CN104577147A - High-stability direct methanol fuel cell membrane electrode based on CNT material - Google Patents
High-stability direct methanol fuel cell membrane electrode based on CNT material Download PDFInfo
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- CN104577147A CN104577147A CN201510031477.0A CN201510031477A CN104577147A CN 104577147 A CN104577147 A CN 104577147A CN 201510031477 A CN201510031477 A CN 201510031477A CN 104577147 A CN104577147 A CN 104577147A
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/94—Non-porous diffusion electrodes, e.g. palladium membranes, ion exchange membranes
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
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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
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
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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
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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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Abstract
The invention discloses a high-stability direct methanol fuel cell membrane electrode based on a CNT material, and belongs to the technical field of proton exchange membrane fuel cells. The membrane electrode is composed of an anode diffusion electrode, a Nafion proton exchange membrane and a cathode diffusion electrode, wherein a diffusion layer of the cathode diffusion electrode is prepared from CNT material paper. According to the membrane electrode disclosed by the invention, the structure of a direct methanol fuel cell can be simplified; the volume of the fuel cell is reduced; meanwhile, the water logging problem on one side of the cathode in the direct methanol fuel cell is well solved, so that the oxygen mass transfer of the cathode is increased; the stability of the cell for lastingly working for a long period of time is improved; the contact resistance between a collector plate and the membrane electrode is significantly reduced; the problem of internal resistance increase caused by PTFE used as the mass transfer baffle layer in a traditional structure is avoided; and the performance of the battery is improved.
Description
Technical field
The invention belongs to Proton Exchange Membrane Fuel Cells technical field, relate to a kind of direct methanol fuel cell membrane electrode.
Background technology
have benefited from the high-energy-density of liquid methanol, direct methanol fuel cell (Direct Methanol Fuel Cell ﹣ DMFC) theoretical specific energy can reach 4900Wh/L, close to 5 times of lithium battery.But in actual applications, as the dielectric film of methanol fuel cell, there is more serious Methanol permeation problems in Nafion film.This methanol crossover not only can cause the waste of fuel and the reduction of system effectiveness, and adds cathodic polarization, reduces the output voltage of DMFC.Meanwhile, in DMFC, water leaves negative electrode mostly as water vapor.But as 20 ~ 65 DEG C in lower temperature range, the water of negative electrode place more than 95% is accumulated in cathode catalysis layer all in liquid form, causes the utilance of catalyst to decline, hinder oxygen transmission, this phenomenon is negative electrode water logging.Negative electrode water logging can limit energy density and the useful life of battery, i.e. the stability of direct methanol fuel cell.
Summary of the invention
The object of this invention is to provide a kind of high stability direct methanol fuel cell membrane electrode based on CNT material, this membrane electrode not only can simplify the structure of direct methanol fuel cell, reduce its volume, solve the water logging problem of negative electrode side in direct methanol fuel cell well simultaneously, thus add the oxygen mass transfer of negative electrode, improve the stability of the long-time continuous firing of battery, and the contact resistance significantly decreased between collector plate and membrane electrode, and avoid in traditional structure the problem using PTFE to increase as the internal resistance that mass transfer barrier layer is brought, improve the performance of battery.
The object of the invention is to be achieved through the following technical solutions:
A kind of high stability direct methanol fuel cell membrane electrode based on CNT material, be made up of anode diffusion electrode, Nafion proton exchange membrane, cathode diffusion electrode, wherein the diffusion layer of cathode diffusion electrode is by CNT(carbon nano-tube) material obtains, and the Catalytic Layer that cathode diffusion electrode doubles as the mass transfer barrier layer of liquid water (negative electrode) and cathode diffusion electrode supports.
Membrane electrode of the present invention, compared with traditional direct methanol fuel cell membrane electrode, has the following advantages:
(1) glassware for drinking water of CNT paper to its surface has suction-operated and peptizaiton, can reduce the impact that mass transfer difficulty is brought; The capillary-like structures of CNT paper inside can make steam generation capillary condensation phenomenon simultaneously, improves the drainage rates of battery, effectively can solve the negative electrode water logging problem of direct methanol fuel cell.
