollutant also achieves the conversion of luminous energy and chemical energy to electric energy.
The present invention proposes to be that anode prepares three in one membreane electrode using semiconductor catalyst, establishes optical electro-chemistry fuel electricity
Pond, and significantly improve performance practical value；Photoelectricity composite fuel cell based on MEA electrode has can working and room temperature, fast
Speed starting, electroless liquid stream are lost, and product is easily discharged, and the service life is long, the outstanding features such as specific power and specific energy height, Li design synthesis
Based on TiO2Its open-circuit voltage of nano-rod photo-catalyst photoelectricity composite fuel cell and power density can respectively reach 0.615V
With 1.1 μ Wcm-2, its open-circuit voltage of photoelectricity composite fuel cell of the invention and power density can respectively reach 0.93V and
36mW·cm-2Output performance has a distinct increment.
The present invention significantly improves photoelectricity fuel cell output power, and by taking ethyl alcohol as an example, compared with prior art, the present invention is defeated
Power density can reach 36mWcm out-2, it is the highest photoelectricity fuel cell of output power in current report；Working life is significant
It improves, the photoelectricity fuel cell reported at present can only maintain several weeks, operation for months, current only several weeks, the light based on MEA electrode
Replying conjunction fuel cell operating life by cable can achieve 45 days, relatively stable.
The technology of the present invention is low in cost, is relatively suitble to industrialization production, and can integrally improve photoelectrocatalysis efficiency, base
Small organic molecule exhaustive oxidation can be generated into carbon dioxide in photocatalysis.The present invention is a kind of based on MEA electrode by constructing
Photoelectricity composite fuel cell, respectively by photochemical catalyst and cathode hot pressing on proton exchange membrane both sides, under 100mW natural lighting into
Row test, it is found that its open-circuit voltage and power density can respectively reach 0.93V and 36mWcm-2, working life can be up to
45 days.
Detailed description of the invention
Fig. 1 is the photoelectricity composite fuel cell structural schematic diagram provided in an embodiment of the present invention based on MEA electrode；
In figure: 1, photocatalysis anode film；2, cathodic coating；3, proton exchange membrane；4, shell；5, bolt；6, anode chamber；7, negative
Pole room.
Fig. 2 is the cell output curve graph under different illumination intensity provided in an embodiment of the present invention；
Fig. 3 is that intensity of illumination provided in an embodiment of the present invention is 100mWcm-2Under different ethanol concentration battery output work
Rate curve graph.
Fig. 4 is the stability test figure of MEA electrode photochemical catalytic oxidation ethyl alcohol provided in an embodiment of the present invention.
Fig. 5 is optical electro-chemistry fuel cell schematic illustration provided in an embodiment of the present invention.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
Application principle of the invention is further illustrated with reference to the accompanying drawing.
As shown in Figure 1, the photoelectricity composite fuel cell based on MEA electrode of the embodiment of the present invention includes: photocatalysis anode
Film, cathodic coating, proton exchange membrane；The photocatalysis anode film, cathodic coating are compressed on proton exchange membrane left and right sides respectively.
The photoelectricity composite fuel cell based on MEA electrode further includes shell, bolt, anode chamber, cathode chamber；The sun
Pole room and cathode chamber are bolted in shell；The photocatalysis anode film is located in anode chamber；The cathodic coating is located at
In cathode chamber.
The photocatalysis anode film includes；Cathodic coating includes carbon cloth.
The photoelectricity composite fuel cell preparation method based on MEA electrode the following steps are included:
The preparation of MEA electrode: the preparation of the MEA electrode includes the preparation of photocatalysis anode film and the preparation of cathodic coating；
Obtained photocatalysis anode film and cathodic coating are assembled, are added one between photocatalysis anode film and cathodic coating
Nafion film is opened, under the conditions of 180 DEG C, 5MPa~9MPa, hot pressing 1.5 hours, then the PTFE film of anode is removed, in quality
Than making photocatalysis anode film, cathodic coating and Catalytic Layer protonation in the dilute sulfuric acid for 5% again, it is made three-in-one group of membrane electrode
Part；It is assembled into battery with two pieces of PTFE clamping plates, the PTFE containing quartz window is placed on the one side of photocatalysis anode film.
Below with reference to the preparation of MEA electrode, the present invention is further described.
The preparation of MEA electrode:
Photocatalysis anode film preparation: weigh it is nonmetallic modifying after TiO2Nano particle 40mg, addition water and ethyl alcohol mix
It closes object (volume ratio 1:1) ultrasonic disperse 15 minutes, the nafion solution of 50mg 5% is then added, 10mg ammonium oxalate continues to surpass
Acoustic shock is swung 45 minutes, is applied to 5cm after mixing2PTFE film, 70 DEG C of dryings, obtain anode film in air dry oven.
