CN100454634C - Proton exchange membrane of direct alcohol fuel cell and method for preparing membrane electrode - Google Patents

Proton exchange membrane of direct alcohol fuel cell and method for preparing membrane electrode Download PDF

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CN100454634C
CN100454634C CNB2004100568158A CN200410056815A CN100454634C CN 100454634 C CN100454634 C CN 100454634C CN B2004100568158 A CNB2004100568158 A CN B2004100568158A CN 200410056815 A CN200410056815 A CN 200410056815A CN 100454634 C CN100454634 C CN 100454634C
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membrane
nafion
electrode
palladium
proton exchange
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CN1738089A (en
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孙公权
孙海
王素力
刘建国
汪国雄
樊小颖
赵新生
徐恒泳
侯守福
辛勤
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Dalian Institute of Chemical Physics of CAS
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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 present invention provides an alcohol preventing membrane used for a direct alcohol fuel battery, and a preparing method of a membrane electrode, and relates to the technical field of fuel batteries. The alcohol preventing membrane is a palladium membrane or a palladium base alloy membrane, the thickness of the membrane is from 0.05 to 50 um, and the palladium content in the membrane is from 70% to 100%. The membrane electrode composed of the alcohol preventing membrane is in a multi-layer structure and comprises an anode diffusing layer, a cathode diffusing layer, an anode catalyzing layer, a cathode catalyzing layer, an electrolyte membrane and the alcohol preventing membrane positioned at an anode side or a cathode side or between two Nafion electrolyte membranes. The membrane electrode prepared by the present invention has excellent performance when the material is fed at low temperature and under high concentration. The present invention has the great advantage in the aspect of a portable power supply in an automatic respiration type at room temperature. The energy density of the battery is increased, and the present invention has an excellent applying prospect in the aspect of a movable power supply. The electrode with the structure can also be applied to sensors or similar electrochemical components.