(2) CNT paper is used to make cathode diffusion electrode, concentration and the pressure of water in cathode catalysis layer can be improved, the reverse transfer of water anode can be increased, thus the methanol concentration in reduction anode catalyst layer, thus methanol crossover is reduced while realizing DMFC high concentration methanol feed flow, compared with conventional batteries, new fuel cell this provides for improved the power density of battery under can being operated in the methanol solution condition of higher concentration.
(3) cathode diffusion electrode doubles as the mass transfer barrier layer of liquid water (negative electrode) and the Catalytic Layer support of cathode diffusion electrode.
(4) in the present invention, the DMFC of CNT base novel cathode diffusion electrode shows very strong superiority under high-temperature high concentration, the long-time discharge stability of new fuel cell is improved, 30 DEG C, under the methanol concentration of 6mol/L, the constant-current discharge time of new fuel cell is 494min, exceeds 63.5% of conventional batteries.
Accompanying drawing explanation
Fig. 1 is the structural representation based on CNT high stability direct methanol fuel cell membrane electrode of the present invention;
Fig. 2 is the direct methanol fuel cell encapsulating structure schematic diagram being loaded with novel membrane electrode;
Fig. 3 be 30 DEG C, under the methanol concentration of 6mol/L, be loaded with the direct methanol fuel cell working current density of novel membrane electrode and conventional film electrode respectively, wherein: C-paper: carbon paper; CNT: carbon nano-tube.
Embodiment
Embodiment one: as shown in Figure 1, the direct methanol fuel cell membrane electrode of present embodiment is made up of anode diffusion electrode (anode diffusion layer 1, anode catalyst layer 2), proton exchange membrane 3, cathode diffusion electrode (cathode catalysis layer 4, cathode diffusion layer 5), and the left side of proton exchange membrane 3 is followed successively by anode catalyst layer 2, anode diffusion layer 1; Cathode catalysis layer 4, cathode diffusion layer 5 is followed successively by the right side of proton exchange membrane 3.Wherein anode diffusion electrode adopts commercial anode diffusion electrode, and cathode diffusion layer 5 is by CNT(carbon nano-tube) material obtains, and simultaneously above-mentioned two-stage is also respectively as the mass transfer barrier layer of methanol aqueous solution (anode) and liquid water (negative electrode).
Embodiment two: the preparation method that present embodiments provide for a kind of direct methanol fuel cell membrane electrode, its step is as follows:
(1) cathode catalysis layer slurry is prepared:
Weigh the mixture of Pt/C(Pt and C of 30 ~ 50mg, wherein the content of Pt is 40wt.%) catalyst, add the mixing of 0.1 ~ 0.5mL deionized water, with sonic oscillation instrument vibration 5 ~ 10 minutes, until catalyst is completely submerged.Then add Nafion solution and 0.7 ~ 1.5mL isopropyl alcohol that 0.15 ~ 0.3ml concentration is 5wt.%, then vibrate with sonic oscillation instrument and fully stir 1 ~ 2 hour with magnetic stirring apparatus, make cathode inks.
(2) cathode diffusion electrode is prepared:
CNT material paper ultra-pure water is carried out Ultrasonic clean, drying at room temperature, makes cathode diffusion layer; Cut out about 2cm × 2cm cathode diffusion layer CNT material paper, fix and brush about 12 ~ 40mg cathode inks at its surface uniform, smear in process and dry under heat lamp after each brushing, be i.e. obtained described cathode diffusion electrode.
In this step, described cathode catalysis layer Pt carrying capacity is 1 ~ 4mg/ cm
2.
(3) hot pressing film forming electrode process is as follows:
By commercial anode diffusion electrode, Nafion proton exchange membrane and cathode diffusion electrode, arrange by order from left to right respectively, and stick together, subsequently by three under the pressure of the temperature of 130 ~ 140 DEG C and 20MPa, about 5 minutes of hot pressing, namely obtained a kind of based on CNT high stability direct methanol fuel cell membrane electrode (MEA).