The preparation of cathodic coating: weighing 40mg XC-72 carbon dust, and mixture (volume ratio 1:1) ultrasound point of water and ethyl alcohol is added
It dissipates 15 minutes, the nafion solution of 100mg 5% is added, 10mg ammonium oxalate continues ultrasonic disperse 45 minutes, applies after mixing
Overlay on 5cm2(Taiwan carbon energy WOS1002 hydrophilic carbon cloth) 70 DEG C of dryings in air dry oven, obtain on the front and back sides of carbon cloth
Cathodic coating.
Obtained anode film and cathodic coating are assembled, a nafion film is added between them, on 180 DEG C of left sides
Under the conditions of right, 5~9MPa, hot pressing 1.5 hours, then the PTFE film of anode is removed, 5% dilute sulfuric acid (mass ratio) again
Film and Catalytic Layer are protonated, three-in-one membrane electrode assembly is made.It is assembled into battery with two pieces of PTFE clamping plates, wherein containing quartz
The PTFE of window is placed on the one side of light anode.
Below with reference to performance test, the present invention is further described.
The performance that the photoelectricity composite fuel cell of the MEA electrode prepared is carried out to fuel cell under room temperature (25 DEG C) is surveyed
Examination.Solution selects the aqueous solution of ethyl alcohol, and output power, such as Fig. 2 are tested it under different illumination intensity.
In a sunlight intensity (100mWcm-2) under test different ethanol concentration cell output, such as Fig. 3 light
It is 100mWcm according to intensity-2Under different ethanol concentration cell output curve graph；
The stability test figure of Fig. 4 MEA electrode photochemical catalytic oxidation ethyl alcohol.
The photoelectricity composite fuel cell that experimental result can be seen that the MEA electrode that the present invention designs has biggish output work
Rate, the 1.1 μ Wcm of output power reported in the literature much larger than before-2(article of Li), working life also have compared with before compared with
Big raising can be up to 45 days.
1) when doing cathod catalyst while noble metal or its carbon supported catalyst can be selected, for example, Pt, Pd, Ru, Rh,
Pt/C, Pd/C, Ru/C, Rh/C etc.；
2) common readily volatilized pore creating material such as ammonium hydrogen carbonate, ammonium oxalate or soluble pore creating material sodium chloride, potassium chloride,
Lithium carbonate etc., using ammonium oxalate pore creating material in the present embodiment.
It is as shown in Figure 5: since photochemical catalyst can produce electron-hole after illumination, and then small organic molecule to be carried out
Catalytic decomposition is to produce electricl energy.This stronger photoelectrocatalysis ability is but also optical electro-chemistry fuel cell is selecting fuel
There are more selectivity (for example, waste water, biomass etc.) than traditional fuel cell when source.Based on photo-electrocatalytic technology, originally
Invention proposes optical electro-chemistry fuel cell (PEFC) this concept, by using optical electro-chemistry catalyst (with TiO2For
Example), the catalysis oxidation chemical substance under the auxiliary of sunlight, including small organic molecule, organic contamination in biological substance and water
Object etc., by matching suitable cathode, composition battery is produced electricl energy, and the organic pollutant in the water that can not only degrade also is realized
The conversion of luminous energy and chemical energy to electric energy.
The present invention constructs a kind of photoelectricity hybrid fuel electricity based on MEA electrode by building optical electro-chemistry fuel cell
Photochemical catalyst and cathode hot pressing are tested under 100mW natural lighting on proton exchange membrane both sides respectively, find it by pond
Open-circuit voltage and power density can respectively reach 0.93V and 36mWcm-2, working life can be up to 45 days.The work is
It realizes that solar energy and chemical energy collaboration utilize, and its provides new possibility to the conversion of electric energy.But optical electro-chemistry combustion at present
Expect that cell output is very poor, universality is very poor.Tracing it to its cause is no suitable electrode structure, causes the internal resistance of electrode big,
Proton transfer rate is low, electro-catalysis inefficient.To solve the above-mentioned problems, the present invention proposes using semiconductor catalyst to be anode
Three in one membreane electrode is prepared, optical electro-chemistry fuel cell is established, and significantly improves performance practical value.Based on MEA electrode
Photoelectricity composite fuel cell have can working and room temperature, quick start, electroless liquid stream loses, and product is easily discharged, and the service life is long, compares function
The outstanding features such as rate and specific energy height, output performance has a distinct increment compared with photoelectricity composite fuel cell before.