Description

A kind of membrane electrode preparation method of direct alcohol fuel battery
Technical field
The present invention relates to the fuel cell technology field, particularly a kind of preparation that is used for the proton exchange membrane and the membrane electrode of direct alcohol fuel battery.
Background technology
The present invention relates to a kind of film electrode structure and technology of preparing thereof that is used for Proton Exchange Membrane Fuel Cells.In recent years, the fast development of multifunctional portable electronic product, the battery consumption sharply increases, and commercial power density once various or secondary cell is lower at present, need increase the need for electricity that volume of battery and weight could satisfy electronic product by a relatively large margin.And once or secondary cell have problem of environmental pollution.Directly the methyl alcohol types of fuel cells is directly to be fuel with methyl alcohol, chemical energy is converted into a class Blast Furnace Top Gas Recovery Turbine Unit (TRT) of electric energy.Because the methanol fuel source is abundant, low price, specific energy density height (6000Wh/kg, the specific energy density of lithium ion battery is about 600Wh/kg), be easy to carry and store, and fuel does not need reformer (comparing with outer reformation of methyl alcohol) directly at anode generation electrocatalysis oxidation reaction, entire cell has characteristics such as simple in structure, convenient, flexible, has broad application prospects.For example, can be used for small-sized independent current source; The particular power source of national defence communication, individual combat power supply and other military field; Uninterrupted power supplys such as family, shop, hospital, school, factory etc.Such battery not only can be applicable to the individual combat power supply, also can be used for small-sized civilian removable power supply such as notebook computer, video camera, mobile phone, senser element etc., also can be used as the traffic electrical source of power, be applied to aspects such as vehicle using motor, automobile, submarine, can also be applied to outlying place or household small-size power stations such as desert, desert island with the Compact Power Plant that fixes.The directly research and development of alcohol fuel battery, not only help the development of energy industry and battery industry, and will promote the technological progress in fields such as electronics, material, medical communication, significant to improving national strategy demands such as resource utilization and solution problem of environmental pollution.
At present, direct methanol fuel cell is applied to removable power supply, also has many problems to wait in solution, and wherein methyl alcohol sees through proton exchange membrane from anode to be penetrated into negative electrode is one of subject matter.Methyl alcohol passes dielectric film from anode and is penetrated into negative electrode, can produce mixed potential at negative electrode, has reduced the power output of battery, reduces fuel availability.When using high concentration methanol, the methanol permeation problem is serious.Though use low concentration methyl alcohol can alleviate the methanol crossover problem, the shared volume and weight of fuel is bigger, and the specific energy density of battery reduces.Reducing and even eliminating methanol crossover is one of target of pursuing of researchers always.
Document 1 WO 02/45188 has introduced the method for preparing catalyst slurry and preparing membrane electrode in the direct methanol fuel cell, utilize water to prepare catalyst slurry, utilize brushing or be sprayed on diffusion layer, PTFE film or the dielectric film to prepare membrane electrode as dispersant.This kind electrode structure is not owing to contain resistance alcohol layer, and methanol crossover is more serious.
Document 2 USP5759712 have introduced a kind of semi permeable plasticity electrode structure, and this structure electrode contains a large amount of wettable holes, its surface deposition last layer palladium film, can effectively stop fuel infiltration, but because the existence of hydrogen embrittlement phenomenon, embrittlement takes place in palladium film easily, and easily and matrix peel off.
Document 3 USP5846669 have introduced the soda acid fuel cell hybrid systems, and this system contains acidic electrolyte bath and alkaline electrolyte, separate with palladium base hybrid films between two kinds of electrolyte.This electrode structure adopts the palladium film to stop the infiltration of alcohol, and still because there is the hydrogen embrittlement phenomenon in the palladium film, embrittlement, not easy care take place simple palladium film easily.
Document 4 USP2002/0048703 have introduced a kind of metal (palladium, niobium, tantalum, vanadium etc.) film resistance alcohol infiltration electrode structure.At first on silicon matrix, form the aciculiform hole that arrives the surface, again in the saturating hydrogen metal film of resistance alcohol of its surface deposition one deck atresia by etching method.This invention is mainly used in hydrogen oxygen fuel cell, and system contains soda acid two kinds of electrolyte, not easy cares.
Document 5 Pu et al. (Journal of the Electrochemical Society 142 (1995) L119) have introduced a kind of compound film electrode structure.This structure places palladium dense film (25um is thick) between two Nafion 115 films, though this structure can reduce methanol crossover, the poor-performing of the electrode of this structure means that proton conduction is subjected to very big influence.
Document 6 Choi et al. (Journal of Power Sources 96 (2001) 411) have introduced a kind of preparation method who hinders pure electrode in the direct methanol fuel cell.They use sputter deposition to deposit one deck palladium film on Nafion 117 films, and find when the palladium film thickness is 20nm, and the DMFC performance improves a lot than the performance of the electrode of simple Nafion 117 film preparations.
Document 7 Yoon et al. (Journal of Power Sources 106 (2002) 215) use sputtering method at Nafion 117 surface sputtering one deck palladium films equally, methanol crossover is decreased, but find that proton conductivity also reduces simultaneously, electrode performance descends to some extent.
Document 8 Ma et al. (Journal of Membrane Science 5571 (2003) 1) are for overcoming the crisp problem of palladium film hydrogen, use sputtering method at surface sputtering one deck palladium-silver alloy film, and it is pressed between two Nafion 117, electrode performance is increased.
Above-mentioned electrode structure adopts traditional diffusion layer, Catalytic Layer, electrolytic membrane structure, and proton exchange membrane mainly adopts the physical method preparation.A little less than proton exchange membrane combined with dielectric film, long-time operation was easy to peel off problem, and electrode poor-performing under cryogenic conditions.
Summary of the invention