Embodiment three: as shown in Figure 2, first uses anode current collector plate 8 and cathode collector plate 9 novel membrane electrode 10 is clamped and fixes.Then use the polymethyl methacrylate end plate 7 that two pieces of centres are rectangle opening to fix together with anode pole collector plate 8, novel membrane electrode 10 and cathode collector plate 9 three parts, finally the polymethyl methacrylate end plate 7 of liquid storage cylinder 6 with jointed anode side is linked together.
After encapsulation, activation carried out to battery and tentatively tests discovery, being loaded with the direct methanol fuel cell of novel membrane electrode than the stability using the battery of conventional film electrode to have higher performance and work long hours, as shown in Figure 3.
Above-mentioned execution mode does not just limit its protection range to the exemplary illustration of this patent; those skilled in the art can also carry out local to it and change; as long as no the Spirit Essence exceeding this patent, be all considered as the equivalent replacement to this patent, all within the protection range of this patent.
Claims (5)
1. based on a high stability direct methanol fuel cell membrane electrode for CNT material, be made up of anode diffusion electrode, Nafion proton exchange membrane, cathode diffusion electrode, it is characterized in that the diffusion layer of described cathode diffusion electrode is obtained by CNT material paper.
2. the high stability direct methanol fuel cell membrane electrode based on CNT material according to claim 1, is characterized in that described cathode diffusion electrode adopts following steps preparation:
(1) the Pt/C catalyst of 30 ~ 50mg is weighed, add the mixing of 0.1 ~ 0.5mL deionized water, with sonic oscillation instrument vibration 5 ~ 10 minutes, then 0.15 ~ 0.3ml Nafion solution and 0.7 ~ 1.5mL isopropyl alcohol is added, vibrate with sonic oscillation instrument again and fully stir 1 ~ 2 hour with magnetic stirring apparatus, making cathode inks;
(2) CNT material paper is clean with ultrapure water, drying at room temperature, makes the diffusion layer of cathode diffusion layer electrode;
(3) cathode inks is brushed at diffusion layer surface uniform, i.e. obtained cathode diffusion electrode.
3. the high stability direct methanol fuel cell membrane electrode based on CNT material according to claim 2, is characterized in that in described Pt/C catalyst, and the content of Pt is 40wt.%.
4. the high stability direct methanol fuel cell membrane electrode based on CNT material according to claim 2, it is characterized in that in described cathode diffusion electrode, in CNT material paper, Pt carrying capacity is 1 ~ 4mg/ cm
2.
5. the high stability direct methanol fuel cell membrane electrode based on CNT material according to claim 2, is characterized in that the concentration of described Nafion solution is 5wt.%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510031477.0A CN104577147A (en) | 2015-01-22 | 2015-01-22 | High-stability direct methanol fuel cell membrane electrode based on CNT material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105958084A (en) * | 2016-07-06 | 2016-09-21 | 哈尔滨工业大学 | Metal-air battery cathode material and one-step synthesis method thereof |
| CN112186198A (en) * | 2020-09-17 | 2021-01-05 | 北京航空航天大学 | Direct methanol fuel cell with anode using carbon nanotube paper as diffusion layer |
| CN114597429A (en) * | 2022-03-16 | 2022-06-07 | 昆明理工大学 | Method for improving cathode flooding of miniature direct methanol fuel cell |
-
2015
- 2015-01-22 CN CN201510031477.0A patent/CN104577147A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105958084A (en) * | 2016-07-06 | 2016-09-21 | 哈尔滨工业大学 | Metal-air battery cathode material and one-step synthesis method thereof |
| CN112186198A (en) * | 2020-09-17 | 2021-01-05 | 北京航空航天大学 | Direct methanol fuel cell with anode using carbon nanotube paper as diffusion layer |
| CN114597429A (en) * | 2022-03-16 | 2022-06-07 | 昆明理工大学 | Method for improving cathode flooding of miniature direct methanol fuel cell |
| CN114597429B (en) * | 2022-03-16 | 2023-08-04 | 昆明理工大学 | Method for improving cathode flooding of miniature direct methanol fuel cell |
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