The photoelectricity composite fuel cell based on MEA electrode of the embodiment of the present invention, bears respectively in the two sides of proton exchange membrane
When small organic molecule flows into anode chamber oxidation reaction can occur under solar irradiation for photochemical catalyst and cathod catalyst in load,
Electronics flows to cathode by external circuit and hydrogen reduction occurs on its surface, thus to extraneous output electric energy.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (1)
1. a kind of photoelectricity composite fuel cell based on MEA electrode, which is characterized in that should the compound combustion of photoelectricity based on MEA electrode
Expect that battery includes photocatalysis anode film, cathodic coating and proton exchange membrane；The photocatalysis anode film, cathodic coating are compressed on matter respectively
Proton exchange left and right sides；
The photoelectricity composite fuel cell based on MEA electrode further includes shell, bolt, anode chamber and cathode chamber；The anode
Room and cathode chamber are bolted in shell；The photocatalysis anode film is located in anode chamber；The cathodic coating is located at yin
In pole room；
The photocatalysis anode film includes: uniform coating TiO2Carbon cloth；
The photoelectricity composite fuel cell preparation method based on MEA electrode the following steps are included:
The preparation of MEA electrode: the preparation of the MEA electrode includes the preparation of photocatalysis anode film and the preparation of cathodic coating；
Obtained photocatalysis anode film and cathodic coating are assembled, one is added between photocatalysis anode film and cathodic coating
Nafion film, under the conditions of within the scope of 130 DEG C~190 DEG C, 5MPa~9MPa, hot pressing 1.5 hours, then the PTFE film of anode
Removing makes photocatalysis anode film, cathodic coating and Catalytic Layer protonation again in the dilute sulfuric acid that mass ratio is 5%, film electricity is made
Pole three-in-one component；It is assembled into battery with two pieces of PTFE clamping plates, the PTFE containing quartz window is placed on photocatalysis anode film
On one side；
Photocatalysis anode film the preparation method comprises the following steps:
Weigh it is nonmetallic modifying after TiO2Nano particle 20mg~60mg, the volume ratio that water and ethyl alcohol is added is the mixing of 1:1
Object, ultrasonic disperse 10~20 minutes, the nafion solution that then addition 30~80mg concentration is 5%, 10mg~30mg ammonium oxalate,
Continue ultrasonic vibration 30~60 minutes；It is applied to 5cm after mixing2PTFE film, 70 DEG C of dryings, obtain light in air dry oven
Catalyticing anode film；
Cathodic coating the preparation method comprises the following steps:
40mgXC-72 carbon dust is weighed, the volume ratio that water and ethyl alcohol is added is the mixture of 1:1, ultrasonic disperse 15 minutes, is added
The nafion solution that 100mg concentration is 5%, 10mg ammonium oxalate continue ultrasonic disperse 45 minutes；It is coated in 5cm after mixing2
On the front and back sides of carbon cloth, 70 DEG C of dryings, obtain cathodic coating in air dry oven.
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| CN201610737222.0A CN106207236B (en) | 2016-08-25 | 2016-08-25 | A kind of photoelectricity composite fuel cell based on MEA electrode |
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| CN106207236B true CN106207236B (en) | 2019-03-29 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101038968A (en) * | 2007-04-27 | 2007-09-19 | 新源动力股份有限公司 | Compound film electrode of catalytic layer supported proton exchange film fuel cells and method for making same |
| CN102188902A (en) * | 2011-05-06 | 2011-09-21 | 中国科学院广州能源研究所 | Method for treating organic gas by combining photocatalytic fuel cell photoelectrocatalysis and phase transfer |
| CN102701316A (en) * | 2012-05-09 | 2012-10-03 | 河海大学 | Photoelectric catalysis reactor taking photocatalysis fuel battery as power supply |
| CN105047948A (en) * | 2015-08-19 | 2015-11-11 | 浙江大学 | Photocatalysis fuel cell |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2553751A4 (en) * | 2010-04-01 | 2014-07-16 | Trenergi Corp | High temperature membrane electrode assembly with high power density and corresponding method of making |
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- 2016-08-25 CN CN201610737222.0A patent/CN106207236B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101038968A (en) * | 2007-04-27 | 2007-09-19 | 新源动力股份有限公司 | Compound film electrode of catalytic layer supported proton exchange film fuel cells and method for making same |
| CN102188902A (en) * | 2011-05-06 | 2011-09-21 | 中国科学院广州能源研究所 | Method for treating organic gas by combining photocatalytic fuel cell photoelectrocatalysis and phase transfer |
| CN102701316A (en) * | 2012-05-09 | 2012-10-03 | 河海大学 | Photoelectric catalysis reactor taking photocatalysis fuel battery as power supply |
| CN105047948A (en) * | 2015-08-19 | 2015-11-11 | 浙江大学 | Photocatalysis fuel cell |
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