The purpose of this invention is to provide a kind of proton exchange membrane that is used for direct methanol fuel cell, this proton exchange membrane can reduce the infiltration of alcohol, the proton conductivity of not obvious again reduction film of while, thus improve battery performance, improve fuel availability.
Another object of the present invention provides a kind of preparation method of alcohol-resistant membrane electrode of direct methanol fuel cell, be at the saturating hydrogen thin metal layer of proton exchange membrane surface deposition one deck resistance alcohol by chemical method, proton exchange membrane is combined with proton-conductive films closely, be difficult for peeling off, overcome the shortcoming of the proton exchange membrane of physical method preparation; And the swelling problem of alleviation proton-conductive films under high concentration.
For achieving the above object, technical solution of the present invention provides a kind of proton exchange membrane of direct alcohol fuel battery, and it is palladium film or palladium base alloy films, and film thickness is 0.05～50 μ m, and the content of palladium is 70～100% in the film.
Described proton exchange membrane, its described palladium-base alloy are (Pd-Ag of palladium-Yin) or (Pd-Au of palladium-Jin).
The membrane electrode that described proton exchange membrane constitutes is made up of anode diffusion layer, cathode diffusion layer, anode catalyst layer, cathode catalysis layer and dielectric film; It also is provided with proton exchange membrane, and the position of proton exchange membrane is at anode-side or cathode side or place between the two Nafion dielectric films.
The membrane electrode that described proton exchange membrane constitutes is applied to direct alcohol fuel battery, electrochemical sensor or electrochemical device.
The membrane electrode preparation method that described proton exchange membrane constitutes, for:
A) Nafion dielectric film preliminary treatment: the Nafion dielectric film is cut into required size, uses 3%H successively 2O 2Solution, deionized water, 0.5M H 2SO 4Solution, deionized water after boiling 1 hour respectively under 80 ℃ the temperature, are positioned in the deionized water standby;
B) preparation of proton exchange membrane: get handle well the Nafion film, adopt the method for chemical plating, plate the proton exchange membrane that thickness is 0.05～50 μ m on its surface;
C) processing of Pd/Nafion composite membrane: with the H of Pd/Nafion composite membrane with 0.5M 2SO 4Solution was handled 2～12 hours under 40～100 ℃ of temperature, with behind the deionized water processing secondary, handled 2～12 hours with 0.5M NaOH again, handled secondary with deionized water again.
D) Catalytic Layer preparation: adopt directly spraying or change the method for pressing, the cathode and anode Catalytic Layer is covered in the both sides of Pd/Nafion combined films respectively;
E) activation of multilayer film electrode: the H that MEA is placed 0.5M 2SO 4In the solution, under 40～100 ℃ of temperature, handled 2～12 hours, handle secondary with deionized water again.
Described membrane electrode preparation method, the method for its described employing chemical plating, for:
A) PdCl of configuration 1N 2Solution, the HCl solution 10mL of adding 1N impregnated in the Nafion dielectric film of handling well in the solution that configures, under 30-60 ℃ of condition, kept 5 minutes-48 hours, taking-up is also used deionized water rinsing, and the hydrazine solution of putting into 1N again reduced 6 minutes-50 hours, repeated 3～15 times;
B) configuration plating bath, the consisting of of plating bath: PdCl 26g/L, EDTA 67g/L, NH 3H 2O350mL/L, N 2NNH 2, 0.5ml/L, surfactant: 1% volume ,+ethyl group sodium sulfonate;
C) in the middle of the Nafion dielectric film immersion plating bath after the activation sensitization, plating bath is stirred, under 30 ℃ of conditions, learn deposition last layer proton exchange membrane at Nafion dielectric film laterality with magnetic stick.
Described membrane electrode preparation method, it is at d) in the Catalytic Layer preparation process, the position of proton exchange membrane is at anode-side or cathode side or place between the two Nafion dielectric films.
The present invention introduced a kind of be used for direct methanol fuel cell contain sandwich construction electrode of proton exchange membrane and preparation method thereof.The sandwich construction electrode of this method preparation can stop methanol permeation, improves the utilance of fuel, prolongs electrode life.The membrane electrode of the present invention's preparation has good performance when low temperature, high concentration charging, be applied under the room temperature condition, and self-respiration type portable power supplies aspect should have bigger advantage.Improve the energy density of battery, had application promise in clinical practice aspect the removable power supply.This structure electrode also can be applicable to senser element or similar electrochemical device.
The present invention compared with prior art, its advantage is as follows:
1. compare with document 1WO 02/45188, contain the pure dense film of resistance in the multi-layer electrode structure of the present invention, can effectively stop methanol crossover, improve electrode performance.This structure electrode has more excellent performance when room temperature, high concentration charging, have certain advantage.
2. compare with document 2USP5759712, metal film of the present invention can effectively stop fuel infiltration.
The metal film of this method preparation is not easy to peel off with polymer film.Though embrittlement also may take place in metal film, can cover the shortage mutually with polymer film, can effectively reduce methanol crossover.
3. compare with document 3USP5846669, polymer proton conductive membranes of the present invention and palladium film or its alloy film are mutually promoted, and the infiltration of alcohols material can be eliminated or reduce to palladium film or its alloy film, and the polymer proton conductive membranes can remedy the leakage of the caused material of hydrogen embrittlement.
4. compare with document 4USP2002/0048703, the present invention only contains a kind of solid electrolyte, and compact conformation is easy to safeguard.
Effect of the present invention:
1. in electrode production process, adopt the pure dense film of chemical plating method preparation resistance, mild condition, easy operating.
2. membrane electrode has sandwich construction, has reduced the infiltration of methyl alcohol from the anode to the negative electrode, and this structure electrode has preferable performance under normal temperature, high concentration feed conditions.
3. the metal hydrogen permeation membrane by the preparation of this chemical method combines closely with proton exchange membrane, be difficult for peeling off, and has overcome the shortcoming that physical method prepares proton exchange membrane.
4. proton exchange membrane swelling problem when having alleviated high concentration.
Description of drawings
Fig. 1 is the membrane electrode schematic diagram with sandwich construction Catalytic Layer;
Fig. 2 is a membrane electrode methanol crossover limiting current comparison curves;
Fig. 3 is embodiment 2, embodiment 4, embodiment 6 membrane electrode performance curves;
Fig. 4 is embodiment 3, embodiment 5 membrane electrode performance curves.
Embodiment
As shown in Figure 1, be the film electrode structure figure of the direct alcohol fuel battery that has proton exchange membrane of the present invention.Identical with prior art, the film electrode structure of direct alcohol fuel battery of the present invention is a sandwich construction, is made up of anode diffusion layer, cathode diffusion layer, anode catalyst layer, cathode catalysis layer and dielectric film; But between anode catalyst layer and dielectric film, or between cathode catalysis layer and dielectric film, or between two-layer dielectric film, one deck proton exchange membrane is set.
The proton exchange membrane thin layer is the alloy film (as palladium-Yin, palladium-Jin etc.) of palladium film or palladium, and the employing chemical plating method prepares the saturating hydrogen metal film thin layer of resistance alcohol in the multi-layer electrode structure.Its manufacture method is as follows:
1.Nafion dielectric film preliminary treatment: will (Du Pont) dielectric film is cut into 5 * 5cm 2Size is used 3%H successively 2O 2Solution, deionized water, 0.5M H 2SO 4Solution, deionized water after boiling 1 hour respectively under 80 ℃ the temperature, are positioned in the deionized water standby.
2. the preparation of proton exchange membrane: get handle well the Nafion film, adopt the method for chemical plating, plate thickness on its surface and be 0.05～50 palladium (Pd) film.
3.Pd/Nafion the processing of combined films: with the H of Pd/Nafion combined films with 0.5M 2SO 4Solution was handled 2～12 hours under 40～100 ℃ of temperature, again with after the deionized water processing 2～12 hours (2 times).Handled 2～12 hours with 0.5M NaOH, handle 2～12 hours (2 times) with deionized water again.
4. Catalytic Layer preparation: adopt directly spraying or change the method for pressing, the cathode and anode Catalytic Layer is covered in the both sides of Pd/Nafion combined films respectively.The visual specific requirement in position that hinders pure palladium (Pd) film places cathode side or anode-side or is pressed in the middle of two Nafion dielectric films
5. the activation of multilayer film electrode (MEA): the H that MEA is placed 0.5M 2SO 4In the solution, under 40～100 ℃ of temperature, handled 2～12 hours, handle 2～12 hours (2 times) with deionized water again.
Embodiment 1
The PdCl of configuration 1N 2Solution, the HCl solution 10mL of adding 1N.With the 4 * 4cm that handles well 2Nafion 115 film immersions kept 5 minutes under 30 ℃ of conditions in the solution that configures, and taking-up is also used deionized water rinsing, and the hydrazine solution of putting into 1N again reduced 6 minutes, repeated 5 times, so that film is handled.Nafion 115 films of activation after the sensitization are immersed in the middle of the plating bath the consisting of of plating bath: PdCl 26g/L, EDTA 67g/L, NH 3H 2O 350mL/L, N 2NNH 2, 0.5ml/L, surfactant: 1% volume ,+ethyl group sodium sulfonate.Plating bath stirs with magnetic stick, under 30 ℃ of conditions, learns deposition last layer Pd film at Nafion 115 film lateralities, and the thickness of Pd film is about 5 μ m.Directly spray Pt/Ru black and Pt black catalyst respectively in Pd/Nafion 115 film both sides, the Pd film is positioned at anode-side, and anode catalyst is Pt/Ru black, and loading is 3.5mg/cm 2, Nafion content is 15wt.%.Cathod catalyst is a Pt black catalyst, and loading is 3.0mg/cm 2, Nafion content is 5wt.%.
Behind electrode activation, assemble single pond test methanol crossover limiting current.As shown in Figure 2, be membrane electrode methanol crossover limiting current comparison curves, test condition is the 1mol/L methanol aqueous solution for the anode-side charging, and flow velocity is 2ml/min.The cathode side air inlet is the 0.2MPa high pure nitrogen, and flow is respectively 90 ℃ and 75 ℃ for the 4.5ml/s. operating temperature.Cathode side is a work electrode, and anode-side is to electrode and reference electrode.The linear scan scope is 0.1V-0.9V, and speed is 2mV/s.Electrode is the membrane electrode according to patent WO 02/45188 usefulness Nafion 115 film preparations by comparison, and catalyst loading amount and test condition are with noted earlier identical.
Embodiment 2
Prepare electrode according to embodiment 1 step.Anode catalyst is Pt/Ru black, and the catalyst loading amount is 3.7mg/cm 2, Nafion content is 15%.Cathod catalyst is Pt black, and the catalyst loading amount is 3.0mg/cm 2, Nafion content is 5%.Single pond performance is surveyed in the activation back.Experiment condition is: anode feed is the 1M methanol aqueous solution, 1ml/min, and the negative electrode charging is an oxygen, and flow is 4.0ml/s, and operating temperature is 30 ℃.The battery performance curve is seen Fig. 3.
Embodiment 3
Prepare electrode according to embodiment 1 step, catalyst loading amount and Catalytic Layer are formed with example 2.Single pond performance is surveyed in the activation back.Experiment condition is: anode feed is the 5M methanol aqueous solution, 1ml/min, and the negative electrode charging is an oxygen, and flow is 4.0ml/s, and operating temperature is 30 ℃.The battery performance curve is seen Fig. 4.
Embodiment 4
Prepare Pd/Nafion 115 according to embodiment 1 step, the anode and cathode catalyst sprays on the poly-polytetrafluoroethylene film in advance, is pressed onto Pd/Nafion 115 both sides in commentaries on classics, and catalyst loading amount and Catalytic Layer are formed with example 2.Hinder pure palladium film and be positioned at cathode side, the palladium film thickness is 10 μ m.Single pond performance is surveyed in the activation back.Experiment condition is: anode feed is the 1M methanol aqueous solution, 1ml/min, and the negative electrode charging is an oxygen, and flow is 4.0ml/s, and operating temperature is 30 ℃.The battery performance curve is seen Fig. 3.
Embodiment 5
Plate the Pd-Ag alloy film according to embodiment 1 step in a side of Nafion 115 films, operating temperature is 30 ℃.The content of Pd is 20% in the alloy film, and thickness is 2 μ m.Preparation electrode step such as embodiment 1, alloy film is positioned at anode-side, and the catalyst loading amount is: anode is Pt/Ru black, 3.7mg/cm 2, Nafion content is 15%.Cathod catalyst is Pt black, 3.0mg/cm 2, Nafion content is 5%.Single pond performance is surveyed in the activation back.Experiment condition is: anode feed is the 1M methanol aqueous solution, 1ml/min, and the negative electrode charging is an oxygen, and flow is 4.0ml/s, and operating temperature is for as shown in the figure.The battery performance curve is seen Fig. 4.
Embodiment 6
Prepare electrode according to embodiment 1 step, catalyst loading amount and Catalytic Layer are formed with example 2.The palladium film is sandwich between two Nafion115 films.Single pond performance is surveyed in the activation back.Experiment condition is: anode feed is the 1M methanol aqueous solution, 1ml/min, and the negative electrode charging is an oxygen, and flow is 4.0ml/s, and operating temperature is 30 ℃.The battery performance curve is seen Fig. 3.

Claims (2)

1, a kind of membrane electrode preparation method of direct alcohol fuel battery; It is characterized in that: comprise step:
A) Nafion dielectric film preliminary treatment: the Nafion dielectric film is cut into required size, uses 3%H successively 2O 2Solution, deionized water, 0.5M H 2SO 4Solution, deionized water after boiling 1 hour respectively under 80 ℃ the temperature, are positioned in the deionized water standby;
B) preparation of proton exchange membrane: get the Nafion dielectric film of handling well and impregnated in the PdCl that configures 2Activate sensitization in the solution, the Nafion dielectric film after the activation sensitization is immersed in the plating bath again, learn deposition last layer palladium proton exchange membrane at Nafion dielectric film laterality, obtain the Pd/Nafion composite membrane, wherein the thickness of palladium proton exchange membrane is 0.05～50 μ m;
C) processing of Pd/Nafion composite membrane: with the H of Pd/Nafion composite membrane with 0.5M 2SO 4Solution was handled 2～12 hours under 40～100 ℃ of temperature, with behind the deionized water processing secondary, handled 2～12 hours with 0.5M NaOH again, handled secondary with deionized water again;
D) Catalytic Layer preparation: adopt directly spraying or change the method for pressure, the cathode and anode Catalytic Layer is covered in the both sides of Pd/Nafion composite membrane respectively, make membrane electrode;
E) activation of membrane electrode: the H that membrane electrode is placed 0.5M 2SO 4In the solution, under 40～100 ℃ of temperature, handled 2～12 hours, handle secondary with deionized water again.
2. membrane electrode preparation method as claimed in claim 1 is characterized in that: at d) in the Catalytic Layer preparation process, the position of palladium proton exchange membrane is at anode-side or cathode side or place between the two Nafion dielectric films.
CNB2004100568158A 2004-08-20 2004-08-20 Proton exchange membrane of direct alcohol fuel cell and method for preparing membrane electrode Expired - Fee Related CN100454634C (en)

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KR100738062B1 (en) * 2006-05-16 2007-07-10 삼성에스디아이 주식회사 Membrane and electrode assembly, and fuel cell using the same
KR100846478B1 (en) 2006-05-16 2008-07-17 삼성에스디아이 주식회사 Supported Catalyst, manufacturing method thereof, and fuel cell using the same
CN101235268B (en) * 2007-12-27 2010-04-21 中国科学院长春应用化学研究所 Moisture-absorption water-retention composite film and preparation method thereof
CN103840174B (en) * 2012-11-20 2016-06-22 中国科学院大连化学物理研究所 A kind of direct alcohol fuel cell diaphragm electrode and preparation thereof and application
CN108493388A (en) * 2018-05-11 2018-09-04 合肥国轩高科动力能源有限公司 A kind of vanadium cell cation-exchange membrane and preparation method thereof
CN108725823B (en) * 2018-06-13 2024-04-09 浙江氢航科技有限公司 Unmanned aerial vehicle take-off platform powered by fuel cell

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5846669A (en) * 1994-05-12 1998-12-08 Illinois Institute Of Technology Hybrid electrolyte system
JP2003242997A (en) * 1999-09-30 2003-08-29 Toshiba Corp Manufacturing method of ion conductive membrane

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5846669A (en) * 1994-05-12 1998-12-08 Illinois Institute Of Technology Hybrid electrolyte system
JP2003242997A (en) * 1999-09-30 2003-08-29 Toshiba Corp Manufacturing method of ion conductive membrane

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"低甲醇透过直接甲醇燃料电池". 杜荣兵，徐维林，邢巍，陆天虹，桑革."应用化学"，第Vol. 20卷第No. 8期. 2003 *
A Palladium－alloy deposited Nafion membrane for directmethanol fuel cells. Z.Q.Ma，P.Cheng，T.S.Zhao.Journal of Membrane Science,Vol.215卷 . 2003 *